WorldWideScience

Sample records for uranium reaction pathways

  1. Competing retention pathways of uranium upon reaction with Fe(II)

    Science.gov (United States)

    Massey, Michael S.; Lezama-Pacheco, Juan S.; Jones, Morris E.; Ilton, Eugene S.; Cerrato, José M.; Bargar, John R.; Fendorf, Scott

    2014-10-01

    Biogeochemical retention processes, including adsorption, reductive precipitation, and incorporation into host minerals, are important in contaminant transport, remediation, and geologic deposition of uranium. Recent work has shown that U can become incorporated into iron (hydr)oxide minerals, with a key pathway arising from Fe(II)-induced transformation of ferrihydrite, (Fe(OH)3·nH2O) to goethite (α-FeO(OH)); this is a possible U retention mechanism in soils and sediments. Several key questions, however, remain unanswered regarding U incorporation into iron (hydr)oxides and this pathway's contribution to U retention, including: (i) the competitiveness of U incorporation versus reduction to U(IV) and subsequent precipitation of UO2; (ii) the oxidation state of incorporated U; (iii) the effects of uranyl aqueous speciation on U incorporation; and, (iv) the mechanism of U incorporation. Here we use a series of batch reactions conducted at pH ∼7, [U(VI)] from 1 to 170 μM, [Fe(II)] from 0 to 3 mM, and [Ca] at 0 or 4 mM coupled with spectroscopic examination of reaction products of Fe(II)-induced ferrihydrite transformation to address these outstanding questions. Uranium retention pathways were identified and quantified using extended X-ray absorption fine structure (EXAFS) spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. Analysis of EXAFS spectra showed that 14-89% of total U was incorporated into goethite, upon reaction with Fe(II) and ferrihydrite. Uranium incorporation was a particularly dominant retention pathway at U concentrations ⩽50 μM when either uranyl-carbonato or calcium-uranyl-carbonato complexes were dominant, accounting for 64-89% of total U. With increasing U(VI) and Fe(II) concentrations, U(VI) reduction to U(IV) became more prevalent, but U incorporation remained a functioning retention pathway. These findings highlight the potential importance of U(V) incorporation within iron

  2. Uranium fluoride chemistry. Part 1. The gas phase reaction of uranium hexafluoride with alcohols

    International Nuclear Information System (INIS)

    Schnautz, N.G.; Venter, P.J.

    1992-01-01

    The reaction between uranium hexafluoride (UF 6 ) and simple alcohols in the gas phase was observed to proceed by way of three possible reaction pathways involving dehydration, deoxygenative fluorination, and ether formation. These reactions can best be explained by assuming that alcohols first react with UF 6 to afford the alkoxy uranium pentafluoride intermediate ROUF 5 , which reacts further to give the dehydration, deoxygenative fluorination, and ether products. In each of the above three reaction pathways, UF 6 is transformed to UOF 4 , which being as reactive toward alcohols as UF 6 , reacts further with the alcohol in question to finally afford the unreactive uranyl fluoride (UO 2 F 2 ). 6 refs., 2 tabs

  3. TRIMOLECULAR REACTIONS OF URANIUM HEXAFLUORIDE WITH WATER

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, M.; Becnel, J.; Garrison, S.

    2010-02-25

    The hydrolysis reaction of uranium hexafluoride (UF{sub 6}) is a key step in the synthesis of uranium dioxide (UO{sub 2}) powder for nuclear fuels. Mechanisms for the hydrolysis reactions are studied here with density functional theory and the Stuttgart small-core scalar relativistic pseudopotential and associated basis set for uranium. The reaction of a single UF{sub 6} molecule with a water molecule in the gas phase has been previously predicted to proceed over a relatively sizeable barrier of 78.2 kJ {center_dot} mol{sup -1}, indicating this reaction is only feasible at elevated temperatures. Given the observed formation of a second morphology for the UO{sub 2} product coupled with the observations of rapid, spontaneous hydrolysis at ambient conditions, an alternate reaction pathway must exist. In the present work, two trimolecular hydrolysis mechanisms are studied with density functional theory: (1) the reaction between two UF{sub 6} molecules and one water molecule, and (2) the reaction of two water molecules with a single UF{sub 6} molecule. The predicted reaction of two UF{sub 6} molecules with one water molecule displays an interesting 'fluorine-shuttle' mechanism, a significant energy barrier of 69.0 kJ {center_dot} mol{sup -1} to the formation of UF{sub 5}OH, and an enthalpy of reaction ({Delta}H{sub 298}) of +17.9 kJ {center_dot} mol{sup -1}. The reaction of a single UF{sub 6} molecule with two water molecules displays a 'proton-shuttle' mechanism, and is more favorable, having a slightly lower computed energy barrier of 58.9 kJ {center_dot} mol{sup -1} and an exothermic enthalpy of reaction ({Delta}H{sub 298}) of -13.9 kJ {center_dot} mol{sup -1}. The exothermic nature of the overall UF{sub 6} + 2 {center_dot} H{sub 2}O trimolecular reaction and the lowering of the barrier height with respect to the bimolecular reaction are encouraging; however, the sizable energy barrier indicates further study of the UF{sub 6} hydrolysis reaction

  4. Study of reactions between uranium-plutonium mixed oxide and uranium nitride and between uranium oxide and uranium nitride; Etude des reactions entre l`oxyde mixte d`uranium-plutonium et le nitrure d`uranium et entre l`oxyde d`uranium et le nitrure d`uranium

    Energy Technology Data Exchange (ETDEWEB)

    Lecraz, C

    1993-06-11

    A new type of combustible elements which is a mixture of uranium nitride and uranium-plutonium oxide could be used for Quick Neutrons Reactors. Three different studies have been made on the one hand on the reactions between uranium nitride (UN) and uranium-plutonium mixed oxide (U,Pu)O{sub 2}, on the other hand on these between UN and uranium oxide UO{sub 2}. They show a sizeable reaction between nitride and oxide for the studied temperatures range (1573 K to 1973 K). This reaction forms a oxynitride compound, MO{sub x} N{sub y} with M=U or M=(U,Pu), whose crystalline structure is similar to oxide`s. Solubility of nitride in both oxides is studied, as the reaction kinetics. (TEC). 32 refs., 48 figs., 22 tabs.

  5. Uranium redox transition pathways in acetate-amended sediments

    Science.gov (United States)

    Bargar, John R.; Williams, Kenneth H.; Campbell, Kate M.; Long, Philip E.; Stubbs, Joanne E.; Suvorova, Elenal I.; Lezama-Pacheco, Juan S.; Alessi, Daniel S.; Stylo, Malgorzata; Webb, Samuel M.; Davis, James A.; Giammar, Daniel E.; Blue, Lisa Y.; Bernier-Latmani, Rizlan

    2013-01-01

    Redox transitions of uranium [from U(VI) to U(IV)] in low-temperature sediments govern the mobility of uranium in the environment and the accumulation of uranium in ore bodies, and inform our understanding of Earth’s geochemical history. The molecular-scale mechanistic pathways of these transitions determine the U(IV) products formed, thus influencing uranium isotope fractionation, reoxidation, and transport in sediments. Studies that improve our understanding of these pathways have the potential to substantially advance process understanding across a number of earth sciences disciplines. Detailed mechanistic information regarding uranium redox transitions in field sediments is largely nonexistent, owing to the difficulty of directly observing molecular-scale processes in the subsurface and the compositional/physical complexity of subsurface systems. Here, we present results from an in situ study of uranium redox transitions occurring in aquifer sediments under sulfate-reducing conditions. Based on molecular-scale spectroscopic, pore-scale geochemical, and macroscale aqueous evidence, we propose a biotic–abiotic transition pathway in which biomass-hosted mackinawite (FeS) is an electron source to reduce U(VI) to U(IV), which subsequently reacts with biomass to produce monomeric U(IV) species. A species resembling nanoscale uraninite is also present, implying the operation of at least two redox transition pathways. The presence of multiple pathways in low-temperature sediments unifies apparently contrasting prior observations and helps to explain sustained uranium reduction under disparate biogeochemical conditions. These findings have direct implications for our understanding of uranium bioremediation, ore formation, and global geochemical processes.

  6. Reaction of uranium and the fluorocarbon FC-75

    Science.gov (United States)

    Young, R. H.

    1985-04-01

    Because of criticality concerns with water cooling in enriched uranium upgrading, a fluorocarbon has been evaluated as a replacement coolant for internal module components in the Plasma Separation Process (PSP). The interaction of bulk uranium and of powdered uranium with FC-75 has been investigated at temperatures between 200 and 700 C. The gas pressure and the metal temperature were monitored as a function of time. Modest temperature changes of 50 to 100 C were observed for the bulk uranium/fluorocarbon reaction. Much larger changes (up to 1000 C) were noted for the reaction involving high surface area uranium powder. These temperature transients, particularly for the powdered uranium reaction, were short-lived ( 10 seconds) and indicative of the formation of a protective layer of reaction products. Analysis of residual gas products by infrared spectroscopy indicated that one potentially serious hazard, UF6, was not present; however, several small toxic fluorocarbons were produced by thermolysis and/or reaction. X-ray diffraction analysis of the residual solids indicated UF4 and UO2 were the major solid products.

  7. Separation of uranium isotopes by accelerated isotope exchange reactions

    International Nuclear Information System (INIS)

    Seko, M.; Miyake, T.; Inada, K.; Ochi, K.; Sakamoto, T.

    1977-01-01

    A novel catalyst for isotope exchange reaction between uranium(IV) and uranium(VI) compounds enables acceleration of the reaction rate as much as 3000 times to make industrial separation of uranium isotopes economically possible

  8. Reaction between uranium hexafluoride and trimethylsilylhalides

    Energy Technology Data Exchange (ETDEWEB)

    Brown, D; Berry, J A [UKAEA Atomic Energy Research Establishment, Harwell. Chemistry Div.; Holloway, J H; Staunton, G M [Leicester Univ. (UK). Dept. of Chemistry

    1938-07-01

    Reactions involving 1.1:1 molar ratios of uranium hexafluoride to either trimethylsilylchloride or trimethylsilylbromide in halocarbon solutions yield ..beta..-UF/sub 5/ at room temperature. With 2 mol equivalents of trimethylsilylchloride the product is UF/sub 4/. The reactions appear to proceed via the intermediate formation of unstable brown uranium(VI) chloride and bromide fluorides. Calculations show that UClF/sub 5/ and UCl/sub 2/F/sub 4/ are thermodynamically unstable with respect to the loss of chlorine at room temperature.

  9. Compact reaction cell for homogenizing and down-blending highly enriched uranium metal

    Science.gov (United States)

    McLean, W. II; Miller, P.E.; Horton, J.A.

    1995-05-02

    The invention is a specialized reaction cell for converting uranium metal to uranium oxide. In a preferred form, the reaction cell comprises a reaction chamber with increasing diameter along its length (e.g. a cylindrical chamber having a diameter of about 2 inches in a lower portion and having a diameter of from about 4 to about 12 inches in an upper portion). Such dimensions are important to achieve the necessary conversion while at the same time affording criticality control and transportability of the cell and product. The reaction chamber further comprises an upper port and a lower port, the lower port allowing for the entry of reactant gases into the reaction chamber, the upper port allowing for the exit of gases from the reaction chamber. A diffuser plate is attached to the lower port of the reaction chamber and serves to shape the flow of gas into the reaction chamber. The reaction cell further comprises means for introducing gases into the reaction chamber and a heating means capable of heating the contents of the reaction chamber. The present invention also relates to a method for converting uranium metal to uranium oxide in the reaction cell of the present invention. The invention is useful for down-blending highly enriched uranium metal by the simultaneous conversion of highly enriched uranium metal and natural or depleted uranium metal to uranium oxide within the reaction cell. 4 figs.

  10. Compact reaction cell for homogenizing and down-blanding highly enriched uranium metal

    Science.gov (United States)

    McLean, II, William; Miller, Philip E.; Horton, James A.

    1995-01-01

    The invention is a specialized reaction cell for converting uranium metal to uranium oxide. In a preferred form, the reaction cell comprises a reaction chamber with increasing diameter along its length (e.g. a cylindrical chamber having a diameter of about 2 inches in a lower portion and having a diameter of from about 4 to about 12 inches in an upper portion). Such dimensions are important to achieve the necessary conversion while at the same time affording criticality control and transportability of the cell and product. The reaction chamber further comprises an upper port and a lower port, the lower port allowing for the entry of reactant gasses into the reaction chamber, the upper port allowing for the exit of gasses from the reaction chamber. A diffuser plate is attached to the lower port of the reaction chamber and serves to shape the flow of gas into the reaction chamber. The reaction cell further comprises means for introducing gasses into the reaction chamber and a heating means capable of heating the contents of the reaction chamber. The present invention also relates to a method for converting uranium metal to uranium oxide in the reaction cell of the present invention. The invention is useful for down-blending highly enriched uranium metal by the simultaneous conversion of highly enriched uranium metal and natural or depleted uranium metal to uranium oxide within the reaction cell.

  11. Study of reactions for the production of uranium titrafluoride and uranium hexafluoride

    International Nuclear Information System (INIS)

    Guzella, M.F.R.

    1985-01-01

    The main production processes of uranium hexafluoride in pilot plants and industrial facilities are described. The known reactions confirmed in laboratory experiments that lead to Uf 6 or other intermediate fluorides are discussed. For the purpose of determining a thermodinamically feasible reaction involving the sulfur hexafluoride as fluorinating agent, a mock-up facility was designed and constructed as a part of the R and D work planned at the CDTN (Nuclebras Center for Nuclear Technology Development). IN the uranium tatrafluoride synthesis employing U 3 O 8 and SF 6 several experimental parameters are studied. The reaction time, gasflow, temperature and stoechiometic relations among reagents are described in detail. (Author) [pt

  12. Literature information applicable to the reaction of uranium oxides with chlorine to prepare uranium tetrachloride

    International Nuclear Information System (INIS)

    Haas, P.A.

    1992-02-01

    The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl 4 ) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbon monoxide (CO) to give CO or carbon dioxide (CO 2 ) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl 4 -UO 2 shows a reaction to form uranium oxychloride (UOCl 2 ) that has a good solubility in molten UCl 4 . This appears more favorable to good rates of reaction than reaction of solids and gases. There is limited information on U-O-Cl salt properties. Information on the preparation of titanium, zirconium, silicon, and thorium tetrachlorides (TiCl 4 , ZrCl 4 , SiCl 4 , ThCl 4 ) by reaction of oxides with chlorine (Cl 2 ) and carbon has application to the preparation of UCl 4

  13. Literature information applicable to the reaction of uranium oxides with chlorine to prepare uranium tetrachloride

    Energy Technology Data Exchange (ETDEWEB)

    Haas, P.A.

    1992-02-01

    The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl{sub 4}) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbon monoxide (CO) to give CO or carbon dioxide (CO{sub 2}) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl{sub 4}-UO{sub 2} shows a reaction to form uranium oxychloride (UOCl{sub 2}) that has a good solubility in molten UCl{sub 4}. This appears more favorable to good rates of reaction than reaction of solids and gases. There is limited information on U-O-Cl salt properties. Information on the preparation of titanium, zirconium, silicon, and thorium tetrachlorides (TiCl{sub 4}, ZrCl{sub 4}, SiCl{sub 4}, ThCl{sub 4}) by reaction of oxides with chlorine (Cl{sub 2}) and carbon has application to the preparation of UCl{sub 4}.

  14. Uranium oxidation: characterization of oxides formed by reaction with water

    International Nuclear Information System (INIS)

    Fuller, E.L. Jr.; Smyrl, N.R.; Condon, J.B.; Eager, M.H.

    1983-01-01

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures

  15. Uranium/water vapor reactions in gaseous atmospheres

    International Nuclear Information System (INIS)

    Jackson, R.L.; Condon, J.B.; Steckel, L.M.

    1977-07-01

    Experiments have been performed to determine the effect of varying humidities, gaseous atmospheres, and temperatures on the uranium/water vapor reaction. A balance, which allowed continuous in-system weighings, was used to determine the rates of the uranium/water vapor reactions at water vapor pressures of 383, 1586, and 2853 Pa and at temperatures of 80, 100, and 150 0 C in atmospheres of hydrogen, argon, or argon/oxygen mixtures. Based on rate data, the reactions were characterized as hydriding or nonhydriding. Hydriding reactions were found to be preferred in moist hydrogen systems at the higher temperatures and the lower humidities. The presence of hydrogen in hydriding systems was found to initially inhibit the reaction, but causes an acceleration of the rate in the final stages. In general, reaction rates of hydriding systems approached the hydriding rates calculated and observed in dry hydrogen. Hydriding and nonhydriding reaction rates showed a positive correlation to temperature and water vapor pressure. Final reaction rates in moist argon/oxygen mixtures of 1.93, 4.57, and 9.08 mole percent oxygen were greater than the rates observed in moist hydrogen or argon. Final reaction rates were negatively correlated to the oxygen concentration

  16. Applying reaction condition index to predict sandstone type uranium deposit

    International Nuclear Information System (INIS)

    Chen Gongxin; Liu Jinhui; Cheng Hai

    2002-01-01

    On the basic of the explanation of reaction condition index, the deduction of reaction condition index calculation principle, the hydrogeological setting in Gongpoquan basin in Baishan, Gansu province and the study of reaction condition index of its water source point, the north Luotuoquan area in Gongpoquan basin seems to be a favourable place for sandstone type uranium deposit, and the prospect area for sandstone type uranium deposit is delimitated

  17. The reaction of uranium with moist hydrogen

    International Nuclear Information System (INIS)

    Pearce, R.J.; Kay, P.

    1987-10-01

    The reaction of uranium in moist hydrogen at a total pressure of 101 kPa over the temperature range 105 0 -200 0 C and water vapour pressures in the range 5-100 kPa has been examined in a limited thermogravimetric study. It has been shown that initially there is a period during which only linear kinetics are observed with a rate similar to that exhibited in similarly moist argon, i.e. hydrogen has no apparent effect on the reaction. At water vapour pressures of and above 49 kPa, corresponding to hydrogen:water vapour pressure ratios in the range 1:1 to 1:100, over the exposure times studied (not > 20h) only such linear kinetics are observed. Below this water vapour pressure and after an initial period of linear kinetics a continuously increasing reaction rate was observed in some instances resulting from rapid attach on localised areas. The localised reaction rates were approximately 2-3 orders of magnitude faster than the original linear reaction kinetics and the interaction rates in either moist argon or moist air. Comparison with a single experiment carried out at 150 0 C indicated that breakaway rates were approaching that in dry hydrogen. During breakaway attack there was a significant increase in the relative amounts of uranium hydride formed. The duration of the linear kinetics phase was extended by pre-oxidation of the uranium surface, decreasing temperature at a constant water vapour pressure, or increasing water vapour pressure (or water vapour: hydrogen pressure ratio) at a constant temperature. (author)

  18. Reaction of uranium oxides with chlorine and carbon or carbon monoxide to prepare uranium chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Haas, P.A.; Lee, D.D.; Mailen, J.C.

    1991-11-01

    The preferred preparation concept of uranium metal for feed to an AVLIS uranium enrichment process requires preparation of uranium tetrachloride (UCI{sub 4}) by reacting uranium oxides (UO{sub 2}/UO{sub 3}) and chlorine (Cl{sub 2}) in a molten chloride salt medium. UO{sub 2} is a very stable metal oxide; thus, the chemical conversion requires both a chlorinating agent and a reducing agent that gives an oxide product which is much more stable than the corresponding chloride. Experimental studies in a quartz reactor of 4-cm ID have demonstrated the practically of some chemical flow sheets. Experimentation has illustrated a sequence of results concerning the chemical flow sheets. Tests with a graphite block at 850{degrees}C demonstrated rapid reactions of Cl{sub 2} and evolution of carbon dioxide (CO{sub 2}) as a product. Use of carbon monoxide (CO) as the reducing agent also gave rapid reactions of Cl{sub 2} and formation of CO{sub 2} at lower temperatures, but the reduction reactions were slower than the chlorinations. Carbon powder in the molten salt melt gave higher rates of reduction and better steady state utilization of Cl{sub 2}. Addition of UO{sub 2} feed while chlorination was in progress greatly improved the operation by avoiding the plugging effects from high UO{sub 2} concentrations and the poor Cl{sub 2} utilizations from low UO{sub 2} concentrations. An UO{sub 3} feed gave undesirable effects while a feed of UO{sub 2}-C spheres was excellent. The UO{sub 2}-C spheres also gave good rates of reaction as a fixed bed without any molten chloride salt. Results with a larger reactor and a bottom condenser for volatilized uranium show collection of condensed uranium chlorides as a loose powder and chlorine utilizations of 95--98% at high feed rates. 14 refs., 7 figs., 14 tabs.

  19. Kinetic study of the reaction of uranium with various carbon-containing gases; Etude cinetique de la reaction sur l'uranium de differents gaz carbones

    Energy Technology Data Exchange (ETDEWEB)

    Feron, G [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1963-09-15

    The kinetic study of the reaction U + CO{sub 2} and U + CO has been performed by a thermogravimetric method on a spherical uranium powder, in temperature ranges respectively from 460 to 690 deg. C and from 570 to 850 deg. C. The reaction with carbon dioxide leads to uranium dioxide. A carbon deposition takes place at the same time. The global reactions is the result of two reactions: U + 2 CO{sub 2} {yields} UO{sub 2} + 2 CO U + CO{sub 2} {yields} UO{sub 2} + C The reaction with carbon monoxide leads to a mixture of dioxide UO{sub 2}, dicarbide UC{sub 2} and free carbon. The main reaction can be written. U + CO {yields} 1/2 UO{sub 2} + 1/2 UC{sub 2} The free carbon results of the disproportionation of the carbon monoxide. A remarkable separation of the two phases UO{sub 2} and UC{sub 2} can be observed. A mechanism accounting for the phenomenon has been proposed. The two reactions U + CO{sub 2} and U + CO begin with a long germination period, after which, the reaction velocity seems to be limited in both cases by the ionic diffusion of oxygen through the uranium dioxide. (author) [French] L'etude cinetique des reactions U sol + CO{sub 2} gaz et U sol + CO gaz a ete effectuee par thermogravirnetrie sur une poudre d'uranium a grains spheriques, les domaines de temperature etudies s'etendant respectivement de 460 a 690 deg. C et de 570 a 850 deg. C. L'action du dioxyde de carbone conduit au dioxyde d'uranium UO{sub 2}; il se produit en meme temps un depot de carbone. La reaction globale resulte des deux reactions: U + 2 CO{sub 2} {yields} UO{sub 2} + 2 CO U + CO{sub 2} {yields} UO{sub 2} + C Le mono-oxyde de carbone conduit a un melange de dioxyde UO{sub 2}, de dicarbure UC{sub 2} et de carbone libre. La reaction principale s'ecrit: U + CO {yields} 1/2 UO{sub 2} + 1/2 UC{sub 2} Le carbone libre provient de la dismutation du mono-oxyde de carbone. On observe une separation remarquable des deux phases UO{sub 2} et UC{sub 2}; un mecanisme rendant compte de ce phenomene a

  20. Radiation pathways and potential health impacts from inactive uranium mill tailings

    International Nuclear Information System (INIS)

    1978-07-01

    Radiation exposure pathways and potential health impacts were estimated as part of the evaluation of radioactive uranium mill tailings at the sites of inactive mills in eight western states. The purpose of this report is to describe in detail the methodology used in performing the pathway analysis and health effects estimations. In addition, specific parameters are presented for each of the 22 uranium mill sites that were evaluated. A computer program, RADAD, developed as part of this program, is described and listed

  1. Reactions of plutonium and uranium with water: Kinetics and potential hazards

    International Nuclear Information System (INIS)

    Haschke, J.M.

    1995-12-01

    The chemistry and kinetics of reactions between water and the metals and hydrides of plutonium and uranium are described in an effort to consolidate information for assessing potential hazards associated with handling and storage. New experimental results and data from literature sources are presented. Kinetic dependencies on pH, salt concentration, temperature and other parameters are reviewed. Corrosion reactions of the metals in near-neutral solutions produce a fine hydridic powder plus hydrogen. The corrosion rate for plutonium in sea water is a thousand-fold faster than for the metal in distilled water and more than a thousand-fold faster than for uranium in sea water. Reaction rates for immersed hydrides of plutonium and uranium are comparable and slower than the corrosion rates for the respective metals. However, uranium trihydride is reported to react violently if a quantity greater than twenty-five grams is rapidly immersed in water. The possibility of a similar autothermic reaction for large quantities of plutonium hydride cannot be excluded. In addition to producing hydrogen, corrosion reactions convert the massive metals into material forms that are readily suspended in water and that are aerosolizable and potentially pyrophoric when dry. Potential hazards associated with criticality, environmental dispersal, spontaneous ignition and explosive gas mixtures are outlined

  2. The reaction of sintered aluminium products with uranium dioxide and monocarbide

    DEFF Research Database (Denmark)

    Lauritzen, T.; Knudsen, Per

    1965-01-01

    The compatibility of SAP 930 with uranium dioxide and uranium monocarbide was investigated in the temperature range 450–600° C. The results indicate that a severe reaction occurs between SAP 930 and UO2 within 8000 hours at 600° C, a slight reaction at 600° C for 1000 hours and after 11 900 hours...... at 525° C, and no reaction in 14 300 hours at 450° C. Of the three grades of UC tested (hot pressed, arc cast, cold pressed and sintered) the slightly substoichiometric, hot-pressed UC is judged to be least compatible with SAP 930, reaction occurring after 7300 hours at 450° C. No reaction was observed...... between SAP 930 and the other carbides at this temperature. All SAP−UC combinations are incompatible at 600° C for as little as 100 hours of heat treatment. Tests designed to study the effect of a diffusion barrier on the SAP−UC reaction have shown that anodized SAP 930 and the three uranium carbides...

  3. Uranium Metal Reaction Behavior in Water, Sludge, and Grout Matrices

    Energy Technology Data Exchange (ETDEWEB)

    Delegard, Calvin H.; Schmidt, Andrew J.

    2009-05-27

    This report summarizes information and data on the reaction behavior of uranium metal in water, in water-saturated simulated and genuine K Basin sludge, and in grout matrices. This information and data are used to establish the technical basis for metallic uranium reaction behavior for the K Basin Sludge Treatment Project (STP). The specific objective of this report is to consolidate the various sources of information into a concise document to serve as a high-level reference and road map for customers, regulators, and interested parties outside the STP (e.g., external reviewers, other DOE sites) to clearly understand the current basis for the corrosion of uranium metal in water, sludge, and grout.

  4. Uranium Metal Reaction Behavior in Water, Sludge, and Grout Matrices

    Energy Technology Data Exchange (ETDEWEB)

    Delegard, Calvin H.; Schmidt, Andrew J.

    2008-09-25

    This report summarizes information and data on the reaction behavior of uranium metal in water, in water-saturated simulated and genuine K Basin sludge, and in grout matrices. This information and data are used to establish the technical basis for metallic uranium reaction behavior for the K Basin Sludge Treatment Project (STP). The specific objective of this report is to consolidate the various sources of information into a concise document to serve as a high-level reference and road map for customers, regulators, and interested parties outside the STP (e.g., external reviewers, other DOE sites) to clearly understand the current basis for the corrosion of uranium metal in water, sludge, and grout.

  5. Reaction of uranium and plutonium carbides with nitrogen; Reaction avec l'azote des carbures d'uranium et de plutonium

    Energy Technology Data Exchange (ETDEWEB)

    Lorenzelli, R; Martin, A; Schickel, R [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1966-03-01

    Uranium and plutonium carbides react with nitrogen during the grinding process preceding the final sintering. The reaction occurs even in argon atmospheres containing a few percent of residual nitrogen. The resulting contamination is responsible for the appearance of an equivalent quantity of higher carbide in the sintered products; nitrogen remains quantitatively in the monocarbide phase. UC can be transformed completely into nitride under a nitrogen pressure, at a temperature as low as 400 C. The reaction is more sluggish with PuC. The following reactions take places: UC + 0,8 N{sub 2} {yields}> UN{sub 1.60} + C and PuC + 0,5 N{sub 2} {yields} PuN + C. (authors) [French] Les carbures d'uranium et de plutonium reagissent avec l'azote au cours du broyage qui precede le frittage final. Cette reaction est sensible meme sous des atmospheres d'argon ne contenant que quelques pour cent d'azote. Cette contamination se traduit sur les produits frittes par l'apparition d'une quantite equivalente de carbure superieur, l'azote restant fixe quantitativement dans la phase monocarbure. On peut transformer entierement UC en nitrure par action de l'azote sous pression des 400 C. La reaction est plus difficile avec PuC. Les reactions sont les suivantes: UC + 0,8 N{sub 2} {yields} UN{sub 1.60} + C et PuC + 0,5 N{sub 2} {yields} PuN + C.

  6. Study on the surface reaction of uranium metal in hydrogen atmosphere with XPS

    International Nuclear Information System (INIS)

    Wang Xiaolin; Fu Yibei; Xie Renshou; Zuo Changming; Zhao Chunpei; Chen Hong

    1998-01-01

    The surface reactions of uranium metal in hydrogen atmosphere at 25 degree C and 200 degree C and effects of temperature and carbon monoxide to the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between H 2 and uranium metal at 25 degree C leads to the further oxidation of surface layer of metal due to traces of water vapor. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing exposure to H 2 in the initial stages. The U4f 7/2 binding energy of UH 3 has been found to be 378.6 eV. Investigation indicates carbon monoxide inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmosphere

  7. Kinetic study of the reaction of uranium with various carbon-containing gases

    International Nuclear Information System (INIS)

    Feron, G.

    1963-09-01

    The kinetic study of the reaction U + CO 2 and U + CO has been performed by a thermogravimetric method on a spherical uranium powder, in temperature ranges respectively from 460 to 690 deg. C and from 570 to 850 deg. C. The reaction with carbon dioxide leads to uranium dioxide. A carbon deposition takes place at the same time. The global reactions is the result of two reactions: U + 2 CO 2 → UO 2 + 2 CO U + CO 2 → UO 2 + C The reaction with carbon monoxide leads to a mixture of dioxide UO 2 , dicarbide UC 2 and free carbon. The main reaction can be written. U + CO → 1/2 UO 2 + 1/2 UC 2 The free carbon results of the disproportionation of the carbon monoxide. A remarkable separation of the two phases UO 2 and UC 2 can be observed. A mechanism accounting for the phenomenon has been proposed. The two reactions U + CO 2 and U + CO begin with a long germination period, after which, the reaction velocity seems to be limited in both cases by the ionic diffusion of oxygen through the uranium dioxide. (author) [fr

  8. Sintering with a chemical reaction as applied to uranium monocarbide; Frittage-reaction dans le cas du monocarbure d'uranium

    Energy Technology Data Exchange (ETDEWEB)

    Accary, A; Caillat, R [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1960-07-01

    The present paper provides a survey of different investigations whose aim was the preparation and fabrication of uranium monocarbide for nuclear use. If a chemical reaction takes place in the sample during the sintering operation, it may be expected that the atom rearrangements involved in this reaction should favour the sintering process and thereby lower the temperature needed to yield a body of a given density. With this hypothesis in mind, the following methods have been studied: - Sintering of U-C mixtures; - Sintering of UO{sub 2}-C mixtures; - Hot pressing of U-C mixtures; - Extrusion of U-C mixtures. To generalize our result, it could be said that a chemical reaction does not lead to high densification, if one depends on a simple contact between discrete particles. On the contrary, a chemical reaction can help sintering if, as our hot pressing experiments shows, the densification can be achieved prior to the reaction. (author) [French] Le present article resume les etudes faites pour le compte du Commissariat a l'Energie Atomique dans le but de preparer du monocarbure d'uranium pour usage nucleaire. Si, en meme temps que l'on fritte une poudre, celle-ci est le siege d'une reaction chimique, on peut s'attendre a ce que le rearrangement atomique d'une reaction chimique favorise le frittage et, ainsi abaisse la temperature de travail necessaire pour obtenir une densite donnee. Nous avons etudie les methodes suivantes: - frittage des melanges U-C; - frittage des melanges UO{sub 2}-C; - frittage sous charge des melanges U-C; - filage des melanges U-C. Nos resultats montrent qu'une reaction chimique en cours de frittage ne conduit pas a un produit de haute densite si on opere sur un melange de poudres. Par contre, elle permet d'atteindre de hautes densites si la densification peut etre obtenue avant la reaction chimique. (auteur)

  9. Reactions of laser ablated uranium with nitrogen studied using matrix isolation spectroscopy

    International Nuclear Information System (INIS)

    Sankaran, K.; Sundararajan, K.; Viswanathan, K.S.

    1999-01-01

    Unusual reactions were found to occur when uranium was laser ablated in the presence of nitrogen. The reaction products were trapped in a rigid inert gas matrix and studied using infrared spectroscopy. The species formed were strongly dependent on the partial pressure of nitrogen in the matrix gas used during the ablation process; at low nitrogen partial pressures uranium dinitride (NUN) was the major reaction product, while at high partial pressures of nitrogen the mononitride, UN, was the predominant product. (author)

  10. Uranium reactions with water vapor. Final progress report

    International Nuclear Information System (INIS)

    Condon, J.B.; Cristy, S.S.; Kirkpatrick, J.R.

    1983-01-01

    The reaction kinetics and ion microprobe mass analyzer (IMMA) depth-profile data for water-oxygen-uranium reaction is explained in terms of the perfusive-precipitation model. This model is reviewed extensively enough to deal with this interacting, 3-element reaction system. The model, based on simultaneous diffusion and product precipitation, can be applied to several systems in a parameterless fashion. It is applied to the uranium-water reaction in the absence and presence of the oxygen inhibitor. The results of the calculations of the model are compared to the experimental rates and the IMMA depth profiles obtained when 18 O-labeled water is used. The predictions are excellent for the pressure dependence of the rates, the activation energies for both the oxygen-poisoned and oxygen-free reactions, the absolute rates for the oxygen-poisoned case, and the IMMA depth profiles. The prediction of the absolute rate for the oxygen-free case is only within a factor of five due to the approximations made for the thermodynamics of the product layer that fixes the oxygen activity. Comparison of the model to experimental data for other metal-oxidation systems such as iron, silicon, copper, zirconium with oxygen, and thorium with water, is also presented to lend credibility to the modeling technique

  11. Fluorination reaction uranium dioxide by fluorine

    International Nuclear Information System (INIS)

    Ogata, Shinji; Homma, Shunji; Koga, Jiro; Matsumoto, Shiro; Sasahira, Akira; Kawamura, Fumio

    2004-01-01

    Kinetics of the fluorination reaction of uranium dioxide is studied using un-reacted core model with shrinking particles. The model includes the film mass transfer of fluorine gas and its diffusion in the particle. The rate constants of the model are determined by fitting the experimental data for 370-450degC. The model successfully represents the fluorination in this temperature range. The rate control step is identified by examining the rate constants of the model for 300-1,800degC. For temperature range up to 900degC, the fluorination reaction is rate controlling. For over 900degC, both mechanisms of the mass transfer of fluorine and the fluorination reaction control the rate of the fluorination. With further increase of the temperature, however, the fluorination reaction becomes so fast that the mass transfer of fluorine eventually controls the rate of the fluorination. (author)

  12. Kinetics of gaseous uranium hexafluoride reaction with hydrogen chloride

    International Nuclear Information System (INIS)

    Ezubchenko, A.N.; Ilyukhin, A.I.; Merzlyakov, A.V.

    1993-01-01

    Kinetics of decrease of concentration of gaseous uranium hexafluoride in reaction with hydrogen chloride at temperatures close to room ones, was investigated by the method of IR spectroscopy. It was established that the process represented the first order reaction by both UF 6 and HCl. Activation energy of the reaction was determined: 7.6 ± 0.7 kcal/mol. Specific feature of reaction kinetics was noted: inversely proportional dependence of effective constant on UF 6 initial pressure. 5 refs., 3 figs

  13. Compound Nucleus Reactions in LENR, Analogy to Uranium Fission

    Science.gov (United States)

    Hora, Heinrich; Miley, George; Philberth, Karl

    2008-03-01

    The discovery of nuclear fission by Hahn and Strassmann was based on a very rare microanalytical result that could not initially indicate the very complicated details of this most important process. A similarity is discussed for the low energy nuclear reactions (LENRs) with analogies to the yield structure found in measurements of uranium fission. The LENR product distribution measured earlier in a reproducible way in experiments with thin film electrodes and a high density deuteron concentration in palladium has several striking similarities with the uranium fission fragment yield curve.ootnotetextG.H. Miley and J.A. Patterson, J. New Energy 1, 11 (1996); G.H. Miley et al, Proc ICCF6, p. 629 (1997).This comparison is specifically focussed to the Maruhn-Greiner local maximum of the distribution within the large-scale minimum when the fission nuclei are excited. Implications for uranium fission are discussed in comparison with LENR relative to the identification of fission a hypothetical compound nuclear reaction via a element ^306X126 with double magic numbers.

  14. Some potential strategies for the treatment of waste uranium metal and uranium alloys

    International Nuclear Information System (INIS)

    Burns, C.J.; Frankcom, T.M.; Gordon, P.L.; Sauer, N.N.

    1993-01-01

    Large quantities of uranium metal chips and turnings stored throughout the DOE Complex represent a potential hazard, due to the reactivity of this material toward air and water. Methods are being sought to mitigate this by conversion of the metal, via room temperature solutions routes, to a more inert oxide form. In addition, the recycling of uranium and concomitant recovery of alloying metals is a desirable goal. The emphasis of the authors' research is to explore a variety of oxidation and reduction pathways for uranium and its compounds, and to investigate how these reactions might be applied to the treatment of bulk wastes

  15. A kinetic study of the reaction of water vapor and carbon dioxide on uranium

    International Nuclear Information System (INIS)

    Santon, J.P.

    1964-09-01

    The kinetic study of the reaction of water vapour and carbon dioxide with uranium has been performed by thermogravimetric methods at temperatures between 160 and 410 deg G in the first case, 350 and 1050 deg C in the second: Three sorts of uranium specimens were used: uranium powder, thin evaporated films, and small spheres obtained from a plasma furnace. The experimental results led in the case of water vapour, to a linear rate of reaction controlled by diffusion at the lower temperatures, and by a surface reaction at the upper ones. In the case of carbon dioxide, a parabolic law has been found, controlled by diffusional processes. (author) [fr

  16. Advances in heterogeneous autocatalytic reactions applied to uranium dissolution - 5317

    International Nuclear Information System (INIS)

    Marc, P.; Magnaldo, A.; Godard, J.; Schaer, E.

    2015-01-01

    Dissolution and the solubilization of the chemical elements is a milestone of the head-end of hydrometallurgical processes. When dissolving spent nuclear fuels, additional constraints are added due to the permanent need to strictly control and limit the hold-up. Thus the need for kinetic modeling concerning the dissolution of spent nuclear fuels in nitric acid. This study aims at better understanding the chemical and physical-chemical phenomena of uranium dioxide dissolution reactions in nitric medium. It has been documented that the nitric acid attack of sintering-manufactured uranium dioxide solids occurs through preferential attack sites. This non uniform attack leads to the development of cracks in the solids. Optical microscopy observations show that in some cases, the development of these cracks can lead to the solid cleavage. In this case, we show that the dissolution of the detached fragments is much slower than the time required for the complete cleavage of the solid. These points motivated the measurements of dissolution kinetics using optical microscopy and image processing. A comparison of the measured kinetics with the diffusion kinetics by the mean of the external resistance fraction allows discriminating between measured kinetics corresponding to the chemical reaction or mass-transport limitation. This capability to measure, for the very first time, the 'true' chemical kinetics of the reaction has enabled the confirmation of the highly autocatalytic nature of the reaction, and first evaluation of the constants of the chemical reactions kinetic laws. These data are fundamental to set the kinetic parameters of the chemical reactions in a future model of the dissolution of uranium dioxide sintered pellets. (authors)

  17. Interest of uranium complexes for the mechanism study of the McMurry reaction; Interet des complexes de l`uranium pour l`etude du mecanisme de la reaction de McMurry

    Energy Technology Data Exchange (ETDEWEB)

    Maury, O

    1997-07-04

    The reducing coupling reactions of ketones in diols and olefins are generally carried out with titanium or samarium compounds. In this work uranium complexes have been used. They have allowed to study the chemical reaction mechanism. This thesis is divided into three parts: 1) the reduction mechanism of uranium tetrachloride by cyclic voltametry has been studied at first. It has been shown that this reduction is followed by a transfer reaction of chlorides between the reduced specie of the higher electronic density and UCl . 2) In the second part is described: the synthesis, the crystal structure, the reactivity of the chemical agents, the stereochemistry of diols and alkenes formation and the pinacolisation reaction catalysis. 3) In the last part, the limits of the McMurry reaction are given by the study of the aromatic ketones pinacolisation reaction by-products. The obtained results show that the complexes of the metals which present a high reducing and oxo-philic (Ti, Sm, U..) character react in a similar way with the carbonyl compounds. If the uranium compounds are less used than those of the titanium in the field of the organic synthesis applications, they are precious auxiliaries and excellent models for reactions mechanisms study and for the synthesis methods optimization. (O.M.). 284 refs.

  18. A review of the rates of reaction of unirradiated uranium in gaseous atmospheres

    International Nuclear Information System (INIS)

    Pearce, R.J.

    1989-10-01

    The review collates available quantitative rate data for the reaction of unirradiated uranium in dry and moist air, steam and carbon dioxide based atmospheres at temperatures ranging from room temperature to above the melting point of uranium. Reactions in nitrogen and carbon monoxide are also considered. The aim of the review is to provide a compilation of base data for the hazard analysis of fault conditions relating to Magnox fuel. (author)

  19. Reaction of nickel with uranium mononitride; Reaction du nickel avec le nitrure d'uranium

    Energy Technology Data Exchange (ETDEWEB)

    Anselin, F; Calais, D; Lorenzelli, N; Passefort, J C [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1965-07-01

    UN-Ni system has been investigated in solid phase by diffusion couples UN-Ni or by mixed powders pressed and sintered. Studies have been carried out by micrography, X-rays and microanalysis with a CASTAING microprobe. UN-Ni compatibility is quite good up to 600 C; beyond this temperature diffusion zones corresponding to UNi{sub 5} and U{sub 2}N{sub 3} appear in the couples either reaction : 3 U N + 5 Ni {yields} U{sub 2}N{sub 3} + UNi{sub 5}; UN + 5 Ni {yields} UNi{sub 5}+ 1/2 N{sub 2} takes place from 700 C according to nitrogen pressure involved. For temperatures between 800 and 1000 C nickel solubility in uranium nitride is 1500 {+-} 500 wt ppm. (authors) [French] Le systeme UN-Ni a ete etudie par diffusion en phase solide a partir de couples (UN-Ni) ou de melanges pulverulents presses et frittes. Les techniques utilisees sont la micrographie, les rayons X et l'analyse ponctuelle a la microsonde de CASTAING. La compatibilite UN-Ni est bonne jusqu'a 600 C; au-dela il apparait dans les couples de diffusion des zones correspondant a UNi{sub 5} et U{sub 2}N{sub 3}. L'une ou l'autre des deux reactions: 3UN + 5 Ni {yields} U{sub 2}N{sub 3} + UNi{sub 5}; UN + 5 Ni {yields} UNi{sub 5} + 1/2 N{sub 2} se produisant des 700 C suivant la pression d'azote exercee. La solubilite du nickel dans le nitrure d'uranium pour des temperatures comprises entre 800 et 1000 C est de 1500 {+-} 500 ppm en poids. (auteurs)

  20. Aligning Metabolic Pathways Exploiting Binary Relation of Reactions.

    Directory of Open Access Journals (Sweden)

    Yiran Huang

    Full Text Available Metabolic pathway alignment has been widely used to find one-to-one and/or one-to-many reaction mappings to identify the alternative pathways that have similar functions through different sets of reactions, which has important applications in reconstructing phylogeny and understanding metabolic functions. The existing alignment methods exhaustively search reaction sets, which may become infeasible for large pathways. To address this problem, we present an effective alignment method for accurately extracting reaction mappings between two metabolic pathways. We show that connected relation between reactions can be formalized as binary relation of reactions in metabolic pathways, and the multiplications of zero-one matrices for binary relations of reactions can be accomplished in finite steps. By utilizing the multiplications of zero-one matrices for binary relation of reactions, we efficiently obtain reaction sets in a small number of steps without exhaustive search, and accurately uncover biologically relevant reaction mappings. Furthermore, we introduce a measure of topological similarity of nodes (reactions by comparing the structural similarity of the k-neighborhood subgraphs of the nodes in aligning metabolic pathways. We employ this similarity metric to improve the accuracy of the alignments. The experimental results on the KEGG database show that when compared with other state-of-the-art methods, in most cases, our method obtains better performance in the node correctness and edge correctness, and the number of the edges of the largest common connected subgraph for one-to-one reaction mappings, and the number of correct one-to-many reaction mappings. Our method is scalable in finding more reaction mappings with better biological relevance in large metabolic pathways.

  1. Interest of uranium complexes for the mechanism study of the McMurry reaction

    International Nuclear Information System (INIS)

    Maury, O.

    1997-01-01

    The reducing coupling reactions of ketones in diols and olefins are generally carried out with titanium or samarium compounds. In this work uranium complexes have been used. They have allowed to study the chemical reaction mechanism. This thesis is divided into three parts: 1) the reduction mechanism of uranium tetrachloride by cyclic voltametry has been studied at first. It has been shown that this reduction is followed by a transfer reaction of chlorides between the reduced specie of the higher electronic density and UCl . 2) In the second part is described: the synthesis, the crystal structure, the reactivity of the chemical agents, the stereochemistry of diols and alkenes formation and the pinacolisation reaction catalysis. 3) In the last part, the limits of the McMurry reaction are given by the study of the aromatic ketones pinacolisation reaction by-products. The obtained results show that the complexes of the metals which present a high reducing and oxo-philic (Ti, Sm, U..) character react in a similar way with the carbonyl compounds. If the uranium compounds are less used than those of the titanium in the field of the organic synthesis applications, they are precious auxiliaries and excellent models for reactions mechanisms study and for the synthesis methods optimization. (O.M.)

  2. XPS study on the surface reaction of uranium metal in H2 and H2-CO atmospheres

    International Nuclear Information System (INIS)

    Wang Xiaolin; Fu Yibei; Xie Renshou

    1996-04-01

    The surface reactions of uranium metal in H 2 and H 2 -CO atmospheres and the effects of temperature and CO on the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between commercial H 2 and uranium metal at 25 degree C leads mainly to the further oxidation of surface layer of metal due to traces of water vapour. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing the exposure of H 2 . Investigation indicates CO inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmospheres. (13 refs., 10 figs.)

  3. Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide. Factors governing diverse and well-defined cleavage and redox reactions

    International Nuclear Information System (INIS)

    Cleaves, Peter A.; Gardner, Benedict M.; Liddle, Stephen T.; Kefalidis, Christos E.; Maron, Laurent; Tuna, Floriana; McInnes, Eric J.L.; Lewis, William

    2017-01-01

    The reactivity of terminal uranium(V/VI) nitrides with CE 2 (E=O, S) is presented. Well-defined C=E cleavage followed by zero-, one-, and two-electron redox events is observed. The uranium(V) nitride [U(Tren TIPS )(N)][K(B15C5) 2 ] (1, Tren TIPS =N(CH 2 CH 2 NSiiPr 3 ) 3 ; B15C5=benzo-15-crown-5) reacts with CO 2 to give [U(Tren TIPS )(O)(NCO)][K(B15C5) 2 ] (3), whereas the uranium(VI) nitride [U(Tren TIPS )(N)] (2) reacts with CO 2 to give isolable [U(Tren TIPS )(O)(NCO)] (4); complex 4 rapidly decomposes to known [U(Tren TIPS )(O)] (5) with concomitant formation of N 2 and CO proposed, with the latter trapped as a vanadocene adduct. In contrast, 1 reacts with CS 2 to give [U(Tren TIPS )(κ 2 -CS 3 )][K(B15C5) 2 ] (6), 2, and [K(B15C5) 2 ][NCS] (7), whereas 2 reacts with CS 2 to give [U(Tren TIPS )(NCS)] (8) and ''S'', with the latter trapped as Ph 3 PS. Calculated reaction profiles reveal outer-sphere reactivity for uranium(V) but inner-sphere mechanisms for uranium(VI); despite the wide divergence of products the initial activation of CE 2 follows mechanistically related pathways, providing insight into the factors of uranium oxidation state, chalcogen, and NCE groups that govern the subsequent divergent redox reactions that include common one-electron reactions and a less-common two-electron redox event. Caution, we suggest, is warranted when utilising CS 2 as a reactivity surrogate for CO 2 . (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Uranium oxidation: Characterization of oxides formed by reaction with water by infrared and sorption analyses

    Science.gov (United States)

    Fuller, E. L.; Smyrl, N. R.; Condon, J. B.; Eager, M. H.

    1984-04-01

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. The results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. Inert gas sorption analyses and diffuse reflectance infrared studies combined with electron microscopy prove valuable in defining the chemistry and morphology of the oxidic products and hydrated intermediates.

  5. A kinetic study of the reaction of water vapor and carbon dioxide on uranium; Cinetique de la reaction de la vapeur d'eau et du dioxyde de carbone sur l'uranium

    Energy Technology Data Exchange (ETDEWEB)

    Santon, J P [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1964-09-15

    The kinetic study of the reaction of water vapour and carbon dioxide with uranium has been performed by thermogravimetric methods at temperatures between 160 and 410 deg G in the first case, 350 and 1050 deg C in the second: Three sorts of uranium specimens were used: uranium powder, thin evaporated films, and small spheres obtained from a plasma furnace. The experimental results led in the case of water vapour, to a linear rate of reaction controlled by diffusion at the lower temperatures, and by a surface reaction at the upper ones. In the case of carbon dioxide, a parabolic law has been found, controlled by diffusional processes. (author) [French] L'etude cinetique de la reaction de la vapeur d'eau et du dioxyde de carbone sur l'uranium a ete entreprise au moyen de methodes thermogravimetriques, dans te premier cas entre 160 et 410 deg C et dans le second entre 350 et 1050 deg C. Le materiau utilise se presentait sous trois formes: poudres, couches minces evaporees et billes obtenues par fusion en chalumeau a plasma. Les resultats experimentaux ont permis de mettre en evidence, dans le cas de la vapeur d'eau, une cinetique lineaire controlee par la diffusion a basse temperature et d'interface a haute temperature. Dans le cas du dioxyde de carbone par contre, on trouve une cinetique parabolique controlee par la diffusion. (auteur)

  6. Chemometric approach for prediction of uranium pathways in the soil

    International Nuclear Information System (INIS)

    Stojanovic, Mirjana; Nihajlovic, Marija; Petrovic, Jelena; Petrovic, Marija; Sostaric, Tanja; Milojkovic, Jelena; Pezo, Lato

    2014-01-01

    Understanding the effect of soil parameters (pH, Eh and organic and inorganic ligands availability) on uranium mobility under different geochemical conditions is fundamental for reliable prediction of its behaviour and fate in the environment. In this study, the impact of total and available phosphorus content, humus and acidity of Serbian agricultural soils on the content of total and available uranium were evaluated by Response Surface Methodology (RSM), second order polynomial regression models (SOPs) and artificial neural networks (ANNs). The performance of ANNs was compared with the performance of SOPs and experimental results. SOPs showed high coefficients of determination (0.785-0.956), while ANN model performed high prediction accuracy: 0.8893-0.904. According to the results, total and available uranium content in the soil were mostly affected by pH, statistically significant at p < 0.05 level. For the same responses the total phosphorus was found to be also very influential, statistically significant at p < 0.05 and p < 0.10 levels. The impact of available phosphorus and humus was much more influential on total and available uranium content, compared to total phosphorus content. Proposed chemometric approach will be very helpful in preserving the natural resources and practical application for risk assessment modeling of uranium environmental pathways.

  7. Some Investigations of the Reaction of Activated Charcoal with Fluorine and Uranium Hexafluoride

    Energy Technology Data Exchange (ETDEWEB)

    Del Cul, G.D.; Fiedor, J.N.; Simmons, D.W.; Toth, L.M.; Trowbridge, L.D.; Williams

    1998-09-01

    The Molten Salt Reactor Experiment (MSRE) at Oak Ridge National Laboratory has been shut down since 1969, when the fuel salt was drained from the core into two Hastelloy N drain tanks at the reactor site. Over time, fluorine (F{sub 2}) and uranium hexafluoride (UF{sub 6}) moved from the salt through the gas piping to a charcoal bed, where they reacted with the activated charcoal. Some of the immediate concerns related to the migration of F{sub 2} and UF{sub 6} to the charcoal bed were the possibility of explosive reactions between the charcoal and F{sub 2}, the existence of conditions that could induce a criticality accident, and the removal and recovery of the fissile uranium from the charcoal. This report addresses the reactions and reactivity of species produced by the reaction of fluorine and activated charcoal and between charcoal and F{sub 2}-UF{sub 6} gas mixtures in order to support remediation of the MSRE auxiliary charcoal bed (ACB) and the recovery of the fissile uranium. The chemical identity, stoichiometry, thermochemistry, and potential for explosive decomposition of the primary reaction product, fluorinated charcoal, was determined.

  8. Some Investigations of the Reaction of Activated Charcoal with Fluorine and Uranium Hexafluoride

    International Nuclear Information System (INIS)

    Del Cul, G.D.; Fiedor, J.N.; Simmons, D.W.; Toth, L.M.; Trowbridge, L.D.; Williams

    1998-01-01

    The Molten Salt Reactor Experiment (MSRE) at Oak Ridge National Laboratory has been shut down since 1969, when the fuel salt was drained from the core into two Hastelloy N drain tanks at the reactor site. Over time, fluorine (F 2 ) and uranium hexafluoride (UF 6 ) moved from the salt through the gas piping to a charcoal bed, where they reacted with the activated charcoal. Some of the immediate concerns related to the migration of F 2 and UF 6 to the charcoal bed were the possibility of explosive reactions between the charcoal and F 2 , the existence of conditions that could induce a criticality accident, and the removal and recovery of the fissile uranium from the charcoal. This report addresses the reactions and reactivity of species produced by the reaction of fluorine and activated charcoal and between charcoal and F 2 -UF 6 gas mixtures in order to support remediation of the MSRE auxiliary charcoal bed (ACB) and the recovery of the fissile uranium. The chemical identity, stoichiometry, thermochemistry, and potential for explosive decomposition of the primary reaction product, fluorinated charcoal, was determined

  9. Reaction of water vapor with a clean liquid uranium surface

    International Nuclear Information System (INIS)

    Siekhaus, W.

    1985-01-01

    To study the reaction of water vapor with uranium, we have exposed clean liquid uranium surfaces to H 2 O under UHV conditions. We have measured the surface concentration of oxygen as a function of exposure, and determined the maximum attainable surface oxygen concentration X 0 /sup s/ as a function of temperature. We have used these measurements to estimate, close to the melting point, the solubility of oxygen (X 0 /sup b/, -4 ) and its surface segregation coefficient β/sup s/(> 10 3 ). 8 refs., 5 figs., 1 tab

  10. Combustion kinetics and reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Klemm, R.B.; Sutherland, J.W. [Brookhaven National Laboratory, Upton, NY (United States)

    1993-12-01

    This project is focused on the fundamental chemistry of combustion. The overall objectives are to determine rate constants for elementary reactions and to elucidate the pathways of multichannel reactions. A multitechnique approach that features three independent experiments provides unique capabilities in performing reliable kinetic measurements over an exceptionally wide range in temperature, 300 to 2500 K. Recent kinetic work has focused on experimental studies and theoretical calculations of the methane dissociation system (CH{sub 4} + Ar {yields} CH{sub 3} + H + Ar and H + CH{sub 4} {yields} CH{sub 3} + H{sub 2}). Additionally, a discharge flow-photoionization mass spectrometer (DF-PIMS) experiment is used to determine branching fractions for multichannel reactions and to measure ionization thresholds of free radicals. Thus, these photoionization experiments generate data that are relevant to both reaction pathways studies (reaction dynamics) and fundamental thermochemical research. Two distinct advantages of performing PIMS with high intensity, tunable vacuum ultraviolet light at the National Synchrotron Light Source are high detection sensitivity and exceptional selectivity in monitoring radical species.

  11. redox reactions of uranium in the presence of potassium 2-phospho-17-tungstate

    International Nuclear Information System (INIS)

    Maslov, L.P.; Rykov, A.G.; Sirotinkina, L.V.

    1986-01-01

    The redox reactions of uranium in the presence of potassium 2-phospho-17-tungstate (17W2P) - K 10 P 2 W 17 O 61 - were studied by the methods of spectrophotometry and potentiometry. It was established that in the presence of 17W2P the UO /SUP 2/2/ + ion is reduced by iron(II) to uranium(IV) as a result of the binding of U(IV) into a strong complex with composition (U(p 2 W 17 O 61 ) 2 ) 16- . The peculiarities of the coordination of uranium(IV) by voluminous 17W2P ligands are the cause of the different nature of its interaction with various types of oxidizing agents. It was established that under the action of oxidizing agents (K 2 Cr 2 O 7 , KMnO 4 ), the reduced form of which is a complex with 17W2P, there is a conversion of the complex of uranium(IV) to the corresponding complex of uranium(V), evidently with conservation of a structure analogous to that for uranium(IV). It was also shown that uranium(IV) in complex with 17W2P is practically not oxidized in the cold by persulfate ions which react according to a radical mechanism, whereas weaker oxidizing agents, for example, H 2 O 2 , oxidize it to the UO /SUP 2/2/ + ion. Hypotheses are advanced on the possible mechanisms of the occurrence of the corresponding reactions

  12. Purification of free hydrogen or hydrogen combined in a gaseous mixture by chemical reactions with uranium

    International Nuclear Information System (INIS)

    Caron-Charles, M.; Gilot, B.

    1989-01-01

    Within the framework of the European fusion program, the authors are dealing with the tritium technology aspect. Hydrogen, free or under a combined form within a H 2 , N 2 , NH 3 , O 2 , gaseous mixture, can be purified by chemical reactions with uranium metal. The resulting reactions consist in absorbing the impurities without holding back H 2 . Working conditions have been defined according to two main goals: the formation of stable solid products, especially under hydrogenated atmosphere and the optimization of the material quantities to be used. Thermodynamical considerations have shown that the 950-1300 K temperature range should be suitable for this chemical process. Experiments performed with massive uranium set in a closed reactor at 973 K, have produced hydrogen according to the predicted reactions rates. But they have also pointed out the importance of interferences that might occur in the uranium-gas system, on the gases conversion rates. The comparison between the chemical kinetic ratings of the reactions of pure gases and the chemical kinetic ratings of the reactions of the same gases in mixture, has been set up. It proves that simultaneous reactions can modify the working conditions of the solid products formation, and particularly modify their structure. In this case, chemical kinetic ratings are increased up to their maximal value; that means surface phenomena are favoured as with uranium powder gases reactions. (orig.)

  13. Reaction of Tris(cyclopentadienyl)uranium compounds with amines, azides, and related ligands

    International Nuclear Information System (INIS)

    Rosen, R.K.

    1989-12-01

    The trivalent uranium compound, (MeC 5 H 4 ) 3 U(thf), serves as a one- or two-electron reducing agent towards azides, RN 3 . These reactions produce either the uranium(IV) azide, (MeC 5 H 4 ) 3 UN 3 , or uranium(V) imides, (MeC 5 H 4 ) 3 UNR. The role of steric and electronic effects upon this reaction has been investigated using several series of azides. For Me 3 XN 3 , the imides are produced when X = C or Si, both products are formed when X = Ge, and the azide is produced when X = Sn. For Ph 3 XN 3 , the azide is produced when X = C or Sn. For Ph 3-x CH 3 N 3 , the imide is produced when x = 2 and both compounds are produced when x = 1. For substituted phenylazides, RC 6 H 4 N 3 , only the imides are produced. The magnetic properties of uranium diimides, [(MeC 5 H 4 ) 3 U] 2 (μ-NRN), were investigated. Several uranium(III) amines, (MeC 5 H 4 ) 3 U(NH 2 R), were produced from (MeC 5 H 4 ) 3 U(thf) and RNH 2 , and NH 3 was found to be a better ligand towards (MeC 5 H 4 ) 3 U than is PMe 3

  14. Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide. Factors governing diverse and well-defined cleavage and redox reactions

    Energy Technology Data Exchange (ETDEWEB)

    Cleaves, Peter A.; Gardner, Benedict M.; Liddle, Stephen T. [School of Chemistry, The University of Manchester (United Kingdom); Kefalidis, Christos E.; Maron, Laurent [LPCNO, CNRS and INSA, Universite Paul Sabatier, Toulouse (France); Tuna, Floriana; McInnes, Eric J.L. [School of Chemistry and Photon Science Institute, The University of Manchester (United Kingdom); Lewis, William [School of Chemistry, The University of Nottingham (United Kingdom)

    2017-02-24

    The reactivity of terminal uranium(V/VI) nitrides with CE{sub 2} (E=O, S) is presented. Well-defined C=E cleavage followed by zero-, one-, and two-electron redox events is observed. The uranium(V) nitride [U(Tren{sup TIPS})(N)][K(B15C5){sub 2}] (1, Tren{sup TIPS}=N(CH{sub 2}CH{sub 2}NSiiPr{sub 3}){sub 3}; B15C5=benzo-15-crown-5) reacts with CO{sub 2} to give [U(Tren{sup TIPS})(O)(NCO)][K(B15C5){sub 2}] (3), whereas the uranium(VI) nitride [U(Tren{sup TIPS})(N)] (2) reacts with CO{sub 2} to give isolable [U(Tren{sup TIPS})(O)(NCO)] (4); complex 4 rapidly decomposes to known [U(Tren{sup TIPS})(O)] (5) with concomitant formation of N{sub 2} and CO proposed, with the latter trapped as a vanadocene adduct. In contrast, 1 reacts with CS{sub 2} to give [U(Tren{sup TIPS})(κ{sup 2}-CS{sub 3})][K(B15C5){sub 2}] (6), 2, and [K(B15C5){sub 2}][NCS] (7), whereas 2 reacts with CS{sub 2} to give [U(Tren{sup TIPS})(NCS)] (8) and ''S'', with the latter trapped as Ph{sub 3}PS. Calculated reaction profiles reveal outer-sphere reactivity for uranium(V) but inner-sphere mechanisms for uranium(VI); despite the wide divergence of products the initial activation of CE{sub 2} follows mechanistically related pathways, providing insight into the factors of uranium oxidation state, chalcogen, and NCE groups that govern the subsequent divergent redox reactions that include common one-electron reactions and a less-common two-electron redox event. Caution, we suggest, is warranted when utilising CS{sub 2} as a reactivity surrogate for CO{sub 2}. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Mitigation of Hydrogen Gas Generation from the Reaction of Water with Uranium Metal in K Basins Sludge

    International Nuclear Information System (INIS)

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2010-01-01

    Means to decrease the rate of hydrogen gas generation from the chemical reaction of uranium metal with water were identified by surveying the technical literature. The underlying chemistry and potential side reactions were explored by conducting 61 principal experiments. Several methods achieved significant hydrogen gas generation rate mitigation. Gas-generating side reactions from interactions of organics or sludge constituents with mitigating agents were observed. Further testing is recommended to develop deeper knowledge of the underlying chemistry and to advance the technology aturation level. Uranium metal reacts with water in K Basin sludge to form uranium hydride (UH3), uranium dioxide or uraninite (UO2), and diatomic hydrogen (H2). Mechanistic studies show that hydrogen radicals (H·) and UH3 serve as intermediates in the reaction of uranium metal with water to produce H2 and UO2. Because H2 is flammable, its release into the gas phase above K Basin sludge during sludge storage, processing, immobilization, shipment, and disposal is a concern to the safety of those operations. Findings from the technical literature and from experimental investigations with simple chemical systems (including uranium metal in water), in the presence of individual sludge simulant components, with complete sludge simulants, and with actual K Basin sludge are presented in this report. Based on the literature review and intermediate lab test results, sodium nitrate, sodium nitrite, Nochar Acid Bond N960, disodium hydrogen phosphate, and hexavalent uranium [U(VI)] were tested for their effects in decreasing the rate of hydrogen generation from the reaction of uranium metal with water. Nitrate and nitrite each were effective, decreasing hydrogen generation rates in actual sludge by factors of about 100 to 1000 when used at 0.5 molar (M) concentrations. Higher attenuation factors were achieved in tests with aqueous solutions alone. Nochar N960, a water sorbent, decreased hydrogen

  16. Mitigation of Hydrogen Gas Generation from the Reaction of Water with Uranium Metal in K Basins Sludge

    Energy Technology Data Exchange (ETDEWEB)

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2010-01-29

    Means to decrease the rate of hydrogen gas generation from the chemical reaction of uranium metal with water were identified by surveying the technical literature. The underlying chemistry and potential side reactions were explored by conducting 61 principal experiments. Several methods achieved significant hydrogen gas generation rate mitigation. Gas-generating side reactions from interactions of organics or sludge constituents with mitigating agents were observed. Further testing is recommended to develop deeper knowledge of the underlying chemistry and to advance the technology aturation level. Uranium metal reacts with water in K Basin sludge to form uranium hydride (UH3), uranium dioxide or uraninite (UO2), and diatomic hydrogen (H2). Mechanistic studies show that hydrogen radicals (H·) and UH3 serve as intermediates in the reaction of uranium metal with water to produce H2 and UO2. Because H2 is flammable, its release into the gas phase above K Basin sludge during sludge storage, processing, immobilization, shipment, and disposal is a concern to the safety of those operations. Findings from the technical literature and from experimental investigations with simple chemical systems (including uranium metal in water), in the presence of individual sludge simulant components, with complete sludge simulants, and with actual K Basin sludge are presented in this report. Based on the literature review and intermediate lab test results, sodium nitrate, sodium nitrite, Nochar Acid Bond N960, disodium hydrogen phosphate, and hexavalent uranium [U(VI)] were tested for their effects in decreasing the rate of hydrogen generation from the reaction of uranium metal with water. Nitrate and nitrite each were effective, decreasing hydrogen generation rates in actual sludge by factors of about 100 to 1000 when used at 0.5 molar (M) concentrations. Higher attenuation factors were achieved in tests with aqueous solutions alone. Nochar N960, a water sorbent, decreased hydrogen

  17. Reaction rate constant for uranium in water and water vapor

    Energy Technology Data Exchange (ETDEWEB)

    TRIMBLE, D.J.

    1998-11-09

    The literature on uranium oxidation in water and oxygen free water vapor was reviewed. Arrhenius rate equations were developed from the review data. These data and equations will be used as a baseline from which to compare reaction rates measured for K Basin fuel.

  18. Uranium analysis in urine by inductively coupled plasma dynamic reaction cell mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ejnik, John W. [Northern Michigan University, Chemistry Department, Marquette, MI (United States); Todorov, Todor I.; Mullick, Florabel G.; Centeno, Jose A. [Armed Forces Institute of Pathology (AFIP), Division of Biophysical Toxicology, Washington, DC (United States); Squibb, Katherine; McDiarmid, Melissa A. [University of Maryland, School of Medicine, Baltimore, MD (United States)

    2005-05-01

    Urine uranium concentrations are the best biological indicator for identifying exposure to depleted uranium (DU). Internal exposure to DU causes an increased amount of urine uranium and a decreased ratio of {sup 235}U/{sup 238}U in urine samples, resulting in measurements that vary between 0.00725 and 0.002 (i.e., natural and depleted uranium's {sup 235}U/{sup 238}U ratios, respectively). A method based on inductively coupled plasma dynamic reaction cell mass spectrometry (ICP-DRC-MS) was utilized to identify DU in urine by measuring the quantity of total U and the {sup 235}U/{sup 238}U ratio. The quantitative analysis was achieved using {sup 233}U as an internal standard. The analysis was performed both with and without the reaction gas oxygen. The reaction gas converted ionized {sup 235}U{sup +} and {sup 238}U{sup +} into {sup 235}UO{sub 2}{sup +} (m/z=267) and {sup 238}UO{sub 2}{sup +} (m/z=270). This conversion was determined to be over 90% efficient. A polyatomic interference at m/z 234.8 was successfully removed from the {sup 235}U signal under either DRC operating conditions (with or without oxygen as a reaction gas). The method was validated with 15 urine samples of known uranium compositions. The method detection limit for quantification was determined to be 0.1 pg U mL{sup -1} urine and an average coefficient of variation (CV) of 1-2% within the sample measurements. The method detection limit for determining {sup 235}U/{sup 238}U ratio was 3.0 pg U mL{sup -1} urine. An additional 21 patient samples were analyzed with no information about medical history. The measured {sup 235}U/{sup 238}U ratio within the urine samples correctly identified the presence or absence of internal DU exposure in all 21 patients. (orig.)

  19. Estimated dose to man from uranium milling via the terrestrial food-chain pathway

    Energy Technology Data Exchange (ETDEWEB)

    Rayno, D.R.

    1982-01-01

    One of the major pathways of radiological exposure to man from uranium milling operations is through the terrestrial food chain. Studies by various investigators have shown the extent of uptake and distribution of U-238, U-234, Th-230, Ra-226, Pb-210, and Po-210 in plants and animals. These long-lived natural radioisotopes, all nuclides of the uranium decay series, are found in concentrated amounts in uranium mill tailings. Data from these investigations are used to estimate the dose to man from consumption of beef and milk contaminated by the tailings. This dose estimate from this technologically enhanced source is compared with that from average normal dietary intake of these radionuclides from natural sources.

  20. Estimated dose to man from uranium milling via the terrestrial food-chain pathway

    International Nuclear Information System (INIS)

    Rayno, D.R.

    1982-01-01

    One of the major pathways of radiological exposure to man from uranium milling operations is through the terrestrial food chain. Studies by various investigators have shown the extent of uptake and distribution of U-238, U-234, Th-230, Ra-226, Pb-210, and Po-210 in plants and animals. These long-lived natural radioisotopes, all nuclides of the uranium decay series, are found in concentrated amounts in uranium mill tailings. Data from these investigations are used to estimate the dose to man from consumption of beef and milk contaminated by the tailings. This dose estimate from this technologically enhanced source is compared with that from average normal dietary intake of these radionuclides from natural sources

  1. Reaction of Tris(cyclopentadienyl)uranium compounds with amines, azides, and related ligands

    Energy Technology Data Exchange (ETDEWEB)

    Rosen, R.K.

    1989-12-01

    The trivalent uranium compound, (MeC{sub 5}H{sub 4}){sub 3}U(thf), serves as a one- or two-electron reducing agent towards azides, RN{sub 3}. These reactions produce either the uranium(IV) azide, (MeC{sub 5}H{sub 4}){sub 3}UN{sub 3}, or uranium(V) imides, (MeC{sub 5}H{sub 4}){sub 3}UNR. The role of steric and electronic effects upon this reaction has been investigated using several series of azides. For Me{sub 3}XN{sub 3}, the imides are produced when X = C or Si, both products are formed when X = Ge, and the azide is produced when X = Sn. For Ph{sub 3}XN{sub 3}, the azide is produced when X = C or Sn. For Ph{sub 3-x}CH{sub 3}N{sub 3}, the imide is produced when x = 2 and both compounds are produced when x = 1. For substituted phenylazides, RC{sub 6}H{sub 4}N{sub 3}, only the imides are produced. The magnetic properties of uranium diimides, ((MeC{sub 5}H{sub 4}){sub 3}U){sub 2}({mu}-NRN), were investigated. Several uranium(III) amines, (MeC{sub 5}H{sub 4}){sub 3}U(NH{sub 2}R), were produced from (MeC{sub 5}H{sub 4}){sub 3}U(thf) and RNH{sub 2}, and NH{sub 3} was found to be a better ligand towards (MeC{sub 5}H{sub 4}){sub 3}U than is PMe{sub 3}.

  2. Reaction of nickel with uranium mononitride

    International Nuclear Information System (INIS)

    Anselin, F.; Calais, D.; Lorenzelli, N.; Passefort, J.C.

    1965-01-01

    UN-Ni system has been investigated in solid phase by diffusion couples UN-Ni or by mixed powders pressed and sintered. Studies have been carried out by micrography, X-rays and microanalysis with a CASTAING microprobe. UN-Ni compatibility is quite good up to 600 C; beyond this temperature diffusion zones corresponding to UNi 5 and U 2 N 3 appear in the couples either reaction : 3 U N + 5 Ni → U 2 N 3 + UNi 5 ; UN + 5 Ni → UNi 5 + 1/2 N 2 takes place from 700 C according to nitrogen pressure involved. For temperatures between 800 and 1000 C nickel solubility in uranium nitride is 1500 ± 500 wt ppm. (authors) [fr

  3. Influence of uranium hydride oxidation on uranium metal behaviour

    International Nuclear Information System (INIS)

    Patel, N.; Hambley, D.; Clarke, S.A.; Simpson, K.

    2013-01-01

    This work addresses concerns that the rapid, exothermic oxidation of active uranium hydride in air could stimulate an exothermic reaction (burning) involving any adjacent uranium metal, so as to increase the potential hazard arising from a hydride reaction. The effect of the thermal reaction of active uranium hydride, especially in contact with uranium metal, does not increase in proportion with hydride mass, particularly when considering large quantities of hydride. Whether uranium metal continues to burn in the long term is a function of the uranium metal and its surroundings. The source of the initial heat input to the uranium, if sufficient to cause ignition, is not important. Sustained burning of uranium requires the rate of heat generation to be sufficient to offset the total rate of heat loss so as to maintain an elevated temperature. For dense uranium, this is very difficult to achieve in naturally occurring circumstances. Areas of the uranium surface can lose heat but not generate heat. Heat can be lost by conduction, through contact with other materials, and by convection and radiation, e.g. from areas where the uranium surface is covered with a layer of oxidised material, such as burned-out hydride or from fuel cladding. These rates of heat loss are highly significant in relation to the rate of heat generation by sustained oxidation of uranium in air. Finite volume modelling has been used to examine the behaviour of a magnesium-clad uranium metal fuel element within a bottle surrounded by other un-bottled fuel elements. In the event that the bottle is breached, suddenly, in air, it can be concluded that the bulk uranium metal oxidation reaction will not reach a self-sustaining level and the mass of uranium oxidised will likely to be small in relation to mass of uranium hydride oxidised. (authors)

  4. Influence of uranium hydride oxidation on uranium metal behaviour

    Energy Technology Data Exchange (ETDEWEB)

    Patel, N.; Hambley, D. [National Nuclear Laboratory (United Kingdom); Clarke, S.A. [Sellafield Ltd (United Kingdom); Simpson, K.

    2013-07-01

    This work addresses concerns that the rapid, exothermic oxidation of active uranium hydride in air could stimulate an exothermic reaction (burning) involving any adjacent uranium metal, so as to increase the potential hazard arising from a hydride reaction. The effect of the thermal reaction of active uranium hydride, especially in contact with uranium metal, does not increase in proportion with hydride mass, particularly when considering large quantities of hydride. Whether uranium metal continues to burn in the long term is a function of the uranium metal and its surroundings. The source of the initial heat input to the uranium, if sufficient to cause ignition, is not important. Sustained burning of uranium requires the rate of heat generation to be sufficient to offset the total rate of heat loss so as to maintain an elevated temperature. For dense uranium, this is very difficult to achieve in naturally occurring circumstances. Areas of the uranium surface can lose heat but not generate heat. Heat can be lost by conduction, through contact with other materials, and by convection and radiation, e.g. from areas where the uranium surface is covered with a layer of oxidised material, such as burned-out hydride or from fuel cladding. These rates of heat loss are highly significant in relation to the rate of heat generation by sustained oxidation of uranium in air. Finite volume modelling has been used to examine the behaviour of a magnesium-clad uranium metal fuel element within a bottle surrounded by other un-bottled fuel elements. In the event that the bottle is breached, suddenly, in air, it can be concluded that the bulk uranium metal oxidation reaction will not reach a self-sustaining level and the mass of uranium oxidised will likely to be small in relation to mass of uranium hydride oxidised. (authors)

  5. Spectrographic determination of boron and silicon in uranium tetrafluoride: Study of the chemical reactions in the electrode cavity when ZnO is used as a uranium excitation suppressor

    International Nuclear Information System (INIS)

    Alduan, F. A.; Capdevila, C.; Roca, M.

    1973-01-01

    A method has been developed for determining traces of boron and silicon in uranium tetrafluoride. Use is made of zinc oxide to decrease the volatilization of uranium and achieve high sensitivities. The thermochemical reactions which occur in the anode cavity during the arcing process have been investigated. UO 2 and a uranium, zinc and fluorine compound, both less volatile than uranium tetrafluoride, are formed. (Author)

  6. Process for producing uranium oxide rich compositions from uranium hexafluoride

    International Nuclear Information System (INIS)

    DeHollander, W.R.; Fenimore, C.P.

    1978-01-01

    Conversion of gaseous uranium hexafluoride to a uranium dioxide rich composition in the presence of an active flame in a reactor defining a reaction zone is achieved by separately introducing a first gaseous reactant comprising a mixture of uranium hexafluoride and a reducing carrier gas, and a second gaseous reactant comprising an oxygen-containing gas. The reactants are separated by a shielding gas as they are introduced to the reaction zone. The shielding gas temporarily separates the gaseous reactants and temporarily prevents substantial mixing and reacting of the gaseous reactants. The flame occurring in the reaction zone is maintained away from contact with the inlet introducing the mixture to the reaction zone. After suitable treatment, the uranium dioxide rich composition is capable of being fabricated into bodies of desired configuration for loading into nuclear fuel rods. Alternatively, an oxygen-containing gas as a third gaseous reactant is introduced when the uranium hexafluoride conversion to the uranium dioxide rich composition is substantially complete. This results in oxidizing the uranium dioxide rich composition to a higher oxide of uranium with conversion of any residual reducing gas to its oxidized form

  7. Ab initio study on the reaction between uranium and O2

    International Nuclear Information System (INIS)

    Shuai Maobing; Zhao Pengji; Tian Anmin

    2000-08-01

    Optimized geometries, total energies and electronic structures of some gaseous atoms and molecules of uranium-oxygen system are calculated with harmonic vibration analysis using ab initio method. The potential energy surfaces (PESs) of the uranium oxidation process are also constructed. The calculated optimized geometries, infrared vibrational frequencies and the first ionized potential energies are in well accordance with available experimental data. Although U6p, U7s and U6d valence orbital electrons take part in the formation of U - O bond, the U5f electrons play an dominant role in this process and because the energies of U5f, U6d, U7s and Uds atomic orbitals are close to each other, these orbitals may hybrid and interact with O2p orbital, simultaneously, to form molecular orbitals of uranium oxides. The PESs show that different reaction modes result in different product geometries

  8. Reaction of uranium and plutonium carbides with austenitic steels; Reaction des carbures d'uranium et de plutonium avec des aciers austenitiques

    Energy Technology Data Exchange (ETDEWEB)

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

    1967-07-01

    The reaction of uranium and plutonium carbides with austenitic steels has been studied between 650 and 1050 deg. C using UC, steel and (UPu)C, steel diffusion couples. The steels are of the type CN 18.10 with or without addition of molybdenum. The carbides used are hyper-stoichiometric. Tests were also carried out with UCTi, UCMo, UPuCTi and UPuCMo. Up to 800 deg. C no marked diffusion of carbon into stainless steel is observed. Between 800 and 900 deg. C the carbon produced by the decomposition of the higher carbides diffuses into the steel. Above 900 deg. C, decomposition of the monocarbide occurs according to a reaction which can be written schematically as: (U,PuC) + (Fe,Ni,Cr) {yields} (U,Pu) Fe{sub 2} + Cr{sub 23}C{sub 6}. Above 950 deg. C the behaviour of UPuCMo and that of the titanium (CN 18.12) and nickel (NC 38. 18) steels is observed to be very satisfactory. (author) [French] La reaction des carbures d'uranium et de plutonium avec des aciers austenitiques a ete etudiee entre 650 deg. C et 1050 deg. C a partir de couples de diffusion UC, acier et (UPu)C, acier. Les aciers sont du type CN 18.10 avec ou sans addition de molybdene. Les carbures utilises sont hyper-stoechiometriques. En outre on a fait des essais avec UCTi, UCMo, UPuCTi, UPuCMo. Jusqu'a 800 deg. C on ne detecte pas de diffusion sensible du carbone dans l'acier inoxydable. Entre 800 et 900 deg. C il y a diffusion dans l'acier du carbone provenant de la decomposition des carbures superieurs. A partir de 900 deg. C il y a decomposition du monocarbure selon une reaction que l'on ecrit schematiquement: (U,PuC) + (Fe, Ni, Cr) {yields} (U,Pu)Fe{sub 2} + Cr{sub 23}C{sub 6}. Nous notons a 950 deg. C le bon comportement de UPuCMo ainsi que celui des aciers au titane (CN 18. 12) et au nickel (NC 38.18). (auteur)

  9. Characterization of the Environmentally Induced Chemical Transformations of Uranium Tetrafluoride

    Energy Technology Data Exchange (ETDEWEB)

    Wellons, M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-09-29

    A key challenge with nuclear safeguards environmental sampling is identification of the materials post release due to subsequent chemical reactions with ambient water and oxygen. Uranium Tetrafluoride (UF4) is of interest as an intermediate in both the upstream and downstream portions of uranium feedstock and metal production processes used in nuclear fuel production; however minimal published research exists relating to UF4 hydrolysis. FY16 efforts were dedicated to in-situ Raman spectroscopy and X-ray diffraction characterization of UF4 during exposure to various relative humidity conditions. This effort mapped several hydrolysis reaction pathways and identified both intermediate, and terminal progeny species.

  10. The shielded chemistry suite at BNL and its use in the study of the irradiated uranium-water reaction

    International Nuclear Information System (INIS)

    Bannister, G.H.; Tyfield, S.P.

    1977-11-01

    A versatile shielded facility for chemical studies is now in use at Berkeley Nuclear Laboratories. The suite was fully commissioned in 1976 and first utilised to study the aqueous corrosion of irradiated reactor grade uranium. The suite consists of three adjacent interconnected cells; a balance cell, a preparation cell and an experimental cell. The development, design and layout of the facilities are described, as are the details of the equipment installed to undertake a uranium corrosion study. The preparation cell is used for procedures that could results in high levels of contamination, such as cutting of uranium specimens. The uranium samples are corroded in sealed steel capsules installed in the experimental cell. The capsules are heated either isothermally or through a transient and the reaction monitored with a pressure transducer which records the rate of hydrogen evolution from the uranium-water reaction. The experimental results will be reported elsewhere. (author)

  11. Explorations into Chemical Reactions and Biochemical Pathways.

    Science.gov (United States)

    Gasteiger, Johann

    2016-12-01

    A brief overview of the work in the research group of the present author on extracting knowledge from chemical reaction data is presented. Methods have been developed to calculate physicochemical effects at the reaction site. It is shown that these physicochemical effects can quite favourably be used to derive equations for the calculation of data on gas phase reactions and on reactions in solution such as aqueous acidity of alcohols or carboxylic acids or the hydrolysis of amides. Furthermore, it is shown that these physicochemical effects are quite effective for assigning reactions into reaction classes that correspond to chemical knowledge. Biochemical reactions constitute a particularly interesting and challenging task for increasing our understanding of living species. The BioPath.Database is a rich source of information on biochemical reactions and has been used for a variety of applications of chemical, biological, or medicinal interests. Thus, it was shown that biochemical reactions can be assigned by the physicochemical effects into classes that correspond to the classification of enzymes by the EC numbers. Furthermore, 3D models of reaction intermediates can be used for searching for novel enzyme inhibitors. It was shown in a combined application of chemoinformatics and bioinformatics that essential pathways of diseases can be uncovered. Furthermore, a study showed that bacterial flavor-forming pathways can be discovered. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Reduction of uranium hexafluoride to uranium tetrafluoride

    International Nuclear Information System (INIS)

    Chang, I.S.; Do, J.B.; Choi, Y.D.; Park, M.H.; Yun, H.H.; Kim, E.H.; Kim, Y.W.

    1982-01-01

    The single step continuous reduction of uranium hexafluoride (UF 6 ) to uranium tetrafluoride (UF 4 ) has been investigated. Heat required to initiate and maintain the reaction in the reactor is supplied by the highly exothermic reaction of hydrogen with a small amount of elemental fluorine which is added to the uranium hexafluoride stream. When gases uranium hexafluoride and hydrogen react in a vertical monel pipe reactor, the green product, UF 4 has 2.5g/cc in bulk density and is partly contaminated by incomplete reduction products (UF 5 ,U 2 F 9 ) and the corrosion product, presumably, of monel pipe of the reactor itself, but its assay (93% of UF 4 ) is acceptable for the preparation of uranium metal with magnesium metal. Remaining problems are the handling of uranium hexafluoride, which is easily clogging the flowmeter and gas feeding lines because of extreme sensitivity toward moisture, and a development of gas nozzel for free flow of uranium hexafluoride gas. (Author)

  13. Sintering with a chemical reaction as applied to uranium monocarbide

    International Nuclear Information System (INIS)

    Accary, A.; Caillat, R.

    1960-01-01

    The present paper provides a survey of different investigations whose aim was the preparation and fabrication of uranium monocarbide for nuclear use. If a chemical reaction takes place in the sample during the sintering operation, it may be expected that the atom rearrangements involved in this reaction should favour the sintering process and thereby lower the temperature needed to yield a body of a given density. With this hypothesis in mind, the following methods have been studied: - Sintering of U-C mixtures; - Sintering of UO 2 -C mixtures; - Hot pressing of U-C mixtures; - Extrusion of U-C mixtures. To generalize our result, it could be said that a chemical reaction does not lead to high densification, if one depends on a simple contact between discrete particles. On the contrary, a chemical reaction can help sintering if, as our hot pressing experiments shows, the densification can be achieved prior to the reaction. (author) [fr

  14. Some reactions of uranium chloride pentafluoride

    International Nuclear Information System (INIS)

    Downs, A.J.; Gardner, C.J.

    1986-01-01

    The molecule UF 5 Cl has been isolated, together with an excess of UF 6 , in a solid matrix of Ar, N 2 , or CO and characterised by its i.r. spectrum. Under these conditions it dissociates under the action of radiation having wavelengths close to 500 nm to give UF 5 ; OCCl and OCClF are also formed on photolysis in a solid CO matrix, whereas a species believed to be U 2 F 11 is formed on photolysis in a solid N 2 matrix. CCl 3 F solutions of fluoride-rich mixtures of uranium(VI) chloride fluorides have been shown to function as chlorinating, fluorinating, or chlorofluorinating reagents in their reactions with various unsaturated molecules at temperatures low enough to preclude thermal decomposition of the mixed halides ( 0 C). (author)

  15. Estimated dose to man from uranium milling via the beef/milk food-chain pathway

    Energy Technology Data Exchange (ETDEWEB)

    Rayno, D R

    1983-12-01

    One of the major pathways of radiological exposure to man from uranium milling operations is through the beef/milk food chain. Studies by various investigators have shown the extent of uptake and distribution of 238U, 234U, 230Th, 226Ra, 210Pb, and 210Po in plants and cattle. These long-lived natural radioisotopes, all nuclides of the uranium decay series, are found in concentrated amounts in uranium mill tailings. In this paper, data from these investigations are used to estimate the dose to man from consumption of beef and milk from cattle that have fed on forage contaminated with the tailings. The estimated doses from this technologically enhanced source are compared with those resulting from average dietary intake of these radionuclides from natural sources.

  16. Using proteomic data to assess a genome-scale "in silico" model of metal reducing bacteria in the simulation of field-scale uranium bioremediation

    Science.gov (United States)

    Yabusaki, S.; Fang, Y.; Wilkins, M. J.; Long, P.; Rifle IFRC Science Team

    2011-12-01

    A series of field experiments in a shallow alluvial aquifer at a former uranium mill tailings site have demonstrated that indigenous bacteria can be stimulated with acetate to catalyze the conversion of hexavalent uranium in a groundwater plume to immobile solid-associated uranium in the +4 oxidation state. While this bioreduction of uranium has been shown to lower groundwater concentrations below actionable standards, a viable remediation methodology will need a mechanistic, predictive and quantitative understanding of the microbially-mediated reactions that catalyze the reduction of uranium in the context of site-specific processes, properties, and conditions. At the Rifle IFRC site, we are investigating the impacts on uranium behavior of pulsed acetate amendment, acetate-oxidizing iron and sulfate reducing bacteria, seasonal water table variation, spatially-variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. The simulation of three-dimensional, variably saturated flow and biogeochemical reactive transport during a uranium bioremediation field experiment includes a genome-scale in silico model of Geobacter sp. to represent the Fe(III) terminal electron accepting process (TEAP). The Geobacter in silico model of cell-scale physiological metabolic pathways is comprised of hundreds of intra-cellular and environmental exchange reactions. One advantage of this approach is that the TEAP reaction stoichiometry and rate are now functions of the metabolic status of the microorganism. The linkage of in silico model reactions to specific Geobacter proteins has enabled the use of groundwater proteomic analyses to assess the accuracy of the model under evolving hydrologic and biogeochemical conditions. In this case, the largest predicted fluxes through in silico model reactions generally correspond to high abundances of proteins linked to those reactions (e.g. the condensation reaction catalyzed by the protein

  17. Unexpected Reaction Pathway for butyrylcholinesterase-catalyzed inactivation of “hunger hormone” ghrelin

    Science.gov (United States)

    Yao, Jianzhuang; Yuan, Yaxia; Zheng, Fang; Zhan, Chang-Guo

    2016-02-01

    Extensive computational modeling and simulations have been carried out, in the present study, to uncover the fundamental reaction pathway for butyrylcholinesterase (BChE)-catalyzed hydrolysis of ghrelin, demonstrating that the acylation process of BChE-catalyzed hydrolysis of ghrelin follows an unprecedented single-step reaction pathway and the single-step acylation process is rate-determining. The free energy barrier (18.8 kcal/mol) calculated for the rate-determining step is reasonably close to the experimentally-derived free energy barrier (~19.4 kcal/mol), suggesting that the obtained mechanistic insights are reasonable. The single-step reaction pathway for the acylation is remarkably different from the well-known two-step acylation reaction pathway for numerous ester hydrolysis reactions catalyzed by a serine esterase. This is the first time demonstrating that a single-step reaction pathway is possible for an ester hydrolysis reaction catalyzed by a serine esterase and, therefore, one no longer can simply assume that the acylation process must follow the well-known two-step reaction pathway.

  18. Current status of uranium enrichment by way of chemical exchange reactions

    International Nuclear Information System (INIS)

    El Basyouny, A.; Bechthold, H.C.; Knoechel, A.; Vollmer, H.J.

    1985-04-01

    For this report, conference proceedings, patents and other types of literature have been collected to present an account of the current status of uranium enrichment by way of chemical exchange reactions. The report further presents a new concept along with the relevant process strategy developed by the authors. The principal process of the new concept is a chemical exchange process with crown ethers, complexed or free, playing an important part in the reactions. The authors also describe their experiments carried out for establishing suitable chemical systems. (orig./PW) [de

  19. Thermodynamic analysis and experimental study on the chlorination of uranium oxide by gas-solid reaction

    International Nuclear Information System (INIS)

    Shin, Y.J.; Kim, I.S.; Shin, H.S.; Ro, S.G.; Park, H.S.

    1998-01-01

    In order to determine the operating condition of an uranium chlorination process with U 3 O 8 -C-Cl 2 system, the experimental conditions have been evaluated preliminarily by the thermochemical analysis and experimentally confirmed in this study. The dry-type chlorination of U 3 O 8 occurs as irreversible and exothermic reaction and produces many kinds of chloride compounds such as UCl 3 , UCl 4 , UCl 5 , and UCl 6 in the air and humidity controlled argon environment. Taking account of Gibbs free energy and vapor pressure for various chloride compounds, the proper temperature range of chlorination appears to be 863 to 953 K in aspects of increasing reaction rate and the yield of nonvolatile product. In the course of the experimental confirmation the powder of U 3 O 8 is perfectly converted into uranium chlorides within 4 hours above 863 K, and then the maximum fraction of uranium chloride remaining in the reactor is about 30% of total conversion mass. (author)

  20. Reactions of uranium (III) and (IV) compounds with ketones, nitriles and acid chlorides. Towards a use of uranium complexes in organic synthesis

    International Nuclear Information System (INIS)

    Adam, Raymond

    1993-01-01

    In this research thesis, the author shows that various organic molecules can be interestingly transformed into uranium complexes with degrees of oxidation of +3 or +4. In a first part, the author describes reactions of carbonyl compounds with the UCl 4 -Na(Hg) reducing system. Then, he addresses reductions of ketones, nitriles and acid chlorides by a uranium (III) complex: Cp 3 U(THF). The third part reports a detailed study of the reduction of ketones by U(BH 4 ) 4 [fr

  1. Studies of the reactions of uranium pentabromide and hexabromouranate(V) in non-aqueous solvents

    International Nuclear Information System (INIS)

    Dehos, R.F.

    1984-01-01

    With the help of IR and electron spectra, the behaviour of uranium pentabromide and hexabromo uranate in non-aqueous nitromethane, nitroethane, bromine, dichlormethane, dibromomethane and acetonitrile was studied. By comparison of the spectra of the solutions in nitromethane with the solutions using other solvents on one side, and on the other side with the solids spectra of the end products, the redox reactions of the uranium V in nitromethane solutions could be more than clarified. Studies were also carried out on the time-dependency of the uranium IV and uranium V contents of the solutions at room temperature and at -20 0 C. The existence of the HUBr 6 which probably appears as an intermediate product was tested in another experiment. First evidence for the existence of UBr 6 as a disproportionation product of UBr 5 were achieved by tests in solutions of acetonitrile at -47 0 C. (RB) [de

  2. Kynurenine pathway metabolites and enzymes involved in redox reactions.

    Science.gov (United States)

    González Esquivel, D; Ramírez-Ortega, D; Pineda, B; Castro, N; Ríos, C; Pérez de la Cruz, V

    2017-01-01

    Oxido-reduction reactions are a fundamental part of the life due to support many vital biological processes as cellular respiration and glucose oxidation. In the redox reactions, one substance transfers one or more electrons to another substance. An important electron carrier is the coenzyme NAD + , which is involved in many metabolic pathways. De novo biosynthesis of NAD + is through the kynurenine pathway, the major route of tryptophan catabolism, which is sensitive to redox environment and produces metabolites with redox capacity, able to alter biological functions that are controlled by redox-responsive signaling pathways. Kynurenine pathway metabolites have been implicated in the physiology process and in the physiopathology of many diseases; processes that also share others factors as dysregulation of calcium homeostasis, mitochondrial dysfunction, oxidative stress, inflammation and cell death, which impact the redox environment. This review examines in detail the available evidence in which kynurenine pathway metabolites participate in redox reactions and their effect on cellular redox homeostasis, since the knowledge of the main factors and mechanisms that lead to cell death in many neurodegenative disorders and other pathologies, such as mitochondrial dysfunction, oxidative stress and kynurenines imbalance, will allow to develop therapies using them as targets. This article is part of the Special Issue entitled 'The Kynurenine Pathway in Health and Disease'. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Study of reactions for the obtention of uranium tetrafluoride and hexafluoride

    International Nuclear Information System (INIS)

    Guzella, M.F.R.

    1984-01-01

    Based on an exhaustive bibliographical review, the main production processes of uranium hexafluoride in pilot plants and industrial facilities are described. The known reactions, confirmed in laboratory experiments, that lead to UF 6 or other intermediate fluorides, are presented and discussed. In order to determine a new thermodinamically feasible reaction involving the sulfur hexafluoride as fluorinating agent, a mock-up facility was designed and constructed as part of the R and D work planned at CDTN (NUCLEBRAS Center for Nuclear Technology Development, MG - Brazil). For the UF 4 synthesis employing U 3 O 8 and SF 6 , several experimental parameters were studied. The reaction time, gas flow, temperature and stoichiometric relations among reagents are described in detail. Suggestions for further investigations regarding this new reagent are made. (Author) [pt

  4. A review of uranium corrosion by hydrogen and the formation of uranium hydride

    OpenAIRE

    Banos, A.; Harker, N. J.; Scott, T. B.

    2018-01-01

    Uranium hydride (UH3) is the direct product of the reaction between uranium metal and gaseous hydrogen. In the context of uranium storage, this corrosion reaction is considered deleterious, not just because the structure of the metal may become significantly degraded but also because the resulting hydride is pyrophoric and therefore potentially flammable in air if present in significant quantity. The current review draws from the literature surrounding the uranium-hydrogen system accrued over...

  5. Influence of uranyl speciation and iron oxides on uranium biogeochemical redox reactions

    Energy Technology Data Exchange (ETDEWEB)

    Stewart, B.D.; Amos, R.T.; Nico, P.S.; Fendorf, S.

    2010-03-15

    Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates its partitioning between the aqueous- and solid-phases, and thus controls its dissolved concentration and, coupled with groundwater flow, its migration within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO{sub 2}{sup 2+} and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO{sub 2}. However, various factors within soils and sediments may limit biological reduction of U(VI), inclusive of alterations in U(VI) speciation and competitive electron acceptors. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction with specific emphasis on speciation changes induced by dissolved Ca, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite and hematite) varying in free energies of formation on U reduction. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% with no Ca or ferrihydrite present but only 24% (with ferrihydrite) and 14% (no ferrihydrite) were removed for systems with 0.8 mM Ca. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Dissimilatory reduction of Fe(III) and U(VI) can proceed through different enzyme pathways, even within a single organism, thus providing a potential second means by which Fe(III) bearing minerals may impact U(VI) reduction. We quantify rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concentration (0 to 0.8 mM), and using a mathematical construct implemented with the reactive transport code MIN3P, we reveal the predominant influence of uranyl speciation, specifically the formation of uranyl

  6. Reactions of aluminum with uranium fluorides and oxyfluorides

    Energy Technology Data Exchange (ETDEWEB)

    Leitnaker, J.M.; Nichols, R.W.; Lankford, B.S. [Martin Marietta Energy Systems, Inc., Oak Ridge, TN (United States)

    1991-12-31

    Every 30 to 40 million operating hours a destructive reaction is observed in one of the {approximately}4000 large compressors that move UF{sub 6} through the gaseous diffusion plants. Despite its infrequency, such a reaction can be costly in terms of equipment and time. Laboratory experiments reveal that the presence of moderate pressures of UF{sub 6} actually cools heated aluminum, although thermodynamic calculations indicate the potential for a 3000-4000{degrees}C temperature rise. Within a narrow and rather low (<100 torr; 1 torr = 133.322 Pa) pressure range, however, the aluminum is seen to react with sufficient heat release to soften an alumina boat. Three things must occur in order for aluminum to react vigorously with either UF{sub 6} or UO{sub 2}F{sub 2}. 1. An initiating source of heat must be provided. In the compressors, this source can be friction, permitted by disruption of the balance of the large rotating part or by creep of the aluminum during a high-temperature treatment. In the absence of this heat source, compressors have operated for 40 years in UF{sub 6} without significant reaction. 2. The film protecting the aluminum must be breached. Melting (of UF{sub 5} at 620 K or aluminum at 930 K) can cause such a breach in laboratory experiments. In contrast, holding Al samples in UF{sub 6} at 870 K for several hours produces only moderate reaction. Rubbing in the cascade can undoubtedly breach the protective film. 3. Reaction products must not build up and smother the reaction. While uranium products tend to dissolve or dissipate in molten aluminum, AIF{sub 3} shows a remarkable tendency to surround and hence protect even molten aluminum. Hence the initial temperature rise must be rapid and sufficient to move reactants into a temperature region in which products are removed from the reaction site.

  7. Minimum Energy Pathways for Chemical Reactions

    Science.gov (United States)

    Walch, S. P.; Langhoff, S. R. (Technical Monitor)

    1995-01-01

    Computed potential energy surfaces are often required for computation of such parameters as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method to obtain accurate energetics, gives useful results for a number of chemically important systems. The talk will focus on a number of applications to reactions leading to NOx and soot formation in hydrocarbon combustion.

  8. A multi-pathway model for photosynthetic reaction center

    International Nuclear Information System (INIS)

    Qin, M.; Shen, H. Z.; Yi, X. X.

    2016-01-01

    Charge separation occurs in a pair of tightly coupled chlorophylls at the heart of photosynthetic reaction centers of both plants and bacteria. Recently it has been shown that quantum coherence can, in principle, enhance the efficiency of a solar cell, working like a quantum heat engine. Here, we propose a biological quantum heat engine (BQHE) motivated by Photosystem II reaction center (PSII RC) to describe the charge separation. Our model mainly considers two charge-separation pathways which is more than that typically considered in the published literature. We explore how these cross-couplings increase the current and power of the charge separation and discuss the effects of multiple pathways in terms of current and power. The robustness of the BQHE against the charge recombination in natural PSII RC and dephasing induced by environments is also explored, and extension from two pathways to multiple pathways is made. These results suggest that noise-induced quantum coherence helps to suppress the influence of acceptor-to-donor charge recombination, and besides, nature-mimicking architectures with engineered multiple pathways for charge separations might be better for artificial solar energy devices considering the influence of environments.

  9. Experimental study and numerical modelling of geochemical reactions occurring during uranium in situ recovery (ISR) mining

    International Nuclear Information System (INIS)

    Ben Simon, R.

    2011-09-01

    The in situ Recovery (ISR) method consists of ore mining by in situ chemical leaching with acid or alkaline solutions. ISR takes place underground and is therefore limited to the analysis of the pumped solutions, hence ISR mine management is still empirical. Numerical modelling has been considered to achieve more efficient management of this process. Three different phenomena have to be taken into account for numerical simulations of uranium ISR mining: (1) geochemical reactions; (2) the kinetics of these reactions, and (3) hydrodynamic transport with respect to the reaction kinetics. Leaching tests have been conducted on ore samples from an uranium mine in Tortkuduk (Kazakhstan) where ISR is conducted by acid leaching. Two types of leaching experiments were performed: (1) tests in batch reactors; and (2) extraction in flow through columns. The assumptions deduced from the leaching tests were tested and validated by modelling the laboratory experiments with the numerical codes CHESS and HYTEC, both developed at the Geosciences research center of Mines ParisTech. A well-constrained 1D hydrogeochemical transport model of the ISR process at laboratory-scale was proposed. It enables to translate the chemical release sequence that is observed during experiments into a geochemical reaction sequence. It was possible to highlight the controlling factors of uranium dissolution, and the precipitation of secondary mineral phase in the deposit, as well as the determination of the relative importance of these factors. (author)

  10. Monte carlo simulations of Yttrium reaction rates in Quinta uranium target

    Science.gov (United States)

    Suchopár, M.; Wagner, V.; Svoboda, O.; Vrzalová, J.; Chudoba, P.; Tichý, P.; Kugler, A.; Adam, J.; Závorka, L.; Baldin, A.; Furman, W.; Kadykov, M.; Khushvaktov, J.; Solnyshkin, A.; Tsoupko-Sitnikov, V.; Tyutyunnikov, S.; Bielewicz, M.; Kilim, S.; Strugalska-Gola, E.; Szuta, M.

    2017-03-01

    The international collaboration Energy and Transmutation of Radioactive Waste (E&T RAW) performed intensive studies of several simple accelerator-driven system (ADS) setups consisting of lead, uranium and graphite which were irradiated by relativistic proton and deuteron beams in the past years at the Joint Institute for Nuclear Research (JINR) in Dubna, Russia. The most recent setup called Quinta, consisting of natural uranium target-blanket and lead shielding, was irradiated by deuteron beams in the energy range between 1 and 8 GeV in three accelerator runs at JINR Nuclotron in 2011 and 2012 with yttrium samples among others inserted inside the setup to measure the neutron flux in various places. Suitable activation detectors serve as one of possible tools for monitoring of proton and deuteron beams and for measurements of neutron field distribution in ADS studies. Yttrium is one of such suitable materials for monitoring of high energy neutrons. Various threshold reactions can be observed in yttrium samples. The yields of isotopes produced in the samples were determined using the activation method. Monte Carlo simulations of the reaction rates leading to production of different isotopes were performed in the MCNPX transport code and compared with the experimental results obtained from the yttrium samples.

  11. Monte carlo simulations of Yttrium reaction rates in Quinta uranium target

    Directory of Open Access Journals (Sweden)

    Suchopár M.

    2017-01-01

    Full Text Available The international collaboration Energy and Transmutation of Radioactive Waste (E&T RAW performed intensive studies of several simple accelerator-driven system (ADS setups consisting of lead, uranium and graphite which were irradiated by relativistic proton and deuteron beams in the past years at the Joint Institute for Nuclear Research (JINR in Dubna, Russia. The most recent setup called Quinta, consisting of natural uranium target-blanket and lead shielding, was irradiated by deuteron beams in the energy range between 1 and 8 GeV in three accelerator runs at JINR Nuclotron in 2011 and 2012 with yttrium samples among others inserted inside the setup to measure the neutron flux in various places. Suitable activation detectors serve as one of possible tools for monitoring of proton and deuteron beams and for measurements of neutron field distribution in ADS studies. Yttrium is one of such suitable materials for monitoring of high energy neutrons. Various threshold reactions can be observed in yttrium samples. The yields of isotopes produced in the samples were determined using the activation method. Monte Carlo simulations of the reaction rates leading to production of different isotopes were performed in the MCNPX transport code and compared with the experimental results obtained from the yttrium samples.

  12. The Oklo natural nuclear reactors: neutron parameters, age and duration of the reactions, uranium and fission products migrations

    International Nuclear Information System (INIS)

    Ruffenach, J.-C.

    1979-09-01

    Mass spectrometry and isotopic dilution technique are used in order to carry out, on various samples from the fossil nuclear reactors at Oklo, Gabon, isotopic and chemical analyses of some particular elements involved in the nuclear reactions: uranium, lead, bismuth, thorium, rare gases (krypton, xenon), rare earths (neodymium, samarium, europium, gadolinium, dysprosium), ruthenium and palladium. Interpretations of these analyses lead to the determination of many neutron parameters such as the neutron fluence received by the samples, the spectrum index, the conversion coefficient, and also the percentages of fissions due to uranium-238 and plutonium-239 and the total number of fissions relative to uranium. All these results make it possible to determine the age of the nuclear reactions by measuring the amounts of fission rare earths formed, i.e. 1.97 billion years. This study brings some informations to the general problem of radioactive wastes storage in deep geological formations, the storage of uranium, plutonium and many fission products having been carried out naturally, and for about two billion years [fr

  13. Identifying Reaction Pathways and their Environments

    DEFF Research Database (Denmark)

    Maronsson, Jon Bergmann

    Finding the mechanisms and estimating the rate of chemical reactions is an essential part of modern research of atomic scale systems. In this thesis, the application of well established methods for reaction rates and paths to important systems for hydrogen storage is considered before developing...... extensions to further identify the reaction environment for a more accurate rate. Complex borohydrides are materials of high hydrogen storage capacity and high thermodynamic stability (too high for hydrogen storage). In an effort to gain insight into the structural transitions of two such materials, Ca(BH4......-interstitial defects. In good agreement with the experiments, C3-type rotations activate at lower temperature than C2-type rotations. In order to investigate the environment of reaction pathways, a method for finding the ridge between first order saddle points on a multidimensional surface was developed...

  14. 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)

  15. Production of uranium dioxide

    International Nuclear Information System (INIS)

    Hart, J.E.; Shuck, D.L.; Lyon, W.L.

    1977-01-01

    A continuous, four stage fluidized bed process for converting uranium hexafluoride (UF 6 ) to ceramic-grade uranium dioxide (UO 2 ) powder suitable for use in the manufacture of fuel pellets for nuclear reactors is disclosed. The process comprises the steps of first reacting UF 6 with steam in a first fluidized bed, preferably at about 550 0 C, to form solid intermediate reaction products UO 2 F 2 , U 3 O 8 and an off-gas including hydrogen fluoride (HF). The solid intermediate reaction products are conveyed to a second fluidized bed reactor at which the mol fraction of HF is controlled at low levels in order to prevent the formation of uranium tetrafluoride (UF 4 ). The first intermediate reaction products are reacted in the second fluidized bed with steam and hydrogen at a temperature of about 630 0 C. The second intermediate reaction product including uranium dioxide (UO 2 ) is conveyed to a third fluidized bed reactor and reacted with additional steam and hydrogen at a temperature of about 650 0 C producing a reaction product consisting essentially of uranium dioxide having an oxygen-uranium ratio of about 2 and a low residual fluoride content. This product is then conveyed to a fourth fluidized bed wherein a mixture of air and preheated nitrogen is introduced in order to further reduce the fluoride content of the UO 2 and increase the oxygen-uranium ratio to about 2.25

  16. Serpentinization reaction pathways: implications for modeling approach

    Energy Technology Data Exchange (ETDEWEB)

    Janecky, D.R.

    1986-01-01

    Experimental seawater-peridotite reaction pathways to form serpentinites at 300/sup 0/C, 500 bars, can be accurately modeled using the EQ3/6 codes in conjunction with thermodynamic and kinetic data from the literature and unpublished compilations. These models provide both confirmation of experimental interpretations and more detailed insight into hydrothermal reaction processes within the oceanic crust. The accuracy of these models depends on careful evaluation of the aqueous speciation model, use of mineral compositions that closely reproduce compositions in the experiments, and definition of realistic reactive components in terms of composition, thermodynamic data, and reaction rates.

  17. Exposure pathways and biological receptors: baseline data for the canyon uranium mine, Coconino County, Arizona

    Science.gov (United States)

    Hinck, Jo E.; Linder, Greg L.; Darrah, Abigail J.; Drost, Charles A.; Duniway, Michael C.; Johnson, Matthew J.; Méndez-Harclerode, Francisca M.; Nowak, Erika M.; Valdez, Ernest W.; van Riper, Charles; Wolff, S.W.

    2014-01-01

    Recent restrictions on uranium mining within the Grand Canyon watershed have drawn attention to scientific data gaps in evaluating the possible effects of ore extraction to human populations as well as wildlife communities in the area. Tissue contaminant concentrations, one of the most basic data requirements to determine exposure, are not available for biota from any historical or active uranium mines in the region. The Canyon Uranium Mine is under development, providing a unique opportunity to characterize concentrations of uranium and other trace elements, as well as radiation levels in biota, found in the vicinity of the mine before ore extraction begins. Our study objectives were to identify contaminants of potential concern and critical contaminant exposure pathways for ecological receptors; conduct biological surveys to understand the local food web and refine the list of target species (ecological receptors) for contaminant analysis; and collect target species for contaminant analysis prior to the initiation of active mining. Contaminants of potential concern were identified as arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, thallium, uranium, and zinc for chemical toxicity and uranium and associated radionuclides for radiation. The conceptual exposure model identified ingestion, inhalation, absorption, and dietary transfer (bioaccumulation or bioconcentration) as critical contaminant exposure pathways. The biological survey of plants, invertebrates, amphibians, reptiles, birds, and small mammals is the first to document and provide ecological information on .200 species in and around the mine site; this study also provides critical baseline information about the local food web. Most of the species documented at the mine are common to ponderosa pine Pinus ponderosa and pinyon–juniper Pinus–Juniperus spp. forests in northern Arizona and are not considered to have special conservation status by state or federal agencies; exceptions

  18. Reaction of uranium and plutonium carbides with austenitic steels

    International Nuclear Information System (INIS)

    Mouchnino, M.

    1967-01-01

    The reaction of uranium and plutonium carbides with austenitic steels has been studied between 650 and 1050 deg. C using UC, steel and (UPu)C, steel diffusion couples. The steels are of the type CN 18.10 with or without addition of molybdenum. The carbides used are hyper-stoichiometric. Tests were also carried out with UCTi, UCMo, UPuCTi and UPuCMo. Up to 800 deg. C no marked diffusion of carbon into stainless steel is observed. Between 800 and 900 deg. C the carbon produced by the decomposition of the higher carbides diffuses into the steel. Above 900 deg. C, decomposition of the monocarbide occurs according to a reaction which can be written schematically as: (U,PuC) + (Fe,Ni,Cr) → (U,Pu) Fe 2 + Cr 23 C 6 . Above 950 deg. C the behaviour of UPuCMo and that of the titanium (CN 18.12) and nickel (NC 38. 18) steels is observed to be very satisfactory. (author) [fr

  19. Reaction of Antimony-Uranium Composite Oxide in the Chlorination Treatment of Waste Catalyst - 13521

    Energy Technology Data Exchange (ETDEWEB)

    Sawada, Kayo [EcoTopia Science Institute (Japan); Hirabayashi, Daisuke; Enokida, Youichi [Department of Materials, Physics and Energy Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Japan)

    2013-07-01

    The effect of oxygen gas concentration on the chlorination treatment of antimony-uranium composite oxide catalyst waste was investigated by adding different concentrations of oxygen at 0-6 vol% to its chlorination agent of 0.6 or 6 vol% hydrogen chloride gas at 1173 K. The addition of oxygen tended to prevent the chlorination of antimony in the oxide. When 6 vol% hydrogen chloride gas was used, the addition of oxygen up to 0.1 vol% could convert the uranium contained in the catalyst to U{sub 3}O{sub 8} without any significant decrease in the reaction rate compared to that of the treatment without oxygen. (authors)

  20. Reaction of Antimony-Uranium Composite Oxide in the Chlorination Treatment of Waste Catalyst - 13521

    International Nuclear Information System (INIS)

    Sawada, Kayo; Hirabayashi, Daisuke; Enokida, Youichi

    2013-01-01

    The effect of oxygen gas concentration on the chlorination treatment of antimony-uranium composite oxide catalyst waste was investigated by adding different concentrations of oxygen at 0-6 vol% to its chlorination agent of 0.6 or 6 vol% hydrogen chloride gas at 1173 K. The addition of oxygen tended to prevent the chlorination of antimony in the oxide. When 6 vol% hydrogen chloride gas was used, the addition of oxygen up to 0.1 vol% could convert the uranium contained in the catalyst to U 3 O 8 without any significant decrease in the reaction rate compared to that of the treatment without oxygen. (authors)

  1. Sintering uranium oxide in the reaction product of hydrogen-carbon dioxide mixtures

    International Nuclear Information System (INIS)

    De Hollander, W.R.; Nivas, Y.

    1975-01-01

    Compacted pellets of uranium oxide alone or containing one or more additives such as plutonium dioxide, gadolinium oxide, titanium dioxide, silica, and alumina are heated to 900 to 1599 0 C in the presence of a mixture of hydrogen and carbon dioxide, either alone or with an inert carrier gas and held at the desired temperature in this atmosphere to sinter the pellets. The sintered pellets are then cooled in an atmosphere having an oxygen partial pressure of 10 -4 to 10 -18 atm of oxygen such as dry hydrogen, wet hydrogen, dry carbon monoxide, wet carbon monoxide, inert gases such as nitrogen, argon, helium, and neon and mixtures of ayny of the foregoing including a mixture of hydrogen and carbon dioxide. The ratio of hydrogen to carbon dioxide in the gas mixture fed to the furnace is controlled to give a ratio of oxygen to uranium atoms in the sintered particles within the range of 1.98:1 to about 2.10:1. The water vapor present in the reaction products in the furnace atmosphere acts as a hydrolysis agent to aid removal of fluoride should such impurity be present in the uranium oxide. (U.S.)

  2. Oklo natural reactor. Study of uranium and rare earths migration on a core drilled through a reaction zone. Application to determination of the date of the nuclear reaction by measurement of fission products

    International Nuclear Information System (INIS)

    Ruffenach, J.C.

    1977-01-01

    Isotopic and chemical analysis of uranium and five rare earths: neodymium, samarium, europium, gadolinium and dysprosium were effected on fourteen samples taken in the same core drilled through a reaction zone of the Oklo uranium deposit. This study points out the general stability of uranium and fission rare earths; spatial distributions of these elements are quite analogous. Migrations have affected about 5% only of fission neodymium in the core of the reaction zone; corresponding values for samarium and gadolinium are slightly higher. These migration phenomena have carried rare earths to no more than 80 cm out of the core. By study of the europium it is shown that nuclear reactions have stayed in the ground since the time of reactions. On the other hand it is shown by analysis of the dysprosium that rare earths have not undergone an important movement. This study allow also the datation of nuclear reactions from the measurement of the quantity of fission neodymium produced. A value of 1.98x10 9 years is obtained slightly higher than the value obtained by geochronology [fr

  3. Production of uranium peroxide

    International Nuclear Information System (INIS)

    Caropreso, F.E.; Kreuz, D.F.

    1977-01-01

    A process is claimed of recovering uranium values as uranium peroxide from an aqueous uranyl solution containing dissolved vanadium and sodium impurities by treating the uranyl solution with hydrogen peroxide in an amount sufficient to have an excess of at least 0.5 parts H 2 O 2 per part of vanadium (V 2 O 5 ) above the stoichiometric amount required to form the uranium peroxide, the hydrogen peroxide treatment is carried out in three sequential phases consisting of I, a precipitation phase in which the hydrogen peroxide is added to the uranyl solution to precipitate the uranium peroxide and the pH of the reaction medium maintained in the range of 2.5 to 5.5 for a period of from about 1 to 60 minutes after the hydrogen peroxide addition; II, a digestion phase in which the pH of the reaction medium is maintained in the range of 3.0 to 7.0 for a period of about 5 to 180 minutes and III, a final phase in which the pH of the reaction medium is maintained in the range of 4.0 to 7.0 for a period of about 1 to 60 minutes during which time the uranium peroxide is separated from the reaction solution containing the dissolved vanadium and sodium impurities. The excess hydrogen peroxide is maintained during the entire treatment up until the uranium peroxide is separated from the reaction medium

  4. Reaction of hydrogen peroxide with uranium zirconium oxide solid solution - Zirconium hinders oxidative uranium dissolution

    Science.gov (United States)

    Kumagai, Yuta; Takano, Masahide; Watanabe, Masayuki

    2017-12-01

    We studied oxidative dissolution of uranium and zirconium oxide [(U,Zr)O2] in aqueous H2O2 solution to estimate (U,Zr)O2 stability to interfacial reactions with H2O2. Studies on the interfacial reactions are essential for anticipating how a (U,Zr)O2-based molten fuel may chemically degrade after a severe accident. The fuel's high radioactivity induces water radiolysis and continuous H2O2 generation. Subsequent reaction of the fuel with H2O2 may oxidize the fuel surface and facilitate U dissolution. We conducted our experiments with (U,Zr)O2 powder (comprising Zr:U mole ratios of 25:75, 40:60, and 50:50) and quantitated the H2O2 reaction via dissolved U and H2O2 concentrations. Although (U,Zr)O2 reacted more quickly than UO2, the dissolution yield relative to H2O2 consumption was far less for (U,Zr)O2 compared to that of UO2. The reaction kinetics indicates that most of the H2O2 catalytically decomposed to O2 at the surface of (U,Zr)O2. We confirmed the H2O2 catalytic decomposition via O2 production (quantitative stoichiometric agreement). In addition, post-reaction Raman scattering spectra of the undissolved (U,Zr)O2 showed no additional peaks (indicating a lack of secondary phase formation). The (U,Zr)O2 matrix is much more stable than UO2 against H2O2-induced oxidative dissolution. Our findings will improve understanding on the molten fuels and provide an insight into decommissioning activities after a severe accident.

  5. Computed Potential Energy Surfaces and Minimum Energy Pathways for Chemical Reactions

    Science.gov (United States)

    Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

    1994-01-01

    Computed potential energy surfaces are often required for computation of such parameters as rate constants as a function of temperature, product branching ratios, and other detailed properties. For some dynamics methods, global potential energy surfaces are required. In this case, it is necessary to obtain the energy at a complete sampling of all the possible arrangements of the nuclei, which are energetically accessible, and then a fitting function must be obtained to interpolate between the computed points. In other cases, characterization of the stationary points and the reaction pathway connecting them is sufficient. These properties may be readily obtained using analytical derivative methods. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method to obtain accurate energetics, gives usefull results for a number of chemically important systems. The talk will focus on a number of applications including global potential energy surfaces, H + O2, H + N2, O(3p) + H2, and reaction pathways for complex reactions, including reactions leading to NO and soot formation in hydrocarbon combustion.

  6. Influence of a photochemical reaction on the controlled potential coulometric determination of plutonium in a mixture with uranium

    International Nuclear Information System (INIS)

    Le Duigou, Y.; Leidert, W.

    1976-01-01

    Data are provided in support of a photochemical reaction which takes place simultaneously with the electrochemical reduction of quadrivalent plutonium during the controlled potential coulometric determination of plutonium in a mixture with uranium. The interfering effect of this reaction is overcome by placing the cell in a dark environment. (orig.) [de

  7. XPS study on the surface reaction of uranium metal with carbon monoxide at 200 degree C

    International Nuclear Information System (INIS)

    Wang Xiaoling; Fu Yibei; Xie Renshou; Huang Ruiliang

    1996-12-01

    The surface reaction of uranium metal with carbon monoxide at 200 degree C has been studied by X-ray photoelectron spectroscopy (XPS). The carbon monoxide adsorption on the surface oxide layer resulted in U4f peak shifting to the lower binding energy and the content of oxygen in the oxide is decreased. O/U radio decreases with increasing the exposure of carbon monoxide to the surface layer. The investigation indicated the surface layer of uranium metal was further reduced in the atmosphere of carbon monoxide at high temperature. (3 refs., 5 figs.)

  8. Biological pathways of exposure and ecotoxicity values for uranium and associated radionuclides: Chapter D in Hydrological, geological, and biological site characterization of breccia pipe uranium deposits in Northern Arizona

    Science.gov (United States)

    Hinck, Jo E.; Linder, Greg L.; Finger, Susan E.; Little, Edward E.; Tillitt, Donald E.; Kuhne, Wendy

    2010-01-01

    This chapter compiles available chemical and radiation toxicity information for plants and animals from the scientific literature on naturally occurring uranium and associated radionuclides. Specifically, chemical and radiation hazards associated with radionuclides in the uranium decay series including uranium, thallium, thorium, bismuth, radium, radon, protactinium, polonium, actinium, and francium were the focus of the literature compilation. In addition, exposure pathways and a food web specific to the segregation areas were developed. Major biological exposure pathways considered were ingestion, inhalation, absorption, and bioaccumulation, and biota categories included microbes, invertebrates, plants, fishes, amphibians, reptiles, birds, and mammals. These data were developed for incorporation into a risk assessment to be conducted as part of an environmental impact statement for the Bureau of Land Management, which would identify representative plants and animals and their relative sensitivities to exposure of uranium and associated radionuclides. This chapter provides pertinent information to aid in the development of such an ecological risk assessment but does not estimate or derive guidance thresholds for radionuclides associated with uranium. Previous studies have not attempted to quantify the risks to biota caused directly by the chemical or radiation releases at uranium mining sites, although some information is available for uranium mill tailings and uranium mine closure activities. Research into the biological impacts of uranium exposure is strongly biased towards human health and exposure related to enriched or depleted uranium associated with the nuclear energy industry rather than naturally occurring uranium associated with uranium mining. Nevertheless, studies have reported that uranium and other radionuclides can affect the survival, growth, and reproduction of plants and animals. Exposure to chemical and radiation hazards is influenced by a

  9. Multistage reaction pathways in detonating high explosives

    International Nuclear Information System (INIS)

    Li, Ying; Kalia, Rajiv K.; Nakano, Aiichiro; Nomura, Ken-ichi; Vashishta, Priya

    2014-01-01

    Atomistic mechanisms underlying the reaction time and intermediate reaction products of detonating high explosives far from equilibrium have been elusive. This is because detonation is one of the hardest multiscale physics problems, in which diverse length and time scales play important roles. Here, large spatiotemporal-scale reactive molecular dynamics simulations validated by quantum molecular dynamics simulations reveal a two-stage reaction mechanism during the detonation of cyclotrimethylenetrinitramine crystal. Rapid production of N 2 and H 2 O within ∼10 ps is followed by delayed production of CO molecules beyond ns. We found that further decomposition towards the final products is inhibited by the formation of large metastable carbon- and oxygen-rich clusters with fractal geometry. In addition, we found distinct unimolecular and intermolecular reaction pathways, respectively, for the rapid N 2 and H 2 O productions

  10. Multistage reaction pathways in detonating high explosives

    Energy Technology Data Exchange (ETDEWEB)

    Li, Ying [Collaboratory for Advanced Computing and Simulations, Department of Physics and Astronomy, Department of Computer Science, and Department of Chemical Engineering and Materials Science, University of Southern California, Los Angeles, California 90089-0242 (United States); Argonne Leadership Computing Facility, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Kalia, Rajiv K.; Nakano, Aiichiro; Nomura, Ken-ichi; Vashishta, Priya [Collaboratory for Advanced Computing and Simulations, Department of Physics and Astronomy, Department of Computer Science, and Department of Chemical Engineering and Materials Science, University of Southern California, Los Angeles, California 90089-0242 (United States)

    2014-11-17

    Atomistic mechanisms underlying the reaction time and intermediate reaction products of detonating high explosives far from equilibrium have been elusive. This is because detonation is one of the hardest multiscale physics problems, in which diverse length and time scales play important roles. Here, large spatiotemporal-scale reactive molecular dynamics simulations validated by quantum molecular dynamics simulations reveal a two-stage reaction mechanism during the detonation of cyclotrimethylenetrinitramine crystal. Rapid production of N{sub 2} and H{sub 2}O within ∼10 ps is followed by delayed production of CO molecules beyond ns. We found that further decomposition towards the final products is inhibited by the formation of large metastable carbon- and oxygen-rich clusters with fractal geometry. In addition, we found distinct unimolecular and intermolecular reaction pathways, respectively, for the rapid N{sub 2} and H{sub 2}O productions.

  11. Enzyme sequence similarity improves the reaction alignment method for cross-species pathway comparison

    Energy Technology Data Exchange (ETDEWEB)

    Ovacik, Meric A. [Chemical and Biochemical Engineering Department, Rutgers University, Piscataway, NJ 08854 (United States); Androulakis, Ioannis P., E-mail: yannis@rci.rutgers.edu [Chemical and Biochemical Engineering Department, Rutgers University, Piscataway, NJ 08854 (United States); Biomedical Engineering Department, Rutgers University, Piscataway, NJ 08854 (United States)

    2013-09-15

    Pathway-based information has become an important source of information for both establishing evolutionary relationships and understanding the mode of action of a chemical or pharmaceutical among species. Cross-species comparison of pathways can address two broad questions: comparison in order to inform evolutionary relationships and to extrapolate species differences used in a number of different applications including drug and toxicity testing. Cross-species comparison of metabolic pathways is complex as there are multiple features of a pathway that can be modeled and compared. Among the various methods that have been proposed, reaction alignment has emerged as the most successful at predicting phylogenetic relationships based on NCBI taxonomy. We propose an improvement of the reaction alignment method by accounting for sequence similarity in addition to reaction alignment method. Using nine species, including human and some model organisms and test species, we evaluate the standard and improved comparison methods by analyzing glycolysis and citrate cycle pathways conservation. In addition, we demonstrate how organism comparison can be conducted by accounting for the cumulative information retrieved from nine pathways in central metabolism as well as a more complete study involving 36 pathways common in all nine species. Our results indicate that reaction alignment with enzyme sequence similarity results in a more accurate representation of pathway specific cross-species similarities and differences based on NCBI taxonomy.

  12. Enzyme sequence similarity improves the reaction alignment method for cross-species pathway comparison

    International Nuclear Information System (INIS)

    Ovacik, Meric A.; Androulakis, Ioannis P.

    2013-01-01

    Pathway-based information has become an important source of information for both establishing evolutionary relationships and understanding the mode of action of a chemical or pharmaceutical among species. Cross-species comparison of pathways can address two broad questions: comparison in order to inform evolutionary relationships and to extrapolate species differences used in a number of different applications including drug and toxicity testing. Cross-species comparison of metabolic pathways is complex as there are multiple features of a pathway that can be modeled and compared. Among the various methods that have been proposed, reaction alignment has emerged as the most successful at predicting phylogenetic relationships based on NCBI taxonomy. We propose an improvement of the reaction alignment method by accounting for sequence similarity in addition to reaction alignment method. Using nine species, including human and some model organisms and test species, we evaluate the standard and improved comparison methods by analyzing glycolysis and citrate cycle pathways conservation. In addition, we demonstrate how organism comparison can be conducted by accounting for the cumulative information retrieved from nine pathways in central metabolism as well as a more complete study involving 36 pathways common in all nine species. Our results indicate that reaction alignment with enzyme sequence similarity results in a more accurate representation of pathway specific cross-species similarities and differences based on NCBI taxonomy

  13. Stepwise radical cation Diels-Alder reaction via multiple pathways.

    Science.gov (United States)

    Shimizu, Ryo; Okada, Yohei; Chiba, Kazuhiro

    2018-01-01

    Herein we disclose the radical cation Diels-Alder reaction of aryl vinyl ethers by electrocatalysis, which is triggered by an oxidative SET process. The reaction clearly proceeds in a stepwise fashion, which is a rare mechanism in this class. We also found that two distinctive pathways, including "direct" and "indirect", are possible to construct the Diels-Alder adduct.

  14. Tris[bis(trimethylsilyl)amido]uranium: Compounds with tri-, tetra-, and penta-valent uranium

    International Nuclear Information System (INIS)

    Stewart, J.L.

    1988-04-01

    This trivalent uranium compound, serves as a precursor to new tri-, tetra-, and penta-valent uranium species. The geometry about the U atom is pyramidal. Lewis-base coordination compounds of U[N(SiMe 3 ) 2 ] 3 with a one-to-one- ratio of Lewis base to uranium were isolated with pyridine, 4-dimethylamino-pyridine, 2,6-Me 2 -C 6 H 3 NC, and TPO. Two-to-one coordination compounds were obtained with t-butylnitrile and t-butylisocyanide. Compounds with more sterically demanding bases could not be isolated. The expected decrease in U-N(SiMe 3 ) 2 bond length with increase in oxidation state is not observed. Reaction of ClU[N(SiMe 3 ) 2 ] 3 and Li[NH(p-tolyl)] yields the uranium (IV) dimer, U 2 [N(SiMe 3 ) 2 ] 4 [μ-N(p-tolyl)] 2 . Reaction with 2,4,6-triemethylaniline produces a dimer. Analogous substitution products could not be obtained with aniline or p-toluidine. t-Bu 3 CO/sup /minus//, t-Bu 2 CHO/sup /minus//, and t-Bu 3 SiO/sup /minus// are used to synthesize new tetravalent, mononuclear uranium compounds. Reaction of ClU(tritox) 3 with alkyllithium reagents leads to isolation of RU(tritox) 3 . The reaction of U(ditox) 4 with MeLi affords the addition product U(ditox) 4 (Me)Li, whose crystal structure is described. Preparation of uranium silox compounds is reported. 97 refs., 26 figs., 39 tabs

  15. Thermodynamic Simulation of Equilibrium Composition of Reaction Products at Dehydration of a Technological Channel in a Uranium-Graphite Reactor

    Science.gov (United States)

    Pavliuk, A. O.; Zagumennov, V. S.; Kotlyarevskiy, S. G.; Bespala, E. V.

    2018-01-01

    The problems of accumulation of nuclear fuel spills in the graphite stack in the course of operation of uranium-graphite nuclear reactors are considered. The results of thermodynamic analysis of the processes in the graphite stack at dehydration of a technological channel, fuel element shell unsealing and migration of fission products, and activation of stable nuclides in structural elements of the reactor and actinides inside the graphite moderator are given. The main chemical reactions and compounds that are produced in these modes in the reactor channel during its operation and that may be hazardous after its shutdown and decommissioning are presented. Thermodynamic simulation of the equilibrium composition is performed using the specialized code TERRA. The results of thermodynamic simulation of the equilibrium composition in different cases of technological channel dehydration in the course of the reactor operation show that, if the temperature inside the active core of the nuclear reactor increases to the melting temperature of the fuel element, oxides and carbides of nuclear fuel are produced. The mathematical model of the nonstationary heat transfer in a graphite stack of a uranium-graphite reactor in the case of the technological channel dehydration is presented. The results of calculated temperature evolution at the center of the fuel element, the replaceable graphite element, the air gap, and in the surface layer of the block graphite are given. The numerical results show that, in the case of dehydration of the technological channel in the uranium-graphite reactor with metallic uranium, the main reaction product is uranium dioxide UO2 in the condensed phase. Low probability of production of pyrophoric uranium compounds (UH3) in the graphite stack is proven, which allows one to disassemble the graphite stack without the risk of spontaneous graphite ignition in the course of decommissioning of the uranium-graphite nuclear reactor.

  16. Thermogravimetric study of the reaction of uranium oxides with fluorine

    International Nuclear Information System (INIS)

    Komura, Motohiro; Sato, Nobuaki; Kirishima, Akira; Tochiyama, Osamu

    2008-01-01

    Thermogravimetric study of the reaction of uranium oxides with fluorine was conducted by TG-DTA method using anti-corrosion type differential thermobalance. When UO 2 was heated from R.T. to 500 deg. C in 5% F 2 /He atmosphere, the weight increase appeared at ca. 250 deg. C with an exothermic peak. Then the weight decreased slightly with a small exothermic peak followed by the complete volatilization with a large exothermic peak at ca. 350 deg. C. At a flow rate of 15, 30, 60 ml min -1 , there seemed to be no significant change for the fluorination of UO 2 . With the different heating rates of 1, 2, 5 and 10 deg. C min -1 , the fluorination peak shifted to higher temperature with increasing heating rates. For the comparison with thermogravimetric results, phase analysis by XRD method was conducted for the products obtained at different temperatures. At 260 deg. C, the product was UO 2 with a small amount of the intermediate compound, UO 2 F. The amount of this compound increased with increasing temperature up to 320 deg. C. Then another phase of UO 2 F 2 appeared at 340 deg. C but it was immediately fluorinated to the volatile fluoride. When U 3 O 8 was used as a starting material, it was found that the steep weight decrease peak appeared at ca. 350 deg. C and the uranium volatilized completely. This result suggests that fluorination of U 3 O 8 occurs at this temperature forming UF 6 . Uranium trioxide showed the similar fluorination behavior to that of U 3 O 8

  17. Uranium recovery from slags of metallic uranium

    International Nuclear Information System (INIS)

    Fornarolo, F.; Frajndlich, E.U.C.; Durazzo, M.

    2006-01-01

    The Center of the Nuclear Fuel of the Institute of Nuclear Energy Research - IPEN finished the program of attainment of fuel development for research reactors the base of Uranium Scilicet (U 3 Si 2 ) from Hexafluoride of Uranium (UF 6 ) with enrichment 20% in weight of 235 U. In the process of attainment of the league of U 3 Si 2 we have as Uranium intermediate product the metallic one whose attainment generates a slag contend Uranium. The present work shows the results gotten in the process of recovery of Uranium in slags of calcined slags of Uranium metallic. Uranium the metallic one is unstable, pyrophoricity and extremely reactive, whereas the U 3 O 8 is a steady oxide of low chemical reactivity, what it justifies the process of calcination of slags of Uranium metallic. The calcination of the Uranium slag of the metallic one in oxygen presence reduces Uranium metallic the U 3 O 8 . Experiments had been developed varying it of acid for Uranium control and excess, nitric molar concentration gram with regard to the stoichiometric leaching reaction of temperature of the leaching process. The 96,0% income proves the viability of the recovery process of slags of Uranium metallic, adopting it previous calcination of these slags in nitric way with low acid concentration and low temperature of leaching. (author)

  18. Process for electrolytically preparing uranium metal

    Science.gov (United States)

    Haas, Paul A.

    1989-01-01

    A process for making uranium metal from uranium oxide by first fluorinating uranium oxide to form uranium tetrafluoride and next electrolytically reducing the uranium tetrafluoride with a carbon anode to form uranium metal and CF.sub.4. The CF.sub.4 is reused in the fluorination reaction rather than being disposed of as a hazardous waste.

  19. Retention and reduction of uranium on pyrite surface

    International Nuclear Information System (INIS)

    Eglizaud, N.

    2006-12-01

    In the hypothesis of a storage of the spent fuel in a deep geological formation, understanding the uranium dispersion in the environment is important. Pyrite is a reducing mineral present in the Callovo-Oxfordian argilites, the geological formation actually studied for such a storage. However, pyrite impact on uranium migration has already been poorly studied. The aim of the study was to understand the mechanisms of uranium(VI) retention and reduction on the pyrite surface (FeS 2 ). Solution chemistry was therefore coupled with solid spectroscopic studies (XPS and Raman spectroscopy). All uranium-pyrite interactions experiments were performed under an anoxic atmosphere, in a glove box. Pyrite dissolution under anoxic conditions releases sulfoxy-anions and iron(II), which can then be adsorbed on the pyrite surface. This adsorption was confirmed by interaction experiments using iron(II) isotopic dilution. Uranium(VI) is retained by an exchange reaction with iron(II) adsorbed on sulphur sites, with a maximal amount of sorbed uranium at pH ≥ 5.5. Cobalt(II) and europium(III) are also adsorbed on the pyrite surface above pH 5.5 confirming then that reduction is not required for species to adsorb on pyrite. When the concentration of uranium retained is lower than 4 x 10 -9 mol g -1 , an oxidation-reduction reaction leads to the formation of a uranium (VI) (IV) mixed oxide and to solid sulphur (d.o. ≥ -I). During this reaction, iron remains mostly at the +II oxidation degree. The reaction products seem to passivate the pyrite surface: at higher amounts of retained uranium, the oxidation-reduction reaction is no longer observed. The surface is saturated by the retention of (3.4 ± 0.8) x 10 -7 mol L -1 of uranium(VI). Modelling of uranium sorption at high surface coverage (≥ 4 x 10 -9 mol g -1 ) by the Langmuir model yields an adsorption constant of 8 x 10 7 L mol -1 . Finally, a great excess of uranium(VI) above the saturation concentration allows the observation of

  20. Retention and reduction of uranium on pyrite surface; Retention et reduction de l'uranium a la surface de la pyrite

    Energy Technology Data Exchange (ETDEWEB)

    Eglizaud, N

    2006-12-15

    In the hypothesis of a storage of the spent fuel in a deep geological formation, understanding the uranium dispersion in the environment is important. Pyrite is a reducing mineral present in the Callovo-Oxfordian argilites, the geological formation actually studied for such a storage. However, pyrite impact on uranium migration has already been poorly studied. The aim of the study was to understand the mechanisms of uranium(VI) retention and reduction on the pyrite surface (FeS{sub 2}). Solution chemistry was therefore coupled with solid spectroscopic studies (XPS and Raman spectroscopy). All uranium-pyrite interactions experiments were performed under an anoxic atmosphere, in a glove box. Pyrite dissolution under anoxic conditions releases sulfoxy-anions and iron(II), which can then be adsorbed on the pyrite surface. This adsorption was confirmed by interaction experiments using iron(II) isotopic dilution. Uranium(VI) is retained by an exchange reaction with iron(II) adsorbed on sulphur sites, with a maximal amount of sorbed uranium at pH {>=} 5.5. Cobalt(II) and europium(III) are also adsorbed on the pyrite surface above pH 5.5 confirming then that reduction is not required for species to adsorb on pyrite. When the concentration of uranium retained is lower than 4 x 10{sup -9} mol g{sup -1}, an oxidation-reduction reaction leads to the formation of a uranium (VI) (IV) mixed oxide and to solid sulphur (d.o. {>=} -I). During this reaction, iron remains mostly at the +II oxidation degree. The reaction products seem to passivate the pyrite surface: at higher amounts of retained uranium, the oxidation-reduction reaction is no longer observed. The surface is saturated by the retention of (3.4 {+-} 0.8) x 10{sup -7} mol L{sup -1} of uranium(VI). Modelling of uranium sorption at high surface coverage ({>=} 4 x 10{sup -9} mol g{sup -1}) by the Langmuir model yields an adsorption constant of 8 x 10{sup 7} L mol{sup -1}. Finally, a great excess of uranium(VI) above the

  1. Phospholyl-uranium complexes

    International Nuclear Information System (INIS)

    Gradoz, Philippe

    1993-01-01

    After having reported a bibliographical study on penta-methylcyclopentadienyl uranium complexes, and a description of the synthesis and radioactivity of uranium (III) and (IV) boron hydrides compounds, this research thesis reports the study of mono and bis-tetramethyl-phospholyl uranium complexes comprising chloride, boron hydride, alkyl and alkoxide ligands. The third part reports the comparison of structures, stabilities and reactions of homologue complexes in penta-methylcyclopentadienyl and tetramethyl-phospholyl series. The last part addresses the synthesis of tris-phospholyl uranium (III) and (IV) complexes. [fr

  2. A study on the formation of uranium carbide in an induction furnace

    International Nuclear Information System (INIS)

    Song, In Young; Lee, Yoon Sang; Kim, Eung Soo; Lee, Don Bae; Kim, Chang Kyu

    2005-01-01

    Uranium is a typical carbide-forming element. Three carbides, UC, U 2 C 3 and UC 2 , are formed in the uranium-carbon system. The most important of these as fuel is uranium monocarbide UC. It is well known that Uranium carbides can be obtained by three basic methods: 1) by reaction of uranium metal with carbon; 2) by reaction of uranium metal powder with gaseous hydrocarbons; 3) by reaction of uranium oxides with carbon. The use of uranium monocarbide, or materials based on it, has great prospects as fuel for nuclear reactors. It is quite possible that uranium dicarbide UC 2 may also acquire great importance as a fuel, particularly in dispersion fuel elements with graphite matrix. In the present study, uranium carbides are obtained by direct reaction of uranium metal with graphite in a high frequency induction furnace

  3. Kinetics of the chain uranium decay

    International Nuclear Information System (INIS)

    Zel'dovich, Ya.B.; Khariton, Yu.B.

    1984-01-01

    The development of chain reaction in uranium mass, when passing through the mass critical value, is studied. It is shown that thermal expanson is a powerful regulating factor, making the limit passing quite safe. The case of convergence of two uranium masses of precritical dimensions is considered in particular. The critical mass value is assessed and it is shown that its gradual increase above the critical value results in the reaction vibrational regime with the period inversely proportional to the square root of uranium supply rate. The role of delaying neutrons in the fission chain reaction development is pointed out

  4. Reaction of active uranium and thorium with aromatic carbonyls and pinacols in hydrocarbon solvents

    International Nuclear Information System (INIS)

    Kahn, B.E.; Rieke, R.D.

    1988-01-01

    Highly reactive uranium and thorium metal powders have been prepared by reduction of the anhydrous metal(IV) chlorides in hydrocarbon solvents. The reduction employs the crystalline hydrocarbon-soluble reducing agent [(TMEDA)Li] 2 [Nap] (TMEDA = N,N,N',N'-tetramethylethylenediamine, Nap = naphthalene). The resulting active metal powders have been shown to be extremely reactive with oxygen-containing compounds and have been used in the reductive coupling of aromatic ketones giving tetra-arylethylenes. Reactions with pinacols have given some mechanistic insight into the ketone coupling reaction. These finely divided metal powders activate very weakly acidic C-H bonds forming metal hydrides, which can be transferred to organic substrates

  5. Applications of fluorescence techniques to the study of uranium in homogeneous and heterogeneous environments: hydrolysis and photo-reduction reactions on titanium dioxide

    International Nuclear Information System (INIS)

    Eliet, Veronique

    1996-01-01

    This thesis describes the use of Time-Resolved Fluorescence to characterise the spectroscopy of hydroxo-complexes of hexavalent Uranium, and to study photochemical reactions involving these species at mineral/water interfaces. The instrumentation used comprised of either an excimer laser coupled to an optical multichannel analyser OMA or a Nd-YAG laser coupled to a stroboscopic photomultiplier. The hydrolysis of Uranium at a constant temperature of 25 deg. C, has been studied in the pH ranges 0-5 and 9-12. Deconvolution of spectra and fluorescence decay curves for Uranium yielded individual fluorescence spectra and decay times for uranyl UO 2 2+ and its hydroxo-complexes UO 2 OH + , (UO 2 )2(OH) 2 2+ , (UO 2 ) 3 (OH) 5 + et UO 2 (OH) 3 - . The comparison of fluorescence efficiencies for the various species showed that the complex (UO 2 )2(OH) 2 2+ is up to 85 times more fluorescent than uranyl, depending on the emission wavelength. Further, investigations of fluorescence decays as a function of temperature in the pH range 0-6, yielded activation energies for the various Uranium hydroxo species. The knowledge gained in homogeneous media served in the study of the photochemical behaviour of Uranium in suspensions of the semi-conductor mineral, TiO 2 . After UV-light absorption, charge carriers formed at the mineral surface were found to reduce hexavalent Uranium to the tetravalent oxidation state. Time-Resolved Fluorescence Spectroscopy has been used to monitor the kinetics of the oxidation state change. A reaction mechanism is proposed on the basis of results obtained by studying the kinetics of the process at different values of pH The role of humic substances on the heterogeneous redox reaction has also been examined. (author) [fr

  6. Density Functional Theory Study of Competitive Reaction Pathways of Ti+ with Fluorinated Acetone in the Gas Phase

    International Nuclear Information System (INIS)

    Hong, Kiryong; Kim, Tae Kyu

    2012-01-01

    We investigate the doublet and quartet potential energy surfaces associated with the gas-phase reaction between Ti + and CF 3 COCH 3 for two plausible reaction pathways, TiF 2 + and TiO + formation pathways by using the density functional theory (DFT) method. The molecular structures of intermediates and transition states involved in these reaction pathways are optimized at the DFT level by using the PBE0 functional. All transition states are identified by using the intrinsic reaction coordinate (IRC) method, and the resulting reaction coordinates describe how Ti + activates CF 3 COCH 3 and produces TiF 2 + and TiO + as products. On the basis of presented results, we propose the most favorable reaction pathway in the reaction between Ti + and CF 3 COCH 3

  7. Tris(bis(trimethylsilyl)amido)uranium: Compounds with tri-, tetra-, and penta-valent uranium

    Energy Technology Data Exchange (ETDEWEB)

    Stewart, J.L.

    1988-04-01

    This trivalent uranium compound, serves as a precursor to new tri-, tetra-, and penta-valent uranium species. The geometry about the U atom is pyramidal. Lewis-base coordination compounds of U(N(SiMe/sub 3/)/sub 2/)/sub 3/ with a one-to-one- ratio of Lewis base to uranium were isolated with pyridine, 4-dimethylamino-pyridine, 2,6-Me/sub 2/-C/sub 6/H/sub 3/NC, and TPO. Two-to-one coordination compounds were obtained with t-butylnitrile and t-butylisocyanide. Compounds with more sterically demanding bases could not be isolated. The expected decrease in U-N(SiMe/sub 3/)/sub 2/ bond length with increase in oxidation state is not observed. Reaction of ClU(N(SiMe/sub 3/)/sub 2/)/sub 3/and Li(NH(p-tolyl)) yields the uranium (IV) dimer, U/sub 2/(N(SiMe/sub 3/)/sub 2/)/sub 4/(..mu..-N(p-tolyl))/sub 2/. Reaction with 2,4,6-triemethylaniline produces a dimer. Analogous substitution products could not be obtained with aniline or p-toluidine. t-Bu/sub 3/CO/sup /minus//, t-Bu/sub 2/CHO/sup /minus//, and t-Bu/sub 3/SiO/sup /minus// are used to synthesize new tetravalent, mononuclear uranium compounds. Reaction of ClU(tritox)/sub 3/ with alkyllithium reagents leads to isolation of RU(tritox)/sub 3/. The reaction of U(ditox)/sub 4/ with MeLi affords the addition product U(ditox)/sub 4/(Me)Li, whose crystal structure is described. Preparation of uranium silox compounds is reported. 97 refs., 26 figs., 39 tabs.

  8. Study of the reaction of uranium and plutonium with bone char

    International Nuclear Information System (INIS)

    Silver, G.L.; Koenst, J.W.

    1977-01-01

    A study of the reaction of plutonium with a commercial bone char indicates that this bone char has a high capacity for removing plutonium from aqueous wastes. The adsorption of plutonium by bone char is pH dependent, and for plutonium(IV) polymer appears to be maximized near pH 7.3 for plutonium concentrations typical of some waste streams. Adsorption is affected by dissolved salts, especially calcium and phosphate salts. Freundlich isotherms representing the adsorption of uranium and plutonium have been prepared. The low potential imposed upon aqueous solutions by commercial bone char is adequate for reduction of hexavalent plutonium to a lower plutonium oxidation state

  9. Permanganate oxidation of α-amino acids: kinetic correlations for the nonautocatalytic and autocatalytic reaction pathways.

    Science.gov (United States)

    Perez-Benito, Joaquin F

    2011-09-08

    The reactions of permanganate ion with seven α-amino acids in aqueous KH(2)PO(4)/K(2)HPO(4) buffers have been followed spectrophotometrically at two different wavelengths: 526 nm (decay of MnO(4)(-)) and 418 nm (formation of colloidal MnO(2)). All of the reactions studied were autocatalyzed by colloidal MnO(2), with the contribution of the autocatalytic reaction pathway decreasing in the order glycine > l-threonine > l-alanine > l-glutamic acid > l-leucine > l-isoleucine > l-valine. The rate constants corresponding to the nonautocatalytic and autocatalytic pathways were obtained by means of either a differential rate law or an integrated one, the latter requiring the use of an iterative method for its implementation. The activation parameters for the two pathways were determined and analyzed to obtain statistically significant correlations for the series of reactions studied. The activation enthalpy of the nonautocatalytic pathway showed a strong, positive dependence on the standard Gibbs energy for the dissociation of the protonated amino group of the α-amino acid. Linear enthalpy-entropy correlations were found for both pathways, leading to isokinetic temperatures of 370 ± 21 K (nonautocatalytic) and 364 ± 28 K (autocatalytic). Mechanisms in agreement with the experimental data are proposed for the two reaction pathways.

  10. A review of the environmental behavior of uranium derived from depleted uranium alloy penetrators

    Energy Technology Data Exchange (ETDEWEB)

    Erikson, R.L.; Hostetler, C.J.; Divine, J.R.; Price, K.R.

    1990-01-01

    The use of depleted uranium (DU) penetrators as armor-piercing projectiles in the field results in the release of uranium into the environment. Elevated levels of uranium in the environment are of concern because of radioactivity and chemical toxicity. In addition to the direct contamination of the soil with uranium, the penetrators will also chemically react with rainwater and surface water. Uranium may be oxidized and leached into surface water or groundwater and may subsequently be transported. In this report, we review some of the factors affecting the oxidation of the DU metal and the factors influencing the leaching and mobility of uranium through surface water and groundwater pathways, and the uptake of uranium by plants growing in contaminated soils. 29 refs., 10 figs., 3 tabs.

  11. RhoA/ROCK Signaling Pathway Mediates Shuanghuanglian Injection-Induced Pseudo-allergic Reactions.

    Science.gov (United States)

    Han, Jiayin; Zhao, Yong; Zhang, Yushi; Li, Chunying; Yi, Yan; Pan, Chen; Tian, Jingzhuo; Yang, Yifei; Cui, Hongyu; Wang, Lianmei; Liu, Suyan; Liu, Jing; Deng, Nuo; Liang, Aihua

    2018-01-01

    Background: Shuanghuanglian injection (SHLI) is a famous Chinese medicine used as an intravenous preparation for the treatment of acute respiratory tract infections. In the recent years, the immediate hypersensitivity reactions induced by SHLI have attracted broad attention. However, the mechanism involved in these reactions has not yet been elucidated. The present study aims to explore the characteristics of the immediate hypersensitivity reactions induced by SHLI and deciphers the role of the RhoA/ROCK signaling pathway in these reactions. Methods: SHLI-immunized mice or naive mice were intravenously injected (i.v.) with SHLI (600 mg/kg) once, and vascular leakage in the ears was evaluated. Passive cutaneous anaphylaxis test was conducted using sera collected from SHLI-immunized mice. Naive mice were administered (i.v.) with a single dose of 150, 300, or 600 mg/kg of SHLI, and vascular leakage, histamine release, and histopathological alterations in the ears, lungs, and intestines were tested. In vitro , human umbilical vein endothelial cell (HUVEC) monolayer was incubated with SHLI (0.05, 0.1, or 0.15 mg/mL), and the changes in endothelial permeability and cytoskeleton were observed. Western blot analysis was performed and ROCK inhibitor was employed to investigate the contribution of the RhoA/ROCK signaling pathway in SHLI-induced hypersensitivity reactions, both in HUVECs and in mice. Results: Our results indicate that SHLI was able to cause immediate dose-dependent vascular leakage, edema, and exudates in the ears, lungs, and intestines, and histamine release in mice. These were pseudo-allergic reactions, as SHLI-specific IgE was not elicited during sensitization. In addition, SHLI induced reorganization of actin cytoskeleton and disrupted the endothelial barrier. The administration of SHLI directly activated the RhoA/ROCK signaling pathway both in HUVECs and in the ears, lungs, and intestines of mice. Fasudil hydrochloride, a ROCK inhibitor, ameliorated the

  12. Uranium chemistry: significant advances

    International Nuclear Information System (INIS)

    Mazzanti, M.

    2011-01-01

    The author reviews recent progress in uranium chemistry achieved in CEA laboratories. Like its neighbors in the Mendeleev chart uranium undergoes hydrolysis, oxidation and disproportionation reactions which make the chemistry of these species in water highly complex. The study of the chemistry of uranium in an anhydrous medium has led to correlate the structural and electronic differences observed in the interaction of uranium(III) and the lanthanides(III) with nitrogen or sulfur molecules and the effectiveness of these molecules in An(III)/Ln(III) separation via liquid-liquid extraction. Recent work on the redox reactivity of trivalent uranium U(III) in an organic medium with molecules such as water or an azide ion (N 3 - ) in stoichiometric quantities, led to extremely interesting uranium aggregates particular those involved in actinide migration in the environment or in aggregation problems in the fuel processing cycle. Another significant advance was the discovery of a compound containing the uranyl ion with a degree of oxidation (V) UO 2 + , obtained by oxidation of uranium(III). Recently chemists have succeeded in blocking the disproportionation reaction of uranyl(V) and in stabilizing polymetallic complexes of uranyl(V), opening the way to to a systematic study of the reactivity and the electronic and magnetic properties of uranyl(V) compounds. (A.C.)

  13. Experimental Observation of Nuclear Reactions in Palladium and Uranium - Possible Explanation by Hydrex Mode

    International Nuclear Information System (INIS)

    Dufour, J.; Murat, D.; Dufour, X.; Foos, J.

    2001-01-01

    Experiments with uranium are presented that show a highly exothermal reaction, which can only be of nuclear origin. One striking point of these results is that they clearly show that what is being observed is not some kind of fusion reaction of the deuterium present (only exceedingly small amounts of it are present). This is a strong indication that hydrogen can trigger nuclear reactions that seem to involve the nuclei of the lattice (which would yield a fission-like pattern of products). Confronted with a situation where some experiments in the field yield a fusion-like pattern of products (CF experiments) and others a fissionlike one (LENR experiments), one can reasonably wonder whether one is not observing two aspects of the same phenomenon. Thus, it is proposed to describe CF and LENR reactions as essentially the same phenomenon based on the possible existence of a still hypothetical proton/electron resonance, which would catalyze fissionlike reactions with a neutron sink. Finally, a series of experiments is proposed to assess this hypothesis

  14. Dynamic Characteristics and Model for Centralization Reaction of Acidic Tailings From Heap Leaching of Uranium Ore

    International Nuclear Information System (INIS)

    Ding Dexin; Liu Yulong; Li Guangyue; Wang Youtuan

    2010-01-01

    Centralization tests were carried out on acidic tailings from heap leaching of uranium ore by using CaO, NaOH and NH 4 OH. The variations of pH with time were measured for the three centralization systems and the dynamic models for the systems were set up by regressing the measured data. The centralization process consists of the fast reaction phase representing the reaction between the centralization agent and the acid on the surface of the tailing's particles and the slow diffusion-reaction phase representing the diffusion-reaction between the centralization agent and the acid within the tailing's particles. The non-linear coupling and feedback function model for the diffusion-reaction of the centralization agent can reflect the process and mode of the centralization reaction. There is a non-linear oscillation in the variation of pH within the centralization systems. The dynamic model for the tailing's centralization reaction can fit the pH variation within the centralization systems. (authors)

  15. Recovery of uranium by chlorination

    International Nuclear Information System (INIS)

    Komoto, Shigetoshi; Taki, Tomihiro

    1988-01-01

    The recovery of uranium from uraniferous phosphate by conventional process is generally uneconomic, except that uranium is recovered as a by-product. If an economical process by which uranium is recovered efficiently as a chief product is discovered, uraniferous phosphate will be used effectively as uranium ore. By using chiorination which will be expected to be favorable in comparison with conventional process, the recovery of uranium from uraniferous phosphate has been carried out. The paper describes the reaction machanism and general characteristics of the uranium chiorination, and the research done so for. (author)

  16. Uranium Oxide Rate Summary for the Spent Nuclear Fuel (SNF) Project (OCRWM)

    Energy Technology Data Exchange (ETDEWEB)

    PAJUNEN, A.L.

    2000-09-20

    The purpose of this document is to summarize the uranium oxidation reaction rate information developed by the Hanford Spent Nuclear Fuel (SNF) Project and describe the basis for selecting reaction rate correlations used in system design. The selection basis considers the conditions of practical interest to the fuel removal processes and the reaction rate application during design studies. Since the reaction rate correlations are potentially used over a range of conditions, depending of the type of evaluation being performed, a method for transitioning between oxidation reactions is also documented. The document scope is limited to uranium oxidation reactions of primary interest to the SNF Project processes. The reactions influencing fuel removal processes, and supporting accident analyses, are: uranium-water vapor, uranium-liquid water, uranium-moist air, and uranium-dry air. The correlation selection basis will consider input from all available sources that indicate the oxidation rate of uranium fuel, including the literature data, confirmatory experimental studies, and fuel element observations. Trimble (2000) summarizes literature data and the results of laboratory scale experimental studies. This document combines the information in Trimble (2000) with larger scale reaction observations to describe uranium oxidation rate correlations applicable to conditions of interest to the SNF Project.

  17. Uranium Oxide Rate Summary for the Spent Nuclear Fuel (SNF) Project (OCRWM)

    International Nuclear Information System (INIS)

    PAJUNEN, A.L.

    2000-01-01

    The purpose of this document is to summarize the uranium oxidation reaction rate information developed by the Hanford Spent Nuclear Fuel (SNF) Project and describe the basis for selecting reaction rate correlations used in system design. The selection basis considers the conditions of practical interest to the fuel removal processes and the reaction rate application during design studies. Since the reaction rate correlations are potentially used over a range of conditions, depending of the type of evaluation being performed, a method for transitioning between oxidation reactions is also documented. The document scope is limited to uranium oxidation reactions of primary interest to the SNF Project processes. The reactions influencing fuel removal processes, and supporting accident analyses, are: uranium-water vapor, uranium-liquid water, uranium-moist air, and uranium-dry air. The correlation selection basis will consider input from all available sources that indicate the oxidation rate of uranium fuel, including the literature data, confirmatory experimental studies, and fuel element observations. Trimble (2000) summarizes literature data and the results of laboratory scale experimental studies. This document combines the information in Trimble (2000) with larger scale reaction observations to describe uranium oxidation rate correlations applicable to conditions of interest to the SNF Project

  18. Position-specific isotope modeling of organic micropollutants transformation through different reaction pathways

    DEFF Research Database (Denmark)

    Jin, Biao; Rolle, Massimo

    2016-01-01

    The degradation of organic micropollutants occurs via different reaction pathways. Compound specific isotope analysis is a valuable tool to identify such degradation pathways in different environmental systems. We propose a mechanism-based modeling approach that provides a quantitative framework ...

  19. Aquatic pathway variables affecting the estimation of dose commitment from uranium mill tailings

    International Nuclear Information System (INIS)

    Lush, D.L.; Snodgrass, W.J.; McKee, P.

    1982-01-01

    As one of a series of studies being carried out for the Atomic Energy Control Board of Canada, the environmental variables affecting population dose commitment and critical group dose rates from aquatic pathways were investigated. A model was developed to follow uranium and natural thorium decay series radionuclides through aquatic pathways leading both to long-term sediment sinks and to man. Pathways leading to man result in both a population dose commitment and a critical group dose rate. The key variables affecting population dose commitment are suspended particulate concentrations in the receiving aquatic systems, the settling velocities of these particulates and the solid-aqueous phase distribution coefficient associated with each radionuclide. Of secondary importance to population dose commitment are the rate at which radionuclides enter the receiving waters and the value of the water to food transfer coefficients that are used in the model. For the critical group dose rate, the rate at which the radionuclides leave the tailings, the water to food transfer coefficients, the rate of water and fish consumption and the dose conversion factors for 210 Pb and 210 Po are of secondary importance (author)

  20. Investigation of the kinetics of the reactions of oxidation, nitration, and hydrogenation of uranium

    International Nuclear Information System (INIS)

    Adda, Y.

    1955-06-01

    Various physico-chemical methods have been used to investigate the kinetics of the oxidation hydridation and nitridation of uranium. The experimental results show that the kinetics of these reactions are influenced by many factors also the Pilling and Bedworth rule is valid only under very limited conditions. The disagreement between this rule and the experimental results could be explained by the existence of numerous mechanical faults in the compounds obtained by the dry corrosion of the metal. (author) [fr

  1. Uranium dioxide electrolysis

    Science.gov (United States)

    Willit, James L [Batavia, IL; Ackerman, John P [Prescott, AZ; Williamson, Mark A [Naperville, IL

    2009-12-29

    This is a single stage process for treating spent nuclear fuel from light water reactors. The spent nuclear fuel, uranium oxide, UO.sub.2, is added to a solution of UCl.sub.4 dissolved in molten LiCl. A carbon anode and a metallic cathode is positioned in the molten salt bath. A power source is connected to the electrodes and a voltage greater than or equal to 1.3 volts is applied to the bath. At the anode, the carbon is oxidized to form carbon dioxide and uranium chloride. At the cathode, uranium is electroplated. The uranium chloride at the cathode reacts with more uranium oxide to continue the reaction. The process may also be used with other transuranic oxides and rare earth metal oxides.

  2. Tris(Cyclopentadienyl)Uranium-t-Butyl: Synthesis, reactions, and mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Weydert, M.

    1993-04-01

    Compounds (RC[sub 5]H[sub 4])[sub 3]U(t-Bu) were prepared for R = H, Me, Et. Their decomposition products in aromatic solvents are consistent with a radical decomposition pathway induced by solvent-assisted U-C bond homolysis. NMR was used to study the reactions of (RC[sub 5]H[sub 4])[sub 3]UCl with t-BuLi (R = t-Bu, Me[sub 3]Si). Reactions of (MeC[sub 5]H[sub 4])[sub 3]U(t-Bu) with Lewis bases and fluorocarbons were studied. Analogous reaction chemistry between (RC[sub 5]H[sub 4])[sub 3]ThX systems and t-BuLi was also studied, and reactivity differences between U and Th are discussed. Synthesis of sterically crowded (RC[sub 5]H[sub 4])[sub 4]U compounds is next considered. Reaction of the trivalent (RC[sub 5]H[sub 4])[sub 3]U with (RC[sub 5]H[sub 4])[sub 2]Hg results in formation of (RC[sub 5]H[sub 4])[sub 4]U. Steric congestion, cyclopentadienyl ligand exchange, and electron transfer are discussed. (DLC)

  3. Kinetic study of the fluorination by fluorine of some uranium and plutonium compounds; Etude cinetique de la fluoration par le fluor de quelques composes de l'uranium et du plutonium

    Energy Technology Data Exchange (ETDEWEB)

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

    1964-12-15

    The study of fluorination reactions of uranium and plutonium compounds with elementary fluorine, has been carried out using a thermogravimetric method. These reactions are heterogeneous ones, and of the following type: S(solid) + G{sub 1}(gas) - G{sub 2}(gas). The kinetics of these reactions correspond to a uniform attack of the entire surface of the sample. {alpha}: being the degree of completion of the reaction, k(rel): being the relative rate of penetration of the reaction interface, t: being the time, one have the relation: (1-{alpha}){sup 1/3} = 1 - k(rel)*t. The mechanism of the reaction varies according to the nature of the compound: 1) with uranium tetrafluoride and plutonium tetrafluoride, the reaction proceeds in a single step; 2) with uranium oxides, the reaction proceeds in two steps, uranium oxyfluoride being the intermediate compound; 3) with plutonium oxide, the reaction proceeds in two steps, plutonium tetrafluoride being the intermediate compound; and 4) with uranium trichloride, the mechanism is complex: chlorine trifluoride is formed. (author) [French] L'etude des reactions de fluoration par le fluor, de composes de l'uranium et du plutonium a ete faite par thermogravimetrie. Ce sont des reactions heterogenes du type: S(solide) + G{sub 1}(gaz) - G{sub 2}(gaz). La cinetique de ces reactions est celle correspondant a une attaque uniforme de toute la surface de l'echantillon. Si {alpha}: est le degre d'avancement de la reaction, k(rel): est la vitesse relative d'avancement d'un interface reactionnel, t: le temps. On a la relation: (1-{alpha}){sup 1/3} = 1-k(rel)*t. Le mecanisme de la reaction varie selon la nature du compose: 1) tetrafluorure d'uranium et tetrafluorure de plutonium, la reaction s'effectue en un seul stade; 2) Oxydes d'uranium: la reaction s'effectue en deux stades, l'oxyfluorure d'uranium est le compose intermediaire; 3) oxyde de plutonium, la reaction s'effectue en deux stades, la tetrafluorure de plutonium est le compose

  4. A method for integrating and ranking the evidence for biochemical pathways by mining reactions from text

    Science.gov (United States)

    Miwa, Makoto; Ohta, Tomoko; Rak, Rafal; Rowley, Andrew; Kell, Douglas B.; Pyysalo, Sampo; Ananiadou, Sophia

    2013-01-01

    Motivation: To create, verify and maintain pathway models, curators must discover and assess knowledge distributed over the vast body of biological literature. Methods supporting these tasks must understand both the pathway model representations and the natural language in the literature. These methods should identify and order documents by relevance to any given pathway reaction. No existing system has addressed all aspects of this challenge. Method: We present novel methods for associating pathway model reactions with relevant publications. Our approach extracts the reactions directly from the models and then turns them into queries for three text mining-based MEDLINE literature search systems. These queries are executed, and the resulting documents are combined and ranked according to their relevance to the reactions of interest. We manually annotate document-reaction pairs with the relevance of the document to the reaction and use this annotation to study several ranking methods, using various heuristic and machine-learning approaches. Results: Our evaluation shows that the annotated document-reaction pairs can be used to create a rule-based document ranking system, and that machine learning can be used to rank documents by their relevance to pathway reactions. We find that a Support Vector Machine-based system outperforms several baselines and matches the performance of the rule-based system. The success of the query extraction and ranking methods are used to update our existing pathway search system, PathText. Availability: An online demonstration of PathText 2 and the annotated corpus are available for research purposes at http://www.nactem.ac.uk/pathtext2/. Contact: makoto.miwa@manchester.ac.uk Supplementary information: Supplementary data are available at Bioinformatics online. PMID:23813008

  5. On the deduction of chemical reaction pathways from measurements of time series of concentrations.

    Science.gov (United States)

    Samoilov, Michael; Arkin, Adam; Ross, John

    2001-03-01

    We discuss the deduction of reaction pathways in complex chemical systems from measurements of time series of chemical concentrations of reacting species. First we review a technique called correlation metric construction (CMC) and show the construction of a reaction pathway from measurements on a part of glycolysis. Then we present two new improved methods for the analysis of time series of concentrations, entropy metric construction (EMC), and entropy reduction method (ERM), and illustrate (EMC) with calculations on a model reaction system. (c) 2001 American Institute of Physics.

  6. The passivation of uranium metal surfaces by nitrogen bombardment - the formation of uranium nitride

    International Nuclear Information System (INIS)

    Allen, G.C.; Holmes, N.R.

    1987-08-01

    As part of a detailed investigation of the behaviour of metallic uranium in various atmospheres, we have examined the reaction between nitrogen gas and uranium metal. At room temperature there was no evidence of reaction between nitrogen gas and a clean metal surface; the only changes observed could be attributed to reaction between the metal and traces of oxygen (less than 0.1 ppm) in the nitrogen gas. Reaction between the metal and nitrogen was induced however by accelerating nitrogen towards the surface using a fast atom gun. The resulting nitrided surface was characterised by X-ray photoelectron spectroscopy, and its oxidation behaviour was monitored over an extended period in UHV and in air. (author)

  7. The passivation of uranium metal surfaces by nitrogen bombardment - the formation of uranium nitride

    International Nuclear Information System (INIS)

    Allen, G.C.; Holmes, N.R.

    1988-01-01

    As part of a detailed investigation of the behaviour of metallic uranium in various atmospheres, we have examined the reaction between nitrogen gas and uranium metal. At room temperature there was no evidence of reaction between nitrogen gas and a clean metal surface; the only changes observed could be attributed to reaction between the metal and traces of oxygen (less than 0.1 ppm) in the nitrogen gas. Reaction between the metal and nitrogen was induced, however, by accelerating nitrogen towards the surface using a fast atom gun. The resulting nitrided surface was characterized by X-ray photoelectron spectroscopy, and its oxidation behaviour was monitored over an extended period in UHV and in air. (orig.)

  8. Electron exchange reaction in anion exchangers as observed in uranium isotope separation

    International Nuclear Information System (INIS)

    Obanawa, Heiichiro; Takeda, Kunihiko; Seko, Maomi

    1991-01-01

    The mechanism of electron exchange in an ion exchanger, as occurring between U 4+ and UO 2 2+ in uranium isotope separation, was investigated. The height of the separation unit (H q ) in the presence of metal ion catalysts, as obtained from the separation experiments, was found to be almost coincident with the theoretical value of H q as calculated on the basis of the intrasolution acceleration mechanism of the metal ion, suggesting that the electron exchange mechanism in the ion-exchanger is essentially the same as that in the solution when metal ion catalysts are present. Separation experiments with no metal ion catalyst, on the other hand, showed the electron exchange reaction in the ion exchanger to be substantially higher than that in the solution, suggesting an acceleration of the electron exchange reaction by the ion-exchanger which is due to the close existence of higher order Cl - complexes of UO 2 2+ and U 4+ in the vicinity of the ion-exchange group. (author)

  9. Uranium

    International Nuclear Information System (INIS)

    Anon.

    1983-01-01

    Recent decisions by the Australian Government will ensure a significant expansion of the uranium industry. Development at Roxby Downs may proceed and Ranger may fulfil two new contracts but the decision specifies that apart from Roxby Downs, no new mines should be approved. The ACTU maintains an anti-uranium policy but reaction to the decision from the trade union movement has been muted. The Australian Science and Technology Council (ASTEC) has been asked by the Government to conduct an inquiry into a number of issues relating to Australia's role in the nuclear fuel cycle. The inquiry will examine in particular Australia's nuclear safeguards arrangements and the adequacy of existing waste management technology. In two additional decisions the Government has dissociated itself from a study into the feasibility of establishing an enrichment operation and has abolished the Uranium Advisory Council. Although Australian reserves account for 20% of the total in the Western World, Australia accounts for a relatively minor proportion of the world's uranium production

  10. Electrochemical investigation of tetravalent uranium β-diketones for active materials of all-uranium redox flow battery

    International Nuclear Information System (INIS)

    Yamamura, Tomoo; Shiokawa, Yoshinobu; Ikeda, Yasuhisa

    2002-01-01

    For active materials of the all-uranium redox flow battery for the power storage, tetravalent uranium β-diketones were investigated. The electrode reactions of U(ba) 4 and U(btfa) 4 were examined in comparison with that of U(acac) 4 , where ba denotes benzoylacetone, btfa benzoyltrifluoroacetone and acac acetylacetone. The cyclic voltammograms of U(ba) 4 and U(btfa) 4 solutions indicate that there are two series of redox reactions corresponding to the complexes with different coordination numbers of four and three. The electrode kinetics of the U(IV)/U(III) redox reactions for btfa complexes is examined. The obtained result supports that the uranium β-diketone complexes examined in the present study will serve as excellent active materials for negative electrolyte in the redox flow battery. (author)

  11. Depleted uranium: Metabolic disruptor?; Uranium appauvri: perturbateur metabolique?

    Energy Technology Data Exchange (ETDEWEB)

    Souidi, Maamar; Dublineau, Isabelle; Lestaevel, Philippe [Institut de Radioprotection et de Surete Nucleaire - IRSN, Direction de la radioprotection de l' homme, Laboratoire de radiotoxicologie experimentale, Service de radiobiologie et d' epidemiologie, BP 17, 92262 Fontenay-aux-Roses cedex (France)

    2011-11-15

    The presence of uranium in the environment can lead to long-term contamination of the food chain and of water intended for human consumption and thus raises many questions about the scientific and societal consequences of this exposure on population health. Although the biological effects of chronic low-level exposure are poorly understood, results of various recent studies show that contamination by depleted uranium (DU) induces subtle but significant biological effects at the molecular level in organs including the brain, liver, kidneys and testicles. For the first time, it has been demonstrated that DU induces effects on several metabolic pathways, including those metabolizing vitamin D, cholesterol, steroid hormones, acetylcholine and xenobiotics. This evidence strongly suggests that DU might well interfere with many metabolic pathways. It might thus contribute, together with other man-made substances in the environment, to increased health risks in some regions. (authors)

  12. Reactivity of Single-Walled Carbon Nanotubes in the Diels-Alder Cycloaddition Reaction: Distortion-Interaction Analysis along the Reaction Pathway.

    Science.gov (United States)

    Li, Yingzi; Osuna, Sílvia; Garcia-Borràs, Marc; Qi, Xiaotian; Liu, Song; Houk, Kendall N; Lan, Yu

    2016-08-26

    Diels-Alder cycloaddition is one of the most powerful tools for the functionalization of single-walled carbon nanotubes (SWCNTs). Density functional theory at the B3-LYP level of theory has been used to investigate the reactivity of different-diameter SWCNTs (4-9,5) in Diels-Alder reactions with 1,3-butadiene; the reactivity was found to decrease with increasing SWCNT diameter. Distortion/interaction analysis along the whole reaction pathway was found to be a better way to explore the reactivity of this type of reaction. The difference in interaction energy along the reaction pathway is larger than that of the corresponding distortion energy. However, the distortion energy plots for these reactions show the same trend. Therefore, the formation of the transition state can be determined from the interaction energy. A lower interaction energy leads to an earlier transition state, which indicates a lower activation energy. The computational results also indicate that the original distortion of the SWCNTs leads to an increase in the reactivity of the SWCNTs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Electrochemical investigation of uranium β-diketonates for all-uranium redox flow battery

    International Nuclear Information System (INIS)

    Yamamura, Tomoo; Shiokawa, Yoshinobu; Yamana, Hajimu; Moriyama, Hirotake

    2002-01-01

    The redox flow battery using uranium as the negative and the positive active materials in polar aprotic solvents was proposed. In order to establish the guiding principle for the uranium compounds as the active materials, the investigation of uranium β-diketonate complexes was conducted on (i) the solubility of active materials, (ii) the electrode reaction of U(VI) and U(IV) β-diketonate complexes and (iii) the estimation of the open circuit voltage of the battery. The solubilities of higher than 0.8 mol dm -3 of U(VI) complexes and higher than 0.4 mol dm -3 of a U(IV) complex were obtained in the solvents. The electrode reactions of U(pta) 4 , UO 2 (dpm) 2 , UO 2 (fod) 2 and UO 2 (pta) 2 were first studied and the redox potentials of uranium β-diketonates were thermodynamically discussed. The open circuit voltage is estimated more than 1 V by using Hacac or Hdpm. The larger open circuit voltage is expected when a ligand with the larger basicity is used

  14. 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)

  15. Formation mechanism of uranium minerals at sandstone-type uranium deposits

    International Nuclear Information System (INIS)

    Li Shengfu; Zhang Yun

    2004-01-01

    By analyzing the behavior and existence form of uranium in different geochemical environments, existence form of uranium and uranium minerals species, this paper expounds the formation mechanism of main commercial uranium mineral--pitchblende: (1) uranium is a valence-changeable element. It is reactivated and migrates in oxidized environment, and is reduced and precipitated in reducing environment; (2) [UO 2 (CO 3 ) 3 ] 4- , [UO 2 (CO 3 ) 2 ] 2- coming from oxidized environment react with reductants such as organic matter, sulfide and low-valence iron at the redox front to form simple uranium oxide--pitchblende; (3)the adsorption of uranium by organic matter and clay minerals accelerates the reduction and the concentration of uranium. Therefore, it is considered, that the reduction of SO 4 2- by organic matter to form H 2 S, and the reduction of UO 2 2+ by H 2 S are the main reasons for the formation of pitchblende. This reaction is extensively and universally available in neutral and weakly alkaline carbonate solution. The existense of reductants such as H 2 S is the basic factor leading to the decrease of Eh in environments and the oversaturation of UO 2 2+ at the redox front in groundwater, thus accelerating the adsorption and the precipitation of uranium

  16. Tris(Cyclopentadienyl)Uranium-t-Butyl: Synthesis, reactions, and mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Weydert, Marc [Univ. of California, Berkeley, CA (United States)

    1993-04-01

    Compounds (RC5H4)3U(t-Bu) were prepared for R = H, Me, Et. Their decomposition products in aromatic solvents are consistent with a radical decomposition pathway induced by solvent-assisted U-C bond homolysis. NMR was used to study the reactions of (RC5H4)3UCl with t-BuLi (R = t-Bu, Me3Si). Reactions of (MeC5H4)3U(t-Bu) with Lewis bases and fluorocarbons were studied. Analogous reaction chemistry between (RC5H4)3ThX systems and t-BuLi was also studied, and reactivity differences between U and Th are discussed. Synthesis of sterically crowded (RC5H4)4U compounds is next considered. Reaction of the trivalent (RC5H4)3U with (RC5H4)2Hg results in formation of (RC5H4)4U. Steric congestion, cyclopentadienyl ligand exchange, and electron transfer are discussed. (DLC)

  17. Uranium recovery from AVLIS slag

    International Nuclear Information System (INIS)

    D'Agostino, A.E.; Mycroft, J.R.; Oliver, A.J.; Schneider, P.G.; Richardson, K.L.

    2000-01-01

    Uranium metal for the Atomic Vapor Laser Isotope Separation (AVLIS) project was to have been produced by the magnesiothermic reduction of uranium tetrafluoride. The other product from this reaction is a magnesium fluoride slag, which contains fine and entrained natural uranium as metal and oxide. Recovery of the uranium through conventional mill leaching would not give a magnesium residue free of uranium but to achieve more complete uranium recovery requires the destruction of the magnesium fluoride matrix and liberation of the entrapped uranium. Alternate methods of carrying out such treatments and the potential for recovery of other valuable byproducts were examined. Based on the process flowsheets, a number of economic assessments were performed, conclusions were drawn and the preferred processing alternatives were identified. (author)

  18. The passivation of uranium metal surfaces by nitrogen bombardment — the formation of uranium nitride

    Science.gov (United States)

    Allen, Geoffrey C.; Holmes, Nigel R.

    1988-05-01

    As part of a detailed investigation of the behaviour of metallic uranium in various atmospheres, we have examined the reaction between nitrogen gas and uranium metal. At room temperature there was no evidence of reaction between nitrogen gas and a clean metal surface; the only changes observed could be attributed to reaction between the metal and traces of oxygen (less than 0.1 ppm) in the nitrogen gas. Reaction between the metal and nitrogen was induced, however, by accelerating nitrogen towards the surface using a fast atom gun. The resulting nitrided surface was characterized by X-ray photoelectron spectroscopy, and its oxidation behaviour was monitored over an extended period in UHV and in air.

  19. Uranium isotopic effect studies on cation and anion exchange resins

    International Nuclear Information System (INIS)

    Sarpal, S.K.; Gupta, A.R.

    1975-01-01

    Uranium isotope effects in exchange reactions involving hexavalent and tetravalent uranium, on ion exchange resins, have been re-examined. The earlier work on uranium isotope effects in electron exchange reactions involving hexavalent and tetravalent uranium, has been critically reviewed. New experimental data on these systems in hydrochloric acid medium, has been obtained, using break-through technique on anion-exchange columns. The isotope effects in these break-through experiments have been reinterpreted in a way which is consistent with the anion exchange behaviour of the various uranium species in these systems. (author)

  20. Synthesis and reactivity of triscyclopentadienyl uranium (III) and (IV) complexes

    International Nuclear Information System (INIS)

    Berthet, J.C.

    1992-01-01

    The reactions of (RC 5 H 4 ) 3 U with R=trimethylsilylcyclopentadienyl or tertiobutylcyclopentadienyl are studied for the synthesis of new uranium organometallic compounds. Reactions with sodium hydride are first described uranium (III) anionic hydrides obtained are oxidized for synthesis of stable uranium (IV) organometallic hydrides. Stability of these compounds is discussed. Reactivity of these uranium (III) and (IV) hydrides are studied. Formation of new binuclear compounds with strong U-O and U-N bonds is examined and crystal structure are presented. Monocyclooctatetraenylic uranium complexes are also investigated

  1. Exploring the Reaction Pathways of Bioglycerol Hydrodeoxygenation to Propene over Molybdena-Based Catalysts.

    Science.gov (United States)

    Zacharopoulou, Vasiliki; Vasiliadou, Efterpi S; Lemonidou, Angeliki A

    2018-01-10

    The one-step reaction of glycerol with hydrogen to form propene selectively is a particularly challenging catalytic pathway that has not yet been explored thoroughly. Molybdena-based catalysts are active and selective to C-O bond scission; propene is the only product in the gas phase under the standard reaction conditions, and further hydrogenation to propane is impeded. Within this context, this work focuses on the exploration of the reaction pathways and the investigation of various parameters that affect the catalytic performance, such as the role of hydrogen on the product distribution and the effect of the catalyst pretreatment step. Under a hydrogen atmosphere, propene is produced primarily via 2-propenol, whereas under an inert atmosphere propanal and glycerol dissociation products are formed mainly. The reaction most likely proceeds through a reverse Mars-van Krevelen mechanism as partially reduced Mo species drive the reaction to the formation of the desired product. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Reaction pathways for catalytic gas-phase oxidation of glycerol over mixed metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Suprun, W.; Glaeser, R.; Papp, H. [Leipzig Univ. (Germany). Inst. of Chemical Technology

    2011-07-01

    Glycerol as a main by-product from bio-diesel manufacture is a cheap raw material with large potential for chemical or biochemical transformations to value-added C3-chemicals. One possible way of glycerol utilization involves its catalytic oxidation to acrylic acid as an alternative to petrochemical routes. However, this catalytic conversion exhibits various problems such as harsh reaction conditions, severe catalyst coking and large amounts of undesired by-products. In this study, the reaction pathways for gas-phase conversion of glycerol over transition metal oxides (Mo, V und W) supported on TiO{sub 2} and SiO{sub 2} were investigated by two methods: (i) steady state experiments of glycerol oxidation and possible reactions intermediates, i.e., acrolein, 3-hydroxy propionaldehyde and acetaldehyde, and (ii) temperature-programmed surface reaction (TPSR) studies of glycerol conversion in the presence and in the absence of gas-phase oxygen. It is shown that the supported W-, V and Mo-oxides possess an ability to catalyze the oxidation of glycerol to acrylic acid. These investigations allowed us to gain a deeper insight into the reaction mechanism. Thus, based on the obtained results, three possible reactions pathways for the selective oxidation of glycerol to acrylic acid on the transition metal-containing catalysts are proposed. The major pathways in presence of molecular oxygen are a fast successive destructive oxidation of glycerol to CO{sub x} and the dehydration of glycerol to acrolein which is a rate-limiting step. (orig.)

  3. Optimization of uranium leach mining

    International Nuclear Information System (INIS)

    Schecter, R.S.; Bommer, P.M.

    1982-01-01

    The effects of well pattern and well spacing on uranium recovery and oxidant utilization are considered. As expected, formation permeability heterogeneities and anisotropies are found to be important issues requiring careful consideration; however, it also is shown that the oxidant efficiency and the produced uranium solution concentrations are sensitive to the presence of other minerals competing with uranium for oxidant. If the Damkohler number for competing minerals, which measures the speed of the reaction, exceeds that for uranium, the competing mineral will have to be oxidized completely to recover a large proportion of the uranium. If the Damkohler number is smaller, it may be possible to achieve considerable selectivity for uranium by adjusting the well spacing. 9 refs

  4. Analysis of nuclear reaction products and materials; Preliminary treatment of uranium analysis

    International Nuclear Information System (INIS)

    Soedyartomo.

    1976-01-01

    Pre-treatment of samples is necessary to be done in order to achieve the efficient steps and accurate results of uranium analysis. The pre-treatment is particularly affected by the type of sample, the uranium concentration predicated in the sample, and the uranium analytical method which will be applied. A brief discussion about the pre-treatment of uranium analysis in the uranium ore processing and the reprocessing of spent fuel is given. (author)

  5. PROCESSES OF CHLORINATION OF URANIUM OXIDES

    Science.gov (United States)

    Rosenfeld, S.

    1958-09-16

    An improvement is described in the process fur making UCl/sub 4/ from uranium oxide and carbon tetrachloride. In that process, oxides of uranium are contacted with carbon tetrachloride vapor at an elevated temperature. It has been fuund that the reaction product and yield are improved if the uranlum oxide charge is disposed in flat trays in the reaction zone, to a depth of not more than 1/2 centimeter.

  6. Some parameters of uranium hexafluoride plasma produced by products of nuclear reaction

    International Nuclear Information System (INIS)

    Batyrbekov, G.A.; Belyakova, Eh.A.

    1996-01-01

    The probe experimental results of investigation of uranium hexafluoride plasma produced in the centre of nuclear reactor core were demonstrated. Study of uranium hexafluoride plasma is continued by the following reasons: a possibility of U F 6 utilization as nuclear fuel, the utilization of U F 6 as volume source o ionization, search of active laser media compatible with U F 6 that is complicated by lack of constant rates data for most of plasma-chemical reactions with U F 6 and his dissociation products. Cylindrical probe volt-ampere characteristics (VAC) measured in U F 6 plasma at pressure 20 Torr and different thermal neutron fluxes and have following features: -firstly, it is possible to choose a linear part in the field of small positive potentials of probe (0-1) V; - secondary, ion branches of VAC have typical break which current of satiation corresponds to; -thirdly, probe VAC measured at small values of thermal neutron flux density are symmetrical. Diagnostics approaches were used for interpretation VAC of probe. The values of satiation current and linear part of electron branch were calculated, and such plasma parameters as conductivity, diffusion coefficient values of positive and negative ions were determined. The resonance recharge cross section was estimated on diffusion coefficient value

  7. Removal of uranium from uranium plant wastewater using zero-valent iron in an ultrasonic field

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jing; Zhang, Libo; Peng, Jinhui; Ma, Aiyuan; Xia, Hong Ying; Guo, Wen Qian; Yu, Xia [Yunnan Provincial Key Laboratory of Intensification Metallurgy, Kunming (China); Hu, Jinming; Yang, Lifeng [Nuclear Group Two Seven Two Uranium Industry Limited Liability Company, Hengyang (China)

    2016-06-15

    Uranium removal from uranium plant wastewater using zero-valent iron in an ultrasonic field was investigated. Batch experiments designed by the response surface methodology (RSM) were conducted to study the effects of pH, ultrasonic reaction time, and dosage of zero-valent iron on uranium removal efficiency. From the experimental data obtained in this work, it was found that the ultrasonic method employing zero-valent iron powder effectively removes uranium from uranium plant wastewater with a uranium concentration of 2,772.23 μg/L. The pH ranges widely from 3 to 7 in the ultrasonic field, and the prediction model obtained by the RSM has good agreement with the experimental results.

  8. The influence of alkali metal impurities on the uranium dioxide hydrofluorination reaction

    International Nuclear Information System (INIS)

    Ponelis, A.A.

    1989-01-01

    The effect alkali metal impurities (sodium and potassium) in the uranium dioxide (UO 2 ) feed material have on the conversion to uraniumtetrafluoride (UF 4 ) was examined. A direct correlation exists between impurity level and sintering with concomitant reduced conversion. The sintering mechanism is attributable to decreased specific surface area. The typical 'die-off' of reaction or conversion can be explained in terms of increased particle growth rather than an arbitray zero porosity function. Hydrofluorination temperatures varied from 250 to 650 degrees C using pellets varying in size from 0.42 mm to 10 mm. Scanning electron microscope photographs show clearly the particle or grain growth in the pellet as well as the increased size with impurity level. A new dimensionless constant, N KP , is defined to facilitate explanation of the reaction as a function of pellet radius. N KP is defined as the ratio of pellet diffusion resistance to particle diffusion resistance of the reacting HF gas. At high values of this number (N KP >40) the conversion is limited to the outer periphery of the pellet while at low values (N KP KP at higher reaction temperatures which means that the particle diffusion resistance increases with increasing impurity level and results in easier sintering of these materials. 53 refs., 206 figs., 94 tabs

  9. Synthesis of Uranium nitride powders using metal uranium powders

    International Nuclear Information System (INIS)

    Yang, Jae Ho; Kim, Dong Joo; Oh, Jang Soo; Rhee, Young Woo; Kim, Jong Hun; Kim, Keon Sik

    2012-01-01

    Uranium nitride (UN) is a potential fuel material for advanced nuclear reactors because of their high fuel density, high thermal conductivity, high melting temperature, and considerable breeding capability in LWRs. Uranium nitride powders can be fabricated by a carbothermic reduction of the oxide powders, or the nitriding of metal uranium. The carbothermic reduction has an advantage in the production of fine powders. However it has many drawbacks such as an inevitable engagement of impurities, process burden, and difficulties in reusing of expensive N 15 gas. Manufacturing concerns issued in the carbothermic reduction process can be solved by changing the starting materials from oxide powder to metals. However, in nitriding process of metal, it is difficult to obtain fine nitride powders because metal uranium is usually fabricated in the form of bulk ingots. In this study, a simple reaction method was tested to fabricate uranium nitride powders directly from uranium metal powders. We fabricated uranium metal spherical powder and flake using a centrifugal atomization method. The nitride powders were obtained by thermal treating those metal particles under nitrogen containing gas. We investigated the phase and morphology evolutions of powders during the nitriding process. A phase analysis of nitride powders was also a part of the present work

  10. Adsorption of uranium on halloysite

    International Nuclear Information System (INIS)

    Kilislioglu, A.; Bilgin, B.

    2002-01-01

    Adsorption of uranium (U(VI)) from aqueous solutions on halloysite type clay was studied as a function of amount of adsorbent, initial concentration and pH. The values of adsorption data were fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) adsorption isotherms. The mean energy of adsorption was calculated as 5.91 kJ/mol from D-R adsorption isotherm. Lagergren and Bangham equation has been used for dynamic modelling of process and the rate constants of adsorption of uranium on halloysite type clay were calculated at 293, 313 and 333 K. In order to explain the mechanism of adsorption reaction, the rate constants were calculated at high and low uranium concentrations. Adsorption reaction was studied at 293, 303, 313, 323 and 333 K for halloysite type clay and also thermodynamic constants have been calculated. The results show that the adsorption reaction was endothermic and more spontaneous at high temperature. (orig.)

  11. Adsorption of uranium on halloysite

    Energy Technology Data Exchange (ETDEWEB)

    Kilislioglu, A.; Bilgin, B. [Istanbul Univ. (Turkey). Faculty of Engineering

    2002-07-01

    Adsorption of uranium (U(VI)) from aqueous solutions on halloysite type clay was studied as a function of amount of adsorbent, initial concentration and pH. The values of adsorption data were fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) adsorption isotherms. The mean energy of adsorption was calculated as 5.91 kJ/mol from D-R adsorption isotherm. Lagergren and Bangham equation has been used for dynamic modelling of process and the rate constants of adsorption of uranium on halloysite type clay were calculated at 293, 313 and 333 K. In order to explain the mechanism of adsorption reaction, the rate constants were calculated at high and low uranium concentrations. Adsorption reaction was studied at 293, 303, 313, 323 and 333 K for halloysite type clay and also thermodynamic constants have been calculated. The results show that the adsorption reaction was endothermic and more spontaneous at high temperature. (orig.)

  12. Study of the Reactions Controlling the Mobility of Uranium in Ground and Surface Water Systems in Contact with Apatite

    International Nuclear Information System (INIS)

    Taffet, M

    2004-01-01

    The objective of this project was to define the mechanisms, equilibria, kinetics, and extent of sorption of aqueous uranium onto hydroxyapatite (Ca 5 (PO 4 ) 3 (OH)) for a range of pH, ionic strength, aqueous uranium concentration, dissolved carbon/air CO 2 , and mineral surface area. We conducted chemical modeling, batch and flow-through experiments, chemical analysis, x-ray absorption and diffraction measurement, and electron microscopy. Our motivation was the need to immobilize U in water and soil to prevent it's entry into water supplies and ultimately, biological systems. Applying hydroxyapatite to in-situ treatment of uranium-bearing ground water could be an effective, low cost technology. We found that hydroxyapatite quickly, effectively, and reversibly sorbed uranium at a high capacity by inner-sphere complexation over a wide range of conditions. Our results indicate that at aqueous uranium concentrations below 10-20 ppb: (1) equilibrium sorption of uranium to hydroxyapatite occurs in hours, regardless of pH; (2) in ambient and CO 2 -free atmospheres, over 98% of initial uranium is sorbed to hydroxyapatite, (3) in waters in equilibrium with higher air CO 2 concentrations, sorption removed over 97% of aqueous uranium, except above pH 9, where aqueous uranium concentrations were reduced by less than 40%, and (4) at near-neutral pH, bicarbonate alkalinities in excess of 500 slightly retarded sorption of uranium to hydroxyapatite, relative to lower alkalinities. Uranium sorption and precipitation are reversible and are not appreciably affected by ionic strength. The reversibility of these reactions requires that in situ treatment be carefully monitored to avoid breakthrough and de-sorption of uranium unto ground water. At typical surface conditions, sorption is the only mode of uranium sequestration below 20-50 ppb U - above this range, precipitation of uranium phosphate minerals begins to dominate sequestration processes. We verified that one m 2 of

  13. Method for preparation of uranium hydride

    International Nuclear Information System (INIS)

    Gorski, M.S.; Goncalves, Miriam; Mirage, A.; Lima, W. de.

    1985-01-01

    A method for preparation of Uranium Hydride starting from Hidrogen and Uranium is described. In the temperature range of 250 0 up to 350 0 C, and pressures above 10torr, Hydrogen reacts smoothly with Uranium turnings forming a fine black or dark gray powder (UH 3 ). Samples containing a significant amount of oxides show a delay before the reaction begging. (Author) [pt

  14. PROCESS FOR PREPARING URANIUM METAL

    Science.gov (United States)

    Prescott, C.H. Jr.; Reynolds, F.L.

    1959-01-13

    A process is presented for producing oxygen-free uranium metal comprising contacting iodine vapor with crude uranium in a reaction zone maintained at 400 to 800 C to produce a vaporous mixture of UI/sub 4/ and iodine. Also disposed within the maction zone is a tungsten filament which is heated to about 1600 C. The UI/sub 4/, upon contacting the hot filament, is decomposed to molten uranium substantially free of oxygen.

  15. About the elaboration of pure uranium dicarbide

    International Nuclear Information System (INIS)

    Besson, J.; Blum, P.; Guinet, Ph.; Spitz, J.

    1963-01-01

    In order to develop methods for the elaboration of as pure as possible uranium dicarbide, the authors report the study of different elaboration processes based on the reaction between uranium and carbon, or between uranium and hydrocarbon, or between uranium oxide and carbon. They finally choose a method which comprises an arc-induced fusion of a mixture of uranium dioxide and carbon. The fusion process is described. The influence of thermal treatments is discussed as well as the graphite electrode carburization

  16. Method to manufacture a nuclear fuel from uranium-plutonium monocarbide or uranium-plutonium mononitride

    International Nuclear Information System (INIS)

    Krauth, A.; Mueller, N.

    1977-01-01

    Pure uranium carbide or nitride is converted with plutonium oxide and carbon (all in powder form) to uranium-plutonium monocarbide or mononitride by cold pressing and sintering at about 1600 0 C. Pure uranium carbide or uranium nitride powder is firstly prepared without extensive safety measures. The pure uranium carbide or nitride powder can also be inactivated by using chemical substances (e.g. stearic acid) and be handled in air. The sinterable uranium carbide or nitride powder (or also granulate) is then introduced into the plutonium line and mixed with a nonstoichiometrically adjusted, prereacted mixture of plutonium oxide and carbon, pressed to pellets and reaction sintered. The surface of the uranium-plutonium carbide (higher metal content) can be nitrated towards the end of the sinter process in a stream of nitrogen. The protective layer stabilizes the carbide against the water and oxygen content in air. (IHOE) [de

  17. An integral experiment on thorium oxide/depleted uranium cylinders with D-T neutrons for 232Th(n, 2n) reaction

    International Nuclear Information System (INIS)

    Feng, S.; Yang, Y.W.; Lu, X.X.; Liu, R.; Jiang, L.; Zhu, T.H.; Wang, M.; Qin, J.G.

    2015-01-01

    Highlights: • An integral experiment for 232 Th(n, 2n) reaction was carried out on the newly-established ThO 2 /depleted uranium cylinders. • 232 Th(n, 2n) reaction rate distribution was obtained in the assemblies with an uncertainty of about 7%. • Experiments were analyzed by MCNP code with ENDF/B-VI.8, ENDF/B-VII.0, JENDL-4.0 and CENDL-3.1 libraries. • Experimental results could be used to re-evaluate the cross sections of 232 Th(n, 2n) reaction. - Abstract: In order to verify the evaluated cross sections of 232 Th(n, 2n) reaction for the conceptual design of the thorium based subcritical blanket in the fusion–fission hybrid reactor, an integral experiment on thorium oxide/depleted uranium cylinders was carried out with D-T neutrons using the activation technique. 232 Th(n, 2n) reaction rate distribution was obtained at the central axis direction in the assemblies with an uncertainty of about 7%. Experiments were analyzed by using MCNP code with ENDF/B-VI.8, ENDF/B-VII.0, JENDL-4.0 and CENDL-3.1 libraries to validate the nuclear data libraries of 232 Th(n, 2n) reaction, the calculated results with JENDL-4.0 agree with the measurements the best with discrepancies within the experimental uncertainty. The average values of C/E for the three benchmark assemblies are 1.058, 1.044 and 0.980. Calculations with different evaluated libraries in the benchmark assemblies show a large discrepancy. The experimental results can be used to re-evaluate the cross sections of the 232 Th(n, 2n) reaction

  18. Dissolution of metallic uranium and its alloys. Part 1. Review of analytical and process-scale metallic uranium dissolution

    International Nuclear Information System (INIS)

    Laue, C.A.; Gates-Anderson, D.; Fitch, T.E.

    2004-01-01

    This review focuses on dissolution/reaction systems capable of treating uranium metal waste to remove its pyrophoric properties. The primary emphasis is the review of literature describing analytical and production-scale dissolution methods applied to either uranium metal or uranium alloys. A brief summary of uranium's corrosion behavior is included since the corrosion resistance of metals and alloys affects their dissolution behavior. Based on this review, dissolution systems were recommended for subsequent screening studies designed to identify the best system to treat depleted uranium metal wastes at Lawrence Livermore National Laboratory (LLNL). (author)

  19. Dry uranium tetrafluoride process preparation using the uranium hexafluoride reconversion process effluents

    International Nuclear Information System (INIS)

    Silva Neto, Joao Batista da

    2008-01-01

    It is a well known fact that the use of uranium tetrafluoride allows flexibility in the production of uranium suicide and uranium oxide fuel. To its obtention there are two conventional routes, the one which reduces uranium from the UF 6 hydrolysis solution with stannous chloride, and the hydro fluorination of a solid uranium dioxide. In this work we are introducing a third and a dry way route, mainly utilized to the recovery of uranium from the liquid effluents generated in the uranium hexafluoride reconversion process, at IPEN/CNEN-SP. Working in the liquid phase, this route comprises the recuperation of ammonium fluoride by NH 4 HF 2 precipitation. Working with the solid residues, the crystallized bifluoride is added to the solid UO 2 , which comes from the U mini plates recovery, also to its conversion in a solid state reaction, to obtain UF 4 . That returns to the process of metallic uranium production unity to the U 3 Si 2 obtention. This fuel is considered in IPEN CNEN/SP as the high density fuel phase for IEA-R1m reactor, which will replace the former low density U 3 Si 2 -Al fuel. (author)

  20. Study of electrolytic reduction of uranium VI to uranium IV in nitrate systems

    Energy Technology Data Exchange (ETDEWEB)

    Araujo, B.F. de; Almeida, S.G. de; Forbicini, S; Matsuda, H T; Araujo, J.A. de [Instituto de Pesquisas Energeticas e Nucleares, Sao Paulo (Brazil). Centro de Engenharia Quimica

    1980-01-01

    Experimental parameters are optimized in order to obtain uranium (IV) nitrate solutions at maximum yield, using hydrazine as stabilizer. Uranium (VI) electrolytic reduction was chosen because: there is no increase in the volume of radioactive effluents; there are no secondary reactions; there is no need for further separations; all reagents used are not inflammable. The method is, therefore, efficient and of low cost.

  1. Energy consumption of chemical uranium enrichment

    International Nuclear Information System (INIS)

    Miyake, T.; Takeda, K.; Obanawa, H.

    1987-01-01

    A quantitative study of chemical separation energy for enriching uranium-235 by the redox chromatography was conducted. Isotope exchange reactions between U 4+ -UO 2 2+ ions in the enrichment column are maintained by the redox reactions. The chemical separation energy is ultimately supplied by hydrogen and oxygen gas for regenerating redox agents. The redox energy for the isotope separation is theoretically predicted as a function of the dynamic enrichment factor observed in the chromatographic development of uranium adsorption band. Thermodynamic treatments of the equilibrium reactions implies and inverse redox reaction which can be enhanced by the chemical potential of the ion-exchange reaction of oxidant. Experimental results showed 30 to 90% recovery of the redox energy by the inverse reaction. These results will devise a simplified redox chromatography process where a number of columns in one module is reduced

  2. Spectroscopic confirmation of uranium(VI)-carbonato adsorption complexes on hematite

    Science.gov (United States)

    Bargar, John R.; Reitmeyer, Rebecca; Davis, James A.

    1999-01-01

    Evaluating societal risks posed by uranium contamination from waste management facilities, mining sites, and heavy industry requires knowledge about uranium transport in groundwater, often the most significant pathway of exposure to humans. It has been proposed that uranium mobility in aquifers may be controlled by adsorption of U(VI)−carbonato complexes on oxide minerals. The existence of such complexes has not been demonstrated, and little is known about their compositions and reaction stoichiometries. We have used attenuated total reflectance Fourier transform infrared (ATR-FTIR) and extended X-ray absorption fine structure (EXAFS) spectroscopies to probe the existence, structures, and compositions of ≡FeOsurface−U(VI)−carbonato complexes on hematite throughout the pH range of uranyl uptake under conditions relevant to aquifers. U(VI)−carbonato complexes were found to be the predominant adsorbed U(VI) species at all pH values examined, a much wider pH range than previously postulated based on analogy to aqueous U(VI)−carbonato complexes, which are trace constituents at pH carbonato complexes may be of major importance to the groundwater transport of similar actinide contaminants such as neptunium and plutonium.

  3. Pathways of the Maillard reaction under physiological conditions.

    Science.gov (United States)

    Henning, Christian; Glomb, Marcus A

    2016-08-01

    Initially investigated as a color formation process in thermally treated foods, nowadays, the relevance of the Maillard reaction in vivo is generally accepted. Many chronic and age-related diseases such as diabetes, uremia, atherosclerosis, cataractogenesis and Alzheimer's disease are associated with Maillard derived advanced glycation endproducts (AGEs) and α-dicarbonyl compounds as their most important precursors in terms of reactivity and abundance. However, the situation in vivo is very challenging, because Maillard chemistry is paralleled by enzymatic reactions which can lead to both, increases and decreases in certain AGEs. In addition, mechanistic findings established under the harsh conditions of food processing might not be valid under physiological conditions. The present review critically discusses the relevant α-dicarbonyl compounds as central intermediates of AGE formation in vivo with a special focus on fragmentation pathways leading to formation of amide-AGEs.

  4. The kinetics of the cerium(IV)-uranium(IV) reaction at low sulfate concentrations

    International Nuclear Information System (INIS)

    Michaille, P.; Kikindai, T.

    1977-01-01

    The rate of oxidation of uranium(IV) by cerium(IV) was measured with a stopped-flow spectrophotometer at sulfuric acid concentrations of 2 x 10 -6 to 0.5 M. At a constant hydrogen ion concentration of 0.5 M, the maximum rate constant was observed for 2 x 10 -3 M sulfuric acid; at that concentration, two sulfate ions were involved in the activated complex. The dependence of the rate constant on the hydrogen ion concentration showed that the reaction paths involving one or two sulfate ions also involved one hydroxyl ion, whereas one hydrogen ion was involved in the five sulfate dependent path. Spectrophotometric measurements supported the existence of a hydrolyzed monosulfatocomplex of cerium(IV). (author)

  5. Purification of hydrogen under a free or combined form in a gaseous mixture, by chemical reactions with uranium

    International Nuclear Information System (INIS)

    Caron Charles, M.

    1988-03-01

    Within the framework of the european fusion program, we are dealing with the purification of hydrogen (tritium) under a free or combined form, from a H 2 , N 2 , NH 3 , CH 4 , O 2 , gaseous mixture. The process consists in cracking the hydrogenated molecules and absorbing the impurities by chemical reactions with uranium, without holding back hydrogen. In the temperature range: 950 K [fr

  6. Reaction pathways of the dissociation of methylal: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Frey, H -M; Beaud, P; Gerber, T; Mischler, B; Radi, P P; Tzannis, A -P [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    Schemata for modelling combustion processes do not yet include reaction rates for oxygenated fuels like methylal (DMM) which is considered as an additive or replacement for diesel due to its low sooting propensity. Density functional theory (DFT) studies of the possible reaction pathways for different dissociation steps of methylal are presented. Cleavage of a hydrogen bond to the methoxy group or the central carbon atom were simulated at the BLYP/6-311++G{sup **} level of theory. The results are compared to the experiment when dissociating and/or ionising DMM with femtosecond pulses. (author) 1 fig., 1 tab., 1 ref.

  7. Intermediate- and high-energy reactions of uranium with neon and carbon

    International Nuclear Information System (INIS)

    McGaughey, P.L.

    1982-11-01

    Target fragment production from the interactions of 1.0, 3.0, 4.8, and 12 GeV 12 C and 5.0, 8.0, 20, and 42 GeV 20 Ne with uranium has been measured using off-line gamma-ray spectroscopic techniques. The experimental charge and mass yield distributions are generally consistent with the concepts of limiting fragmentation and factorization at energies of 3.0 GeV and above. The total projectile kinetic energy was found to be the relevant scaling parameter for the comparison of reactions induced by projectiles of different sizes. Light fragments with mass number less than 60 were found to violate limiting fragmentation, and had excitation functions that were strongly increasing with projectile energy until 8.0 to 12.0 GeV. With the 1.0 GeV 12 C beam the pattern of mass yields was quite different from that of all the other reactions, with the normal peak in the fission mass region (80 < A < 145), but with much lower yields below mass number 60 and between mass numbers 145 and 210, indicating that these fragments are formed primarily in very energetic reactions in which large excitation energies are transferred to and significant amounts of mass are removed from the target nucleus. Theoretical predictions of the intra-nuclear cascade, nuclear fireball, and nuclear firestreak models are compared with the experimental results. The intra-nuclear cascade and nuclear firestreak models are both able to predict the general shapes of the experimental distributions, with the exception of the yields for the lightest fragments

  8. Sensitivity analysis of uranium solubility under strongly oxidizing conditions

    International Nuclear Information System (INIS)

    Liu, L.; Neretnieks, I.

    1999-01-01

    To evaluate the effect of geochemical conditions in the repository on the solubility of uranium under strongly oxidizing conditions, a mathematical model has been developed to determine the solubility, by utilizing a set of nonlinear algebraic equations to describe the chemical equilibria in the groundwater environment. The model takes into account the predominant precipitation-dissolution reactions, hydrolysis reactions and complexation reactions that may occur under strongly oxidizing conditions. The model also includes the solubility-limiting solids induced by the presence of carbonate, phosphate, silicate, calcium, and sodium in the groundwater. The thermodynamic equilibrium constants used in the solubility calculations are essentially taken from the NEA Thermochemical Data Base of Uranium, with some modification and some uranium minerals added, such as soddyite, rutherfordite, uranophane, uranyl orthophosphate, and becquerelite. By applying this model, the sensitivities of uranium solubility to variations in the concentrations of various groundwater component species are systematically investigated. The results show that the total analytical concentrations of carbonate, phosphate, silicate, and calcium in deep groundwater play the most important role in determining the solubility of uranium under strongly oxidizing conditions

  9. Development of empirical relation for isotope of uranium in enriched uranium matrix

    International Nuclear Information System (INIS)

    Srivastava, S.K.; Vidyasagar, D.; Jha, S.K.; Tripathi, R.M.

    2018-01-01

    Uranium enriched in 235 U is required in commercial light water reactors to produce a controlled nuclear reaction. Enrichment allows the 235 U isotopes to be increased from 0.71% to a range between 2% to 5% depending upon requirement. The enriched uranium in the form of sintered UO 2 pellet is used for any commercially operating boiling light water reactors. The enriched uranium fuel bundle surface swipes sample is being analysed to assess the tramp uranium as a quality control parameter. It is known that the 234 U isotope also enriched along with 235 U isotope in conventional gaseous diffusion enrichment process. The information about enrichment percentage of 234 U helps to characterize isotopic properties of enriched uranium. A few reports provide the empirical equation and graphs for finding out the specific activity, activity percentage, activity ratio of 234 U isotopes for enriched uranium. Most of them have not provided the reference for the data used and their source. An attempt has been made to model the relationship between 234 U and 235 U as a function of uranium enrichment at low level

  10. On the separation of so-called non-volatile uranium fission products of uranium using the conversion of neutron-irradiated uranium dioxide and graphite

    International Nuclear Information System (INIS)

    Elhardt, W.

    1979-01-01

    The investigations are continued in the following work which arose from the concept of separating uranium fission products from uranium. This is achieved in that due to the lattice conversions occurring during the course of solid chemical reactions, fission products can easily pass from the uranium-contained solid to a second solid. The investigations carried out primarily concern the release behaviour of cerium and neodymium in the temperature region of 1200 to 1700 0 C. UO 2 + graphite, both in powder form, are selected as suitable reaction system having the preconditions needed for the lattice conversion for the release effect. The target aimed at from the practical aspect for the improved release of lanthanoids is achieved by an isobar test course - changing temperature from 1200 to 1500 0 C at constant pressure, with a cerium release of 75-80% and a neodynium release of 80-90% (maximum at 1400 0 C). The concepts on the mechanism of the fission product release are related to transport processes in crystal lattices, as well as chemical solid reactions and evaporation processes on the surface of UC 2 grains. (orig./RB) [de

  11. Synthesis of UN coatings on uranium

    International Nuclear Information System (INIS)

    Mar, R.W.; Hastings, J.C.

    1975-04-01

    A single-displacement reaction approach was used to form uranium mononitride as a protective coating for uranium; the source of the nitrogen was a solid nitride, and magnesium nitride was chosen as the most attractive candidate for the experiment. While the goal of synthesizing a single-phase uranium mononitride coating at temperatures lower than 1405 K was met, a number of problems inherent in the process were identified. 6 figures, 2 tables

  12. Position-specific isotope modeling of organic micropollutants transformation through different reaction pathways

    International Nuclear Information System (INIS)

    Jin, Biao; Rolle, Massimo

    2016-01-01

    The degradation of organic micropollutants occurs via different reaction pathways. Compound specific isotope analysis is a valuable tool to identify such degradation pathways in different environmental systems. We propose a mechanism-based modeling approach that provides a quantitative framework to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. To demonstrate specific features of the modeling approach, we simulated the degradation of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model accurately reproduces the multi-element isotope data observed in previous experimental studies. Furthermore, it precisely captures the dual element isotope trends characteristic of different reaction pathways as well as their range of variation consistent with observed bulk isotope fractionation. It was also possible to directly validate the model capability to predict the evolution of position-specific isotope ratios with available experimental data. Therefore, the approach is useful both for a mechanism-based evaluation of experimental results and as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available. - Highlights: • Mechanism-based, position-specific isotope modeling of micropollutants degradation. • Simultaneous description of concentration and primary and secondary isotope effects. • Key features of the model are demonstrated with three illustrative examples. • Model as a tool to explore reaction mechanisms and to design experiments. - We propose a modeling approach incorporating mechanistic information and

  13. Bioaccumulation of uranium and thorium from the solution containing both elements using various microorganisms

    International Nuclear Information System (INIS)

    Tsuruta, T.

    2006-01-01

    The effects of proton, thorium and uranium on the bioaccumulation of thorium and uranium from the solution (pH 3.5) containing uranium and thorium using Streptomyces levoris cells were examined. The amount of thorium accumulated using the cells decreased by the pre-contact between the cells and the solution (pH 3.5) containing no metals, whereas that of uranium was almost unaffected by the treatment. The amount of thorium was almost unaffected by the existence of uranium. On the other hand, the amount of uranium accumulated was strongly affected by the thorium, especially thorium addition after uranium accumulation. The decrease of uranium accumulated by the addition of thorium after the accumulation of uranium was higher than that from the solution containing both elements. Therefore, the contribution of uranium-thorium exchange reaction was higher than that of competition reaction. Accordingly, proton-uranium-thorium exchange reaction was occurred in the accumulation of thorium from the solution containing thorium and uranium. The gram-positive bacteria, such as Micrococcus luteus, Arthrobacter nicotianae, Bacillus subtilis and B. megaterium, has a much higher separation factor as thorium/uranium than that of actinomycetes. These gram-positive bacterial strains can be used for the accumulation of thorium from the solution containing uranium and thorium

  14. The reaction of uranium in the U-O2-H2O and U-H2O systems

    International Nuclear Information System (INIS)

    Pearce, R.J.; Kay, P.

    1987-09-01

    The reaction of uranium in dry air, moist air and oxygen free moisture has been studied thermogravimetrically over the temperature range 105-325 0 C and at water vapour pressures up to 100 kPa. It has been shown that in dry air the kinetics are complex and appear to result from parallel reactions involving both parabolic and linear rate laws. In oxygen free moisture, linear kinetics were obeyed and a near stoichiometric UO 2 reaction product was formed. Oxygen markedly inhibited the moisture reaction at the lower temperatures in the range examined but the degree of inhibition, as shown by weight gain measurements, decreased with increasing temperature such that, at the higher temperatures, there was little difference in reaction rates. At all temperatures, the production of hydrogen was markedly inhibited by the presence of air suggesting that the principal reaction was with free oxygen. However in moist conditions the reaction rate exhibited a dependency on the water vapour pressure according to k α psup(n) where n ∼ 0.3 in air and ∼ 0.5 in oxygen free conditions. The mechanism of the oxidation reaction is discussed. (author)

  15. Reaction pathways of producing and losing particles in atmospheric pressure methane nanosecond pulsed needle-plane discharge plasma

    Science.gov (United States)

    Zhao, Yuefeng; Wang, Chao; Li, Li; Wang, Lijuan; Pan, Jie

    2018-03-01

    In this work, a two-dimensional fluid model is built up to numerically investigate the reaction pathways of producing and losing particles in atmospheric pressure methane nanosecond pulsed needle-plane discharge plasma. The calculation results indicate that the electron collisions with CH4 are the key pathways to produce the neutral particles CH2 and CH as well as the charged particles e and CH3+. CH3, H2, H, C2H2, and C2H4 primarily result from the reactions between the neutral particles and CH4. The charge transfer reactions are the significant pathways to produce CH4+, C2H2+, and C2H4+. As to the neutral species CH and H and the charged species CH3+, the reactions between themselves and CH4 contribute to substantial losses of these particles. The ways responsible for losing CH3, H2, C2H2, and C2H4 are CH3 + H → CH4, H2 + CH → CH2 + H, CH4+ + C2H2 → C2H2+ + CH4, and CH4+ + C2H4 → C2H4+ + CH4, respectively. Both electrons and C2H4+ are consumed by the dissociative electron-ion recombination reactions. The essential reaction pathways of losing CH4+ and C2H2+ are the charge transfer reactions.

  16. Airborne uranium, its concentration and toxicity in uranium enrichment facilities

    International Nuclear Information System (INIS)

    Thomas, J.; Mauro, J.; Ryniker, J.; Fellman, R.

    1979-02-01

    The release of uranium hexafluoride and its hydrolysis products into the work environment of a plant for enriching uranium by means of gas centrifuges is discussed. The maximum permissible mass and curie concentration of airborne uranium (U) is identified as a function of the enrichment level (i.e., U-235/total U), and chemical and physical form. A discussion of the chemical and radiological toxicity of uranium as a function of enrichment and chemical form is included. The toxicity of products of UF 6 hydrolysis in the atmosphere, namely, UO 2 F 2 and HF, the particle size of toxic particulate material produced from this hydrolysis, and the toxic effects of HF and other potential fluoride compounds are also discussed. Results of an investigation of known effects of humidity and temperature on particle size of UO 2 F 2 produced by the reaction of UF 6 with water vapor in the air are reported. The relationship of the solubility of uranium compounds to their toxic effects was studied. Identification and discussion of the standards potentially applicable to airborne uranium compounds in the working environment are presented. The effectiveness of High Efficiency Particulate (HEPA) filters subjected to the corrosive environment imposed by the presence of hydrogen fluoride is discussed

  17. Computed Potential Energy Surfaces and Minimum Energy Pathway for Chemical Reactions

    Science.gov (United States)

    Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

    1994-01-01

    Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO and soot formation in hydrocarbon combustion are discussed.

  18. Uranium fluoride and metallic uranium as target materials for heavy-element experiments at SHIP

    Energy Technology Data Exchange (ETDEWEB)

    Kindler, Birgit [Gesellschaft fuer Schwerionenforschung (GSI), Planckstrasse 1, D-64291 Darmstadt (Germany)], E-mail: b.kindler@gsi.de; Ackermann, Dieter; Hartmann, Willi; Hessberger, Fritz Peter; Hofmann, Sigurd; Huebner, Annett; Lommel, Bettina; Mann, Rido; Steiner, Jutta [Gesellschaft fuer Schwerionenforschung (GSI), Planckstrasse 1, D-64291 Darmstadt (Germany)

    2008-06-01

    In this contribution we describe the production and application of uranium targets for synthesis of heavy elements. The targets are prepared from uranium fluoride (UF{sub 4}) and from metallic uranium with thin carbon foils as backing. Targets of UF{sub 4} were produced by thermal evaporation in a similar way as the frequently applied targets out of Bi, Bi{sub 2}O{sub 3}, Pb, PbS, SmF{sub 3}, and NdF{sub 3,} prepared mostly from isotopically enriched material [Birgit Kindler, et al., Nucl. Instr. and Meth. A 561 (2006) 107; Bettina Lommel, et al., Nucl. Instr. and Meth. A 561 (2006) 100]. In order to use more intensive beams and to avoid scattering of the reaction products in the target, metallic uranium is favorable. However, evaporation of metallic uranium is not feasible at a sustainable yield. Therefore, we established magnetron sputtering of metallic uranium. We describe production and properties of these targets. First irradiation tests show promising results.

  19. Reaction of uranium (IV) with xenon difluoride by chemiluminescence, spectrophotometric, and spectrofluorimetric methods

    Energy Technology Data Exchange (ETDEWEB)

    Mamykin, A.V.; Kazakov, V.P.

    1988-07-01

    A study is made of the kinetics of the chemiluminescent reaction of oxidation of uranium (IV) by xenon difluoride in 1M HClO/sub 4/ U/sup 4 +/ + XeF/sub 2/ ..-->.. UO/sub 2//sup 2 +/ = h/eta/. The optical density D and the intensity of the photoluminescence of the solution I/sub PL/ were measured in parallel with recording of the luminescence intensity I/sub CL/. I/sub CL/ attains a maximum value some time after the beginning of the reaction, after which it decays exponentially. On the kinetic curves of the time dependence of D and I/sub PL/ an induction period is observed, the extent of which depends on concentrations of reagents and temperature of the solution. The maximum of I/sub CL/ coincides with the end of the induction period if the measurements are carried out under identical conditions. The rate of the reaction after the induction period is described by a first order equation in U/sup (IV)/. The rate constants of the reaction, obtained by chemiluminescence, spectrophotometric, and spectrofluorimetric methods, have close values 2.0 +- 0.4, 1.8 +- 0.3, and 2.1 +- 0.3 sec/sup /minus/1/ x 10/sup 2/, respectively. On the basis of the results obtained, we conclude that the stages of formation of UO/sub 2//sup 2 +/ and of chemiluminescence coincide, i.e., formation of the excited state (UD/sub 2//sup 2 +/) and of chemiluminescence coincide, i.e., formation of the excited state (UD/sub 2//sup 2 +/)* takes place during the reaction. It is proposed and experimentally verified that the reaction passes through an intermediate stage of formation of uranyl ion UO/sub 2//sup +/.

  20. Synthesis of uranium metal using laser-initiated reduction of uranium tetrafluoride by calcium metal

    International Nuclear Information System (INIS)

    West, M.H.; Martinez, M.M.; Nielsen, J.B.; Court, D.C.; Appert, Q.D.

    1995-09-01

    Uranium metal has numerous uses in conventional weapons (armor penetrators) and nuclear weapons. It also has application to nuclear reactor designs utilizing metallic fuels--for example, the former Integral Fast Reactor program at Argonne National Laboratory. Uranium metal also has promise as a material of construction for spent-nuclear-fuel storage casks. A new avenue for the production of uranium metal is presented that offers several advantages over existing technology. A carbon dioxide (CO 2 ) laser is used to initiate the reaction between uranium tetrafluoride (UF 4 ) and calcium metal. The new method does not require induction heating of a closed system (a pressure vessel) nor does it utilize iodine (I 2 ) as a chemical booster. The results of five reductions of UF 4 , spanning 100 to 200 g of uranium, are evaluated, and suggestions are made for future work in this area

  1. Recovery and treatment of uranium from uranium-containing solution by liquid membrane emulsion technology

    International Nuclear Information System (INIS)

    Xia Liangshu; Zhou Yantong; Xiao Yiqun; Peng Anguo; Xiao Jingshui; Chen Wei

    2014-01-01

    The recovery and treatment of uranium from uranium-containing solution using liquid membrane emulsion (LME) technology were studied in this paper, which contained the best volume ratio of membrane materials, stirring speed during emulsion process, the conditions of extracting, such as temperature, pH, initial concentration of uranium. Moreover, the mechanism for extracting uranium was also discussed. The best experimental conditions of emulsifying were acquired. The volume fractions of P 204 and liquid paraffin are 0.1 and 0.05, the volume ratios of Span80 and sulphonated kerosene to P 204 are 0.06 and 0.79 respectively, stirring speed is controlled in 2 000 r/min, and the concentration of inner phase is 4 mol/L. The recovery rate of uranium is up to 99% through the LME extracted uranium for 0.5 h at pH 2.5 and room temperature when the initial concentration is less than 400 mg/L and the volume ratio is 5 between the uranium-containing waste water and LME. The calculation results of Gibbs free energy show that the reaction process is spontaneous. (authors)

  2. Kinetic study of uranium carburization by different carbonated gases

    International Nuclear Information System (INIS)

    Feron, Guy

    1963-01-01

    The kinetic study of the reaction U + CO 2 and U + CO has been performed by a thermogravimetric method on a spherical uranium powder, in temperature ranges respectively from 460 to 690 deg. C and from 570 to 850 deg. C. The reaction with carbon dioxide leads to uranium dioxide. A carbon deposition takes place at the same time. The global reactions is the result of two reactions: U + 2 CO 2 → UO 2 + 2 CO U + CO 2 → UO 2 + C The reaction with carbon monoxide leads to a mixture of dioxide UO 2 , dicarbide UC 2 and free carbon. The main reaction can be written. U + CO → 1/2 UO 2 + 1/2 UC 2 The free carbon results of the disproportionation of the carbon monoxide. A remarkable separation of the two phases UO 2 and UC 2 can be observed. A mechanism accounting for the phenomenon has been proposed. The two reactions U + CO 2 and U + CO begin with a long germination period, after which, the reaction velocity seems to be limited in both cases by the ionic diffusion of oxygen through the uranium dioxide. (author) [fr

  3. Comparison of the Environment, Health, And Safety Characteristics of Advanced Thorium- Uranium and Uranium-Plutonium Fuel Cycles

    Science.gov (United States)

    Ault, Timothy M.

    -level waste volumes slightly favor the closed uranium option, although uncertainties are significant in both cases. The high-level waste properties (radioactivity, decay heat, and ingestion radiotoxicity) all significantly favor the closed fuel cycle options (especially the closed thorium option), but an alternative measure of key fission product inventories that drive risk in a repository slightly favors the uranium fuel cycles due to lower production of iodine-129. Resource requirements are much lower for the closed fuel cycle options and are relatively similar between thorium and uranium. In additional to the steady-state results, a variety of potential transition pathways are considered for both uranium and thorium fuel cycle end-states. For dose, low-level waste, and fission products contributing to repository risk, the differences among transition impacts largely reflected the steady-state differences. However, the HLW properties arrived at a distinctly opposite result in transition (strongly favoring uranium, whereas thorium was strongly favored at steady-state), because used present-day fuel is disposed without being recycled given that uranium-233, rather than plutonium, is the primarily fissile nuclide at the closed thorium fuel cycle's steady-state. Resource consumption was the only metric was strongly influenced by the specific transition pathway selected, favoring those pathways that more quickly arrived at steady-state through higher breeding ratio assumptions regardless of whether thorium or uranium was used.

  4. Reaction of UO/sub 2//sup 2 +/ with Chromazurol S and the spectrophotometric determination of uranium in the presence of Septonex

    Energy Technology Data Exchange (ETDEWEB)

    Kanicky, V [Geological Survey Ostrava, Establishment Brno (Czechoslovakia); Havel, J; Sommer, L [Universita J.E. Purkyne, Brno (Czechoslovakia). Prirodovedecka Fakulta

    1980-05-01

    A detailed study is described of the reaction of UO/sub 2//sup 2 +/ with chromazurol S in the presence of cationic surfactant Septonex which was found to be very promising of the group of cationic surfactants. A number of conclusions were drawn regarding the effect of the cationic surfactant on the reaction of triphenylmethane dyes with salicylic acid groups with metal cations. The optimum conditions for the spectrophotometric determination of uranium with chromazurol S in the presence of Septonex were found.

  5. Uranium ... long-term confidence

    International Nuclear Information System (INIS)

    Anon.

    1983-01-01

    Half way through 1983 the outlook for the world's uranium producers was far from bright if one takes a short term view. The readily accessible facts present a gloomy picture. The spot prices of uranium over the past few years decreased from a high of $42-$43/lb to a low of $17 in 1982. It now hovers between $23 and $24. the contract prices negotiated between producers and consumers are not so accessible but they do not reflect the spot price. The reasons why contractual uranium prices do not follow the usual dictates of supply and demand are related to the position in which uranium and associated power industries find themselves. There is public reaction with strong emotional overtones as well as much reduced expectations about the electric power needs of the world. Furthermore the supply of uranium is not guaranteed despite present over production. However the people in the industry, taking the medium- and long-term view, are not despondent

  6. Uranium tetrafluoride production via dioxide by wet process

    International Nuclear Information System (INIS)

    Aquino, A.R. de.

    1988-01-01

    The study for the wet way obtention of uranium tetrafluoride by the reaction of hydrofluoric acid and powder uranium dioxide, is presented. From the results obtained at laboratory scale a pilot plant was planned and erected. It is presently in operation for experimental data aquisition. Time of reaction, temperature, excess of reagents and the hydrofluoric acid / uranium dioxide ratio were the main parameters studied to obtain a product with the following characteristics: - density greater than 1 g/cm 3 , conversion rate greater than 96%, and water content equal to 0,2% that allows its application to heaxafluoride convertion or to magnesiothermic process. (author) [pt

  7. Thermal simulation of the magnesium thermal of metallic uranium reduction

    International Nuclear Information System (INIS)

    Borges, W.A.; Saliba-Silva, A.M.

    2008-01-01

    Metallic uranium production is vital to fabricate fuel elements for nuclear research reactors and to produce radioisotopes and radiopharmaceuticals. Metallic uranium is got via magnesiothermal reduction of UF 4 . This reaction is carried out inside a closed graphite crucible inserted in a metallic reactor adequately sealed without any outside contact. The assembled set is gradually heated up inside a pit furnace up to reach the reaction ignition temperature (between 600-650 deg C). The optimization of the reactive system depends on the mathematical modeling using simulation by finite elements and computational calculation with specialized programs. In this way, the reactants' thermal behavior is forecast until they reach the ignition temperature. The optimization of the uranium production reaction is based on minimization of thermal losses using better the exo thermal reaction heat. As lower the thermal losses, as higher would be the heat amount to raise the temperature of reaction products. This promotes the adequate melting of uranium and slag, so allowing better metal/slag separation with higher metallic yield. This work shows how the mathematical simulation is made and supplies some preliminary results. (author)

  8. Method of precipitating uranium from an aqueous solution and/or sediment

    Science.gov (United States)

    Tokunaga, Tetsu K; Kim, Yongman; Wan, Jiamin

    2013-08-20

    A method for precipitating uranium from an aqueous solution and/or sediment comprising uranium and/or vanadium is presented. The method includes precipitating uranium as a uranyl vanadate through mixing an aqueous solution and/or sediment comprising uranium and/or vanadium and a solution comprising a monovalent or divalent cation to form the corresponding cation uranyl vanadate precipitate. The method also provides a pathway for extraction of uranium and vanadium from an aqueous solution and/or sediment.

  9. Reactivity of Uranium and Ferrous Iron with Natural Iron Oxyhydroxides.

    Science.gov (United States)

    Stewart, Brandy D; Cismasu, A Cristina; Williams, Kenneth H; Peyton, Brent M; Nico, Peter S

    2015-09-01

    Determining key reaction pathways involving uranium and iron oxyhydroxides under oxic and anoxic conditions is essential for understanding uranium mobility as well as other iron oxyhydroxide mediated processes, particularly near redox boundaries where redox conditions change rapidly in time and space. Here we examine the reactivity of a ferrihydrite-rich sediment from a surface seep adjacent to a redox boundary at the Rifle, Colorado field site. Iron(II)-sediment incubation experiments indicate that the natural ferrihydrite fraction of the sediment is not susceptible to reductive transformation under conditions that trigger significant mineralogical transformations of synthetic ferrihydrite. No measurable Fe(II)-promoted transformation was observed when the Rifle sediment was exposed to 30 mM Fe(II) for up to 2 weeks. Incubation of the Rifle sediment with 3 mM Fe(II) and 0.2 mM U(VI) for 15 days shows no measurable incorporation of U(VI) into the mineral structure or reduction of U(VI) to U(IV). Results indicate a significantly decreased reactivity of naturally occurring Fe oxyhydroxides as compared to synthetic minerals, likely due to the association of impurities (e.g., Si, organic matter), with implications for the mobility and bioavailability of uranium and other associated species in field environments.

  10. Kinetic and reaction pathways of methanol oxidation on platinum

    International Nuclear Information System (INIS)

    McCabe, R.W.; McCready, D.F.

    1986-01-01

    Methanol oxidation kinetics were measured on Pt wires in a flow reactor at pressures between 30 and 130 Pa. The kinetics were measured as a function of oxygen-to-methanol equivalence ratio phi and wire temperature. In methanol-lean feeds (phi 2 CO, CO 2 , and H 2 O were the only products; in methanol-rich feeds (phi > 1), CO, H 2 , H 2 CO, CO 2 , and H 2 O were observed. Experiments with 18 O 2 showed that the principal methanol oxidation pathway does not involve C-O bond dissociation. However, the 18 O 2 experiments, together with other features of the methanol oxidation data, also provided evidence for a minor oxidation pathway (accounting for less than 1% of the product CO 2 ) which proceeds through a carbon intermediate. A mathematical model is presented which describes the principal CH 3 OH oxidation pathway as a series reaction involving adsorbed H 2 CO and CO intermediates. Consistent with experimental results, the model predicts that inhibition by adsorbed CO should be weaker for CH 3 OH and H 2 CO oxidation than for CO oxidation. 34 references, 10 figures, 2 tables

  11. Hydrogen oxidation mechanisms on Ni/yttria stabilized zirconia anodes: Separation of reaction pathways by geometry variation of pattern electrodes

    Science.gov (United States)

    Doppler, M. C.; Fleig, J.; Bram, M.; Opitz, A. K.

    2018-03-01

    Nickel/yttria stabilized zirconia (YSZ) electrodes are affecting the overall performance of solid oxide fuel cells (SOFCs) in general and strongly contribute to the cell resistance in case of novel metal supported SOFCs in particular. The electrochemical fuel conversion mechanisms in these electrodes are, however, still only partly understood. In this study, micro-structured Ni thin film electrodes on YSZ with 15 different geometries are utilized to investigate reaction pathways for the hydrogen electro-oxidation at Ni/YSZ anodes. From electrodes with constant area but varying triple phase boundary (TPB) length a contribution to the electro-catalytic activity is found that does not depend on the TPB length. This additional activity could clearly be attributed to a yet unknown reaction pathway scaling with the electrode area. It is shown that this area related pathway has significantly different electrochemical behavior compared to the TPB pathway regarding its thermal activation, sulfur poisoning behavior, and H2/H2O partial pressure dependence. Moreover, possible reaction mechanisms of this reaction pathway are discussed, identifying either a pathway based on hydrogen diffusion through Ni with water release at the TPB or a path with oxygen diffusion through Ni to be a very likely explanation for the experimental results.

  12. Risk evaluation of uranium mining: a new kinetic approach

    Energy Technology Data Exchange (ETDEWEB)

    Scislewski, Alexandro [Brazilian Nuclear Energy Comission (CNEN), Avenida Santana, 680, Centro, Caetite-Bahia, 46400-000 (Brazil); Zuddas, Pierpaolo [Universite Pierre et Marie Curie, Paris-Sorbonne, ISTEP place Jussieu, Tour 56-55, case 116, F75252 Paris Cedex 05 (France)

    2013-07-01

    Release of uranium and associated heavy metals is the main environmental concern regarding exploitation and processing of U-ore. Increasing uranium mining activities potentially increase the risks linked to radiation exposure. As a tool to evaluate these risks, a geochemical inverse modeling approach was developed to estimate the water-mineral interaction in the presence of uranium. Our methodology is based on the estimation of dissolution rate and reactive surface area of the different minerals participating in the reaction by reconstructing the chemical evolution of the interacting fluids. We found that the reactive surface area of parent-rock minerals changes over several orders of magnitude during the investigated reaction time. We propose that the formation of coatings on dissolving mineral surfaces significantly reduces reactivity. Our results show that negatively charged uranium complexes decrease when alkalinity and rock buffer capacity is similarly lower, indicating that the dissolved carbonate is an important parameter impacting uranium mobility. (authors)

  13. Risk evaluation of uranium mining: a new kinetic approach

    International Nuclear Information System (INIS)

    Scislewski, Alexandro; Zuddas, Pierpaolo

    2013-01-01

    Release of uranium and associated heavy metals is the main environmental concern regarding exploitation and processing of U-ore. Increasing uranium mining activities potentially increase the risks linked to radiation exposure. As a tool to evaluate these risks, a geochemical inverse modeling approach was developed to estimate the water-mineral interaction in the presence of uranium. Our methodology is based on the estimation of dissolution rate and reactive surface area of the different minerals participating in the reaction by reconstructing the chemical evolution of the interacting fluids. We found that the reactive surface area of parent-rock minerals changes over several orders of magnitude during the investigated reaction time. We propose that the formation of coatings on dissolving mineral surfaces significantly reduces reactivity. Our results show that negatively charged uranium complexes decrease when alkalinity and rock buffer capacity is similarly lower, indicating that the dissolved carbonate is an important parameter impacting uranium mobility. (authors)

  14. Oxidation of uranium and uranium alloys

    International Nuclear Information System (INIS)

    Orman, S.

    1976-01-01

    The corrosion behaviour of uranium in oxygen, water and water + oxygen mixtures is compared and contrasted. A considerable amount of work, much of it conflicting, has been published on the U + H 2 O and U + H 2 O + O 2 systems. An attempt has been made to summarise this data and to explain the reasons for the lack of agreement between the experimental results. The evidence for the mechanism involving OH - ion diffusion as the reacting entity in both the U + H 2 O and U + O 2 + H 2 O reactions is advanced. The more limited corrosion data on some lean uranium alloys and on some higher addition alloys referred to as stainless materials is summarised together with some previously unreported results obtained with these materials at AWRE. The data indicates that in the absence of oxygen the lean alloys behave in a similar manner to uranium and evolve hydrogen in approximately theoretical quantities. But the stainless alloys absorb most of the product hydrogen and assessments of reactivity based on hydrogen evolution would be very inaccurate. The direction that future corrosion work on these materials should take is recommended

  15. Deep groundwater redox reactions in the Palmottu uranium deposit: The role of uranium and iron in these processes

    International Nuclear Information System (INIS)

    Bruno, J.; Cera, E.; Duro, L.; Ahonen, L.

    1996-12-01

    The reduction oxidation properties of the deep bedrock and groundwater are important geochemical factors with respect to the chemical stability of the multibarrier system, which isolates the disposed nuclear fuel from biosphere. In the report are described the results of the redox experiments carried out in the field using the natural groundwaters of Palmottu, in Nummi-Pusula, Finland. The experiments include (1) measurements of natural water redox potential values during four to eight hours continuous pumping; (2) monitoring of the redox-potential response to an artificial change of pH of the groundwater. Separate tests were made in iron and uranium-rich groundwaters, respectively. The data of the field experiments were used in the redox-modelling of the iron and uranium systems. In accordance with earlier knowledge, it was showed that dissolved iron is an important redox electrolyte in natural waters, at least at concentration levels of milligrams per liter. However, a striking observation was that in the absence of dissolved iron dissolved uranium (in concentrations of about 200 nM or more) seems to be able to give nernstian response on platinum electrode in acid/base titrations. The effective redox properties of the bedrock-groundwater system depend on the availability and reactivity of solid phases able to exchange electrons with dissolved redox electrolytes. The present results indicate that, in the bedrock/groundwater system of the Palmottu uranium mineralization, uranium minerals are important redox buffers. (orig.) (refs.)

  16. Electrochemical preparation of new uranium oxide phases

    International Nuclear Information System (INIS)

    Smolenskij, V.V.; Lyalyushkin, N.V.; Bove, A.L.; Komarov, V.K.; Kapshukov, I.I.

    1992-01-01

    Behaviour of uranium ions in oxidation states 3+ and 4+ in molten chlorides of alkali metals in the temperature range of 700-900 degC in the atmosphere of an inert gas was studied by the method of cyclic voltametry. It is shown that as a result of introduction of crystal uranium dioxide into the salt melt formation of uranium oxide ions of the composition UO + and UO 2+ occurs, the ions participating in electrode reactions and bringing about formation of the following uranium oxides on the cathode: UO and, presumably, U 3 O 4 . Oxides UO and U 3 O 4 are thermodynamically unstable at low temperatures and decompose into uranium oxide of the composition UO 2-x , where x varies from 0 to 0.05, and metal uranium

  17. Extraction photometric determination of uranium (6) with use of malachite green

    International Nuclear Information System (INIS)

    Stepanenko, Yu.V.; Bagdasarov, K.N.; Shchemeleva, G.G.

    1975-01-01

    A study of the reaction between uranium (6) and malachite green in the presence of sodium benzoate has indicated that, in a weakly acid medium (pH 4.5 to 5.5), the reaction yields a poorly soluble greenish compound which tends to be extracted by a 1-to-1 mixture of benzene and chloroform. The compound comprises uranium, a benzoate and a malachite green in a ratio of 1/3/1. A method has been developed for an extraction-photometric determination of uranium in metallic lead

  18. Extraction photometric determination of uranium (6) with use of malachite green

    Energy Technology Data Exchange (ETDEWEB)

    Stepanenko, Yu V; Bagdasarov, K N; Shchemeleva, G G [Rostovskij-na-Donu Gosudarstvennyj Univ. (USSR)

    1975-12-01

    A study of the reaction between uranium (6) and malachite green in the presence of sodium benzoate has indicated that, in a weakly acid medium (pH 4.5 to 5.5), the reaction yields a poorly soluble greenish compound which tends to be extracted by a 1-to-1 mixture of benzene and chloroform. The compound comprises uranium, a benzoate and a malachite green in a ratio of 1/3/1. A method has been developed for an extraction-photometric determination of uranium in metallic lead.

  19. Radium and uranium concentrations and associated hydrogeochemistry in ground water in southwestern Pueblo County, Colorado

    Science.gov (United States)

    Felmlee, J. Karen; Cadigan, Robert Allen

    1979-01-01

    Radium and uranium concentrations in water from 37 wells tapping the aquifer system of the Dakota Sandstone and Purgatoire Formation in southwestern Pueblo County, Colorado, have a wide range of values and define several areas of high radioactivity in the ground water. Radium ranges from 0.3 to 420 picocuries per liter and has a median value of 8.8, and uranium ranges from 0.02 to 180 micrograms per liter and has a median value of 2.4. Radon concentrations, measured in 32 of the 37 wells, range from less than 100 picocuries per liter to as much as 27,000 and have a median value of 580. Relationships among the radioactive elements and 28 other geochemical parameters were studied by using correlation coefficients and R-mode factor analysis. Five factor groups were determined to represent major influences on water chemistry: (1) short-term solution reactions, (2) oxidation reactions, (3) hydrolysis reactions, (4) uranium distribution, and (5) long-term solution reactions. Uranium concentrations are most strongly influenced by oxidation reactions but also are affected by solution reactions and distribution of uranium in the rocks of the aquifer system. Radon and radium concentrations are mostly controlled by uranium distribution; radium also shows a moderate negative relationship with oxidation. To explain the statistical and spatial relationships among the parameters, a model was developed involving the selective leaching of uranium-bearing phases and metal sulfides which occur in discontinuous zones in sandstone and shale. When reducing conditions prevail, uranium is immobile, but radium can be taken into solution. When faults and associated fractured rocks allow oxidizing conditions to dominate, uranium can be taken into solution; radium can also be taken into solution, or it may become immobilized by coprecipitation with iron and manganese oxides or with barite. Several areas within the study area are discussed in terms of the model.

  20. Review of uranium market price

    International Nuclear Information System (INIS)

    Maragatham Kumar; Nik Arlina Nik Ali; Koh You Beng

    2007-01-01

    Uranium is used as an abundant source of concentrated energy and is the principal fuel for the generation of electricity by nuclear reactors. In nuclear reactors, the uranium fuel is assembled in such a way that a controlled fission chain reaction can be achieved. Since uranium is the main source of nuclear energy, demand prospects for uranium has increased dramatically with the renewed global interest in nuclear power generation in recent years. Although the global uranium market is relatively small worldwide, compared to other mineral and energy sources, it is a very important market as nuclear power generation accounts for about 18% of global electricity supply. After reaching historic lows in 1990s, uranium prices have risen substantially in recent years. The outlook for nuclear power has changed since 2000, with concerns over global warming, proven excellent safety record, competitive costs, progress on nuclear waste disposal issues and also continuing new nuclear plant construction around the world. These and various other influencing factors have resulted in the uranium market evolving from one that was driven by excess secondary supplies to that by primary production. This paper reviews the global market prices for the years 1987 until 2006 and the factors, which influence the changes in global uranium market prices. (Author)

  1. Method for the production of uranium chloride salt

    Science.gov (United States)

    Westphal, Brian R.; Mariani, Robert D.

    2013-07-02

    A method for the production of UCl.sub.3 salt without the use of hazardous chemicals or multiple apparatuses for synthesis and purification is provided. Uranium metal is combined in a reaction vessel with a metal chloride and a eutectic salt- and heated to a first temperature under vacuum conditions to promote reaction of the uranium metal with the metal chloride for the production of a UCl.sub.3 salt. After the reaction has run substantially to completion, the furnace is heated to a second temperature under vacuum conditions. The second temperature is sufficiently high to selectively vaporize the chloride salts and distill them into a condenser region.

  2. The behaviour of uranium metal in hydrogen atmospheres

    International Nuclear Information System (INIS)

    Allen, G.C.; Stevens, J.C.H.

    1988-01-01

    The reaction between commercial H 2 and uranium metal leads to the formation of UO 2 due to traces of water vapour or oxygen. When extremely pure H 2 is used uranium hydride may be formed but, even with 99.9999% H 2 , uranium dioxide forms preferentially. The present work identifies the presence of UH 3 in the X-ray photoelectron spectrum of a uranium sample which has been exposed to ca. 10 10 L† H 2 at ca. 200 0 C. This spectrum indicates that the hydride possesses a high degree of covalency, since the oxidation state of uranium in UH 3 appears to be ca. 1.4. (author)

  3. Study of the dry processing of uranium ores

    International Nuclear Information System (INIS)

    Guillet, H.

    1959-02-01

    A description is given of direct fluorination of pre-concentrated uranium ores in order to obtain the hexafluoride. After normal sulfuric acid treatment of the ore to eliminate silica, the uranium is precipitated by a load of lime to obtain: either impure calcium uranate of medium grade, or containing around 10% of uranium. This concentrate is dried in an inert atmosphere and then treated with a current of elementary fluorine. The uranium hexafluoride formed is condensed at the outlet of the reaction vessel and may be used either for reduction to tetrafluoride and the subsequent manufacture of uranium metal or as the initial product in a diffusion plant. (author) [fr

  4. Analytical definition of fission chain reaction parameters for cylindrical uranium bar and energy release evaluations for HIF hybrid targets

    International Nuclear Information System (INIS)

    Imshennik, V.S.

    2006-01-01

    Within the conditions of Heavy-Ion Fusion (HIF) arises a possibility to obtain the fission chain reaction for a cylindrical HIF target. The paper contains the solution interpolated with the diffusion approximation in order to receive the general approximation expressions for the bar critical radius as well as for over-critical state. The obtained critical parameters generalized for uranium envelope are used for rough evaluation of the energy release in HIF hybrid targets [ru

  5. Uranium Pyrophoricity Phenomena and Prediction (FAI/00-39)

    International Nuclear Information System (INIS)

    PLYS, M.G.

    2000-01-01

    The purpose of this report is to provide a topical reference on the phenomena and prediction of uranium pyrophoricity for the Hanford Spent Nuclear Fuel (SNF) Project with specific applications to SNF Project processes and situations. Spent metallic uranium nuclear fuel is currently stored underwater at the K basins in the Hanford 100 area, and planned processing steps include: (1) At the basins, cleaning and placing fuel elements and scrap into stainless steel multi-canister overpacks (MCOs) holding about 6 MT of fuel apiece; (2) At nearby cold vacuum drying (CVD) stations, draining, vacuum drying, and mechanically sealing the MCOs; (3) Shipping the MCOs to the Canister Storage Building (CSB) on the 200 Area plateau; and (4) Welding shut and placing the MCOs for interim (40 year) dry storage in closed CSB storage tubes cooled by natural air circulation through the surrounding vault. Damaged fuel elements have exposed and corroded fuel surfaces, which can exothermically react with water vapor and oxygen during normal process steps and in off-normal situations, A key process safety concern is the rate of reaction of damaged fuel and the potential for self-sustaining or runaway reactions, also known as uranium fires or fuel ignition. Uranium metal and one of its corrosion products, uranium hydride, are potentially pyrophoric materials. Dangers of pyrophoricity of uranium and its hydride have long been known in the U.S. Department of Energy (Atomic Energy Commission/DOE) complex and will be discussed more below; it is sufficient here to note that there are numerous documented instances of uranium fires during normal operations. The motivation for this work is to place the safety of the present process in proper perspective given past operational experience. Steps in development of such a perspective are: (1) Description of underlying physical causes for runaway reactions, (2) Modeling physical processes to explain runaway reactions, (3) Validation of the method

  6. Reaction-transport simulations of non-oxidative methane conversion with continuous hydrogen removal: Homogeneous-heterogeneous methane reaction pathways

    International Nuclear Information System (INIS)

    Li, Lin; Borry, Richard W.; Iglesia, Enrique

    2000-01-01

    Detailed kinetic-transport models were used to explore thermodynamic and kinetic barriers in the non-oxidative conversion of CH4 via homogeneous and homogeneous-heterogeneous pathways and the effects of continuous hydrogen removal and of catalytic sites on attainable yields of useful C2-C10 products. The homogeneous kinetic model combines separately developed models for low-conversion pyrolysis and for chain growth to form large aromatics and carbon. The H2 formed in the reaction decreases CH4 pyrolysis rates and equilibrium conversions and it favors the formation of lighter products. The removal of H2 along tubular reactors with permeable walls increases reaction rates and equilibrium CH4 conversions. C2-C10 yields reach values greater than 90 percent at intermediate values of dimensionless transport rates (delta=1-10), defined as the ratio hydrogen transport and methane conversion rates. Homogeneous reactions require impractical residence times, even with H2 removal, because of slow initiation and chain transfer rates. The introduction of heterogeneous chain initiation pathways using surface sites that form methyl radicals eliminates the induction period without influencing the homogeneous product distribution. Methane conversion, however, occurs predominately in the chain transfer regime, within which individual transfer steps and the formation of C2 intermediates become limited by thermodynamic constraints. Catalytic sites alone cannot overcome these constraints. Catalytic membrane reactors with continuous H2 removal remove these thermodynamic obstacles and decrease the required residence time. Reaction rates become limited by homogeneous reactions of C2 products to form C6+ aromatics. Higher delta values lead to subsequent conversion of the desired C2-C10 products to larger polynuclear aromatics. We conclude that catalytic methane pyrolysis at the low temperatures required for restricted chain growth and the elimination of thermodynamics constraints via

  7. A coupled transport and solid mechanics formulation with improved reaction kinetics parameters for modeling oxidation and decomposition in a uranium hydride bed.

    Energy Technology Data Exchange (ETDEWEB)

    Salloum, Maher N.; Shugard, Andrew D.; Kanouff, Michael P.; Gharagozloo, Patricia E.

    2013-03-01

    Modeling of reacting flows in porous media has become particularly important with the increased interest in hydrogen solid-storage beds. An advanced type of storage bed has been proposed that utilizes oxidation of uranium hydride to heat and decompose the hydride, releasing the hydrogen. To reduce the cost and time required to develop these systems experimentally, a valid computational model is required that simulates the reaction of uranium hydride and oxygen gas in a hydrogen storage bed using multiphysics finite element modeling. This SAND report discusses the advancements made in FY12 (since our last SAND report SAND2011-6939) to the model developed as a part of an ASC-P&EM project to address the shortcomings of the previous model. The model considers chemical reactions, heat transport, and mass transport within a hydride bed. Previously, the time-varying permeability and porosity were considered uniform. This led to discrepancies between the simulated results and experimental measurements. In this work, the effects of non-uniform changes in permeability and porosity due to phase and thermal expansion are accounted for. These expansions result in mechanical stresses that lead to bed deformation. To describe this, a simplified solid mechanics model for the local variation of permeability and porosity as a function of the local bed deformation is developed. By using this solid mechanics model, the agreement between our reacting bed model and the experimental data is improved. Additionally, more accurate uranium hydride oxidation kinetics parameters are obtained by fitting the experimental results from a pure uranium hydride oxidation measurement to the ones obtained from the coupled transport-solid mechanics model. Finally, the coupled transport-solid mechanics model governing equations and boundary conditions are summarized and recommendations are made for further development of ARIA and other Sandia codes in order for them to sufficiently implement the model.

  8. The present state of laser isotope separation of uranium

    International Nuclear Information System (INIS)

    Tashiro, Hideo; Nemoto, Koshichi.

    1994-01-01

    As the methods of uranium enrichment, gas diffusion method and centrifugal separation method in which power consumption is less and the cost is low have been carried out. On the other hand, as the future technology, the research and development of laser isotope separation technology have been carried out. There are the atomic laser separation process in which the laser beam of visible light is irradiated to atomic state uranium and the molecular laser separation process in which far infrared laser beam is irradiated to uranium hexafluoride molecules. The atomic process is divided into three steps, that is, the processes of uranium evaporation, the reaction of uranium with laser beam and the recovery of enriched uranium. The principle of the laser separation is explained. The state of development of laser equipment and separation equipment is reported. The principle and the present state of development of the molecular separation process which consists of the cooling of UF 6 gas, the generation of high power 16 μm laser pulses and the collection of the reaction product are explained. The present state of both processes in foreign countries is reported. (K.I.)

  9. Selective recovery of uranium from Ca-Mg uranates by chlorination

    International Nuclear Information System (INIS)

    Pomiro, Federico J.; Gaviría, Juan P.; Quinteros, Raúl D.

    2017-01-01

    A chlorination process is proposed for the uranium extraction and separation using Calcium−Magnesium uranates such as starting reactants which were obtained by precipitation from uranyl nitrate solutions with calcium hydroxide. The study is based on thermodynamic and reaction analysis using chlorine gas as chlorination agent. The results showed that the chlorination reaction of Ca uranate is more feasible to occur than the Mg uranate. The products obtained after chlorination reactions were washed with deionized water to remove the chlorides produced and analyzed. The XRD patterns of the washed products indicated that the chlorination between 400 and 500 °C result in a single phase of calcium uranate (CaUO 4 ) as reaction product. The formation of U 3 O 8 and MgU 3 O 10 was observed at temperatures between 600 °C and 700 °C for 8 hs. The optimal conditions to recover uranium were 3 l h −1 of chlorine and 10 hs of reaction at 700 °C being U 3 O 8 the single uranium product obtained. - Highlights: •The chlorination is an effective method for the recovery uranium from Ca-Mg uranates. •The optimal conditions were: 10 hs of reaction time at 700 °C using 3 l/h of Cl 2 (g). •U 3 O 8 is recovery by washing out the chlorination by-products.

  10. Research on using depleted uranium as nuclear fuel for HWR

    International Nuclear Information System (INIS)

    Zhang Jiahua; Chen Zhicheng; Bao Borong

    1999-01-01

    The purpose of our work is to find a way for application of depleted uranium in CANDU reactor by using MOX nuclear fuel of depleted U and Pu instead of natural uranium. From preliminary evaluation and calculation, it was shown that MOX nuclear fuel consisting of depleted uranium enrichment tailings (0.25% 235 U) and plutonium (their ratio 99.5%:0.5%) could replace natural uranium in CANDU reactor to sustain chain reaction. The prospects of application of depleted uranium in nuclear energy field are also discussed

  11. Gas-Phase Reaction Pathways and Rate Coefficients for the Dichlorosilane-Hydrogen and Trichlorosilane-Hydrogen Systems

    Science.gov (United States)

    Dateo, Christopher E.; Walch, Stephen P.

    2002-01-01

    As part of NASA Ames Research Center's Integrated Process Team on Device/Process Modeling and Nanotechnology our goal is to create/contribute to a gas-phase chemical database for use in modeling microelectronics devices. In particular, we use ab initio methods to determine chemical reaction pathways and to evaluate reaction rate coefficients. Our initial studies concern reactions involved in the dichlorosilane-hydrogen (SiCl2H2--H2) and trichlorosilane-hydrogen (SiCl2H-H2) systems. Reactant, saddle point (transition state), and product geometries and their vibrational harmonic frequencies are determined using the complete-active-space self-consistent-field (CASSCF) electronic structure method with the correlation consistent polarized valence double-zeta basis set (cc-pVDZ). Reaction pathways are constructed by following the imaginary frequency mode of the saddle point to both the reactant and product. Accurate energetics are determined using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations (CCSD(T)) extrapolated to the complete basis set limit. Using the data from the electronic structure calculations, reaction rate coefficients are obtained using conventional and variational transition state and RRKM theories.

  12. Selective recovery of uranium from Ca-Mg uranates by chlorination

    Science.gov (United States)

    Pomiro, Federico J.; Gaviría, Juan P.; Quinteros, Raúl D.; Bohé, Ana E.

    2017-07-01

    A chlorination process is proposed for the uranium extraction and separation using Calciumsbnd Magnesium uranates such as starting reactants which were obtained by precipitation from uranyl nitrate solutions with calcium hydroxide. The study is based on thermodynamic and reaction analysis using chlorine gas as chlorination agent. The results showed that the chlorination reaction of Ca uranate is more feasible to occur than the Mg uranate. The products obtained after chlorination reactions were washed with deionized water to remove the chlorides produced and analyzed. The XRD patterns of the washed products indicated that the chlorination between 400 and 500 °C result in a single phase of calcium uranate (CaUO4) as reaction product. The formation of U3O8 and MgU3O10 was observed at temperatures between 600 °C and 700 °C for 8 hs. The optimal conditions to recover uranium were 3 l h-1 of chlorine and 10 hs of reaction at 700 °C being U3O8 the single uranium product obtained.

  13. A study on chlorination of uranium metal using ammonium chloride

    International Nuclear Information System (INIS)

    Eun, H.C.; Kim, T.J.; Jang, J.H.; Kim, G.Y.; Lee, S.J.; Hur, J.M.

    2017-01-01

    In this study, the chlorination of uranium metal using ammonium chloride (NH 4 Cl) was conducted to derive an easy and simple uranium chloride production method without impurities. In thermodynamic equilibrium calculations, it was predicted that only uranium chlorides can be produced by the reactions between uranium metal and NH 4 Cl. Experimental conditions for the chlorination of uranium metal were determined using a chlorination test of cerium metal using NH 4 Cl. It was confirmed that UCl 3 and UCl 4 in the form of particles as uranium chlorination products can be obtained from the chlorination method using NH 4 Cl. (author)

  14. Investigation of the kinetics of the reactions of oxidation, nitration, and hydrogenation of uranium; Etude cinetique de l'oxydation, de la nitruration et de l'hydruration de l'uranium

    Energy Technology Data Exchange (ETDEWEB)

    Adda, Y [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1955-06-15

    Various physico-chemical methods have been used to investigate the kinetics of the oxidation hydridation and nitridation of uranium. The experimental results show that the kinetics of these reactions are influenced by many factors also the Pilling and Bedworth rule is valid only under very limited conditions. The disagreement between this rule and the experimental results could be explained by the existence of numerous mechanical faults in the compounds obtained by the dry corrosion of the metal. (author) [French] Les cinetiques d'oxydation, d'hydruration et de nitruration de l'uranium ont ete etudiees au moyen de differentes methodes physico-chimiques. Les resultats experimentaux obtenus indiquent qu'un grand nombre de facteurs influencent les cinetiques d'attaque et que la regle de Pilling et Bedworth n'est verifiee que dans des cas tres limites. Les desaccords entre cette regle et les resultats experimentaux s'expliqueraient par l'existence de nombreux defauts mecaniques dans les composes obtenus par corrosion seche du metal. (auteur)

  15. Spectroscopic Confirmation of Uranium (VI)-Carbonato Adsorption Complexes on Hematite

    International Nuclear Information System (INIS)

    Bargar, John R

    1999-01-01

    Evaluating societal risks posed by uranium contamination from waste management facilities, mining sites, and heavy industry requires knowledge about uranium transport in groundwater, often the most significant pathway of exposure to humans. It has been proposed that uranium mobility in aquifers may be controlled by adsorption of U(VI)-carbonato complexes on oxide minerals. The existence of such complexes has not been demonstrated, and little is known about their compositions and reaction stoichiometries. We have used Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopies to probe the existence, structures, and compositions of FeO surface -U(VI)-carbonato complexes on hematite throughout the pH range of uranyl uptake under conditions relevant to aquifers. U(VI)-carbonato complexes were found to be the predominant adsorbed U(VI) species at all pH values examined, a much wider pH range than previously postulated based on analogy to aqueous U(VI)-carbonato complexes, which are trace constituents at pH < 6. This result indicates the inadequacy of the common modeling assumption that the compositions and predominance of adsorbed species can be inferred from aqueous species. By extension, adsorbed carbonato complexes may be of major importance to the groundwater transport of similar actinide contaminants such as neptunium and plutonium

  16. Contribution to Yttria corrosion study by liquid uranium

    International Nuclear Information System (INIS)

    Tournier, C.

    1995-02-01

    We are studying liquid uranium and polycrystalline Yttria interactions under secondary vacuum. The type, morphology and thickness of interfacial reaction products between U and Y 2 O 3 are examined by optical and confocal microscopy, SEM, X ray diffraction, X analysis and XPS. The most important parameters are the stoechiometry and microstructure of the Yttria, the oxygen partial pressure of the furnace atmosphere, pO 2 , and the duration and temperature of experiments. In the thermodynamic modelization, we take into account exchanges at the ceramic/metal interface and exchanges between the molten metal and the furnace atmosphere. Liquid uranium reacts with Yttria to form UO 2 at the interface which gradually changes into a solid solution UO 2 -Y 2 O 3 . The total thickness of reaction products results from two opposing reactions: (i) oxidation of uranium by Yttria (low pO 2 ) or by the atmosphere (high pO 2 ), controlled by migration of oxygen vacancies at Yttria grain boundaries. (ii) deoxidation caused by the formation of volatile uranium monoxide. On the other hand, we observed a transition of the type ''non-wettability → wettability '' which occurs subsequent to an increase of the stoichiometric variation x in Y 2 O 3-x . (author). 69 refs., 76 figs., 30 tabs

  17. Evidence for Single Metal Two Electron Oxidative Addition and Reductive Elimination at Uranium

    OpenAIRE

    Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; Mcinnes, Eric; Tuna, Floriana; Wooles, Ashley; Maron, Laurent; Liddle, Stephen

    2017-01-01

    Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here, we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido compl...

  18. Development of practical decontamination process for the removal of uranium from gravel.

    Science.gov (United States)

    Kim, Ilgook; Kim, Gye-Nam; Kim, Seung-Soo; Choi, Jong-Won

    2018-01-01

    In this study, a practical decontamination process was developed to remove uranium from gravel using a soil washing method. The effects of critical parameters including particle size, H 2 SO 4 concentration, temperature, and reaction time on uranium removal were evaluated. The optimal condition for two-stage washing of gravel was found to be particle size of 1-2 mm, 1.0 M H 2 SO 4 , temperature of 60°C, and reaction time of 3 h, which satisfied the required uranium concentration for self-disposal. Furthermore, most of the extracted uranium was removed from the waste solution by precipitation, implying that the treated solution can be reused as washing solution. These results clearly demonstrated that our proposed process can be indeed a practical technique to decontaminate uranium-polluted gravel.

  19. Basic research on high-uranium density fuels for research and test reactors

    International Nuclear Information System (INIS)

    Ugajin, M.; Itoh, A.; Akabori, M.

    1992-01-01

    High-uranium density fuels, uranium silicides (U 3 Si 2 , U 3 Si) and U 6 Me-type uranium alloys (Me = Fe, Mn, Ni), were prepared and examined metallurgically as low-enriched uranium (LEU) fuels for research and test reactors. Miniature aluminum-dispersion plate-type fuel (miniplate) and aluminum-clad disk-type fuel specimens were fabricated and subjected to the neutron irradiation in JMTR (Japan Materials Testing Reactor). Fuel-aluminum compatibility tests were conducted to elucidate the extent of reaction and to identify reaction products. The relative stability of the fuels in an aluminum matrix was established at 350degC or above. Experiments were also performed to predict the chemical form of the solid fission-products in the uranium silicide (U 3 Si 2 ) simulating a high burnup anticipated for reactor service. (author)

  20. Spectrographic determination of boron and silicon in uranium tetrafluoride: Study of the chemical reactions in the electrode cavity when ZnO is used as a uranium excitation suppressor; Determinacion espectrografica de Boro y Silicio en Tetrafluoruro de Unraio: Estudio de las reacciones quimicas que tienen lugar en el crater del electrodo al autilizar ZnO como supresor de la excitacion del Uranio

    Energy Technology Data Exchange (ETDEWEB)

    Alduan, F. A.; Capdevila, C.; Rosa, M.

    1973-07-01

    A method has been developed for determining traces of boron and silicon in uranium tetrafluoride. Use is made of zinc oxide to decrease the volatilization of uranium and achieve high sensitivities. The thermochemical reactions which occur in the anode cavity during the arcing process have been investigated. UO{sub 2} and a uranium, zinc and fluorine compound, both less volatile than uranium tetrafluoride, are formed. (Author)

  1. Influence of the reduction-crucible material on the uranium properties

    International Nuclear Information System (INIS)

    Braga, F.J.C.; Bose, A.; Freitas, C.T. de

    1979-01-01

    The uranium obtained by UF 4 reduction using Mg in bombs coated with different materials such as alumina, blast furnace slag, Zirconia and graphite was studied. The reduction process involves a reaction that altains temperatures of the order of 1600 0 C at tightly closed enclosure environment. Assuming in this process that the only possible influencial agent on the reaction main product, i.e., metallic uranium is the own bomb coaling, different properties, mechanical-metallurgical and phase-transformation characteristics were examined and the influences of the coating materials were compared. The comparison of these properties was also studied in uranium refined by arc fusion. (Author) [pt

  2. The preparation of uranium tetrafluoride from dioxide by aqueous way

    International Nuclear Information System (INIS)

    Aquino, A.R. de; Abrao, A.

    1990-01-01

    This paper describes the study for the wet way obtention of uranium tetrafluoride by the reaction of hydrofluoric acid and powder uranium dioxide. With the results obtained at laboratory scale a pilot plant was planned and erected. It is presently in operation for experimental data aquisition. Time of reaction, temperature, excess of reagents and the hydrofluoric acid / uranium dioxide ratio were the main parameters studied to obtain a product with the following characteristics: - density greater than 1 g/cm 3 , - conversion rate greater than 96%, -water content equal to 0,2%, that allows its application to hexafluoride convertion or to magnesiothermic process. (authOr) [pt

  3. Medical effects of internal contamination with uranium.

    Science.gov (United States)

    Duraković, A

    1999-03-01

    The purpose of this work is to present an outline of the metabolic pathways of uranium isotopes and compounds, medical consequences of uranium poisoning, and an evaluation of the therapeutic alternatives in uranium internal contamination. The chemical toxicity of uranium has been recognized for more than two centuries. Animal experiments and human studies are conclusive about metabolic adverse affects and nephro- toxicity of uranium compounds. Radiation toxicity of uranium isotopes has been recognized since the beginning of the nuclear era, with well documented evidence of reproductive and developmental toxicity, as well as mutagenic and carcinogenic consequences of uranium internal contamination. Natural uranium (238U), an alpha emitter with a half-life of 4.5x10(9) years, is one of the primordial substances of the universe. It is found in the earth's crust, combined with 235U and 234U, alpha, beta, and gamma emitters with respective half-lives of 7.1x10(8) and 2.5x10(5) years. A special emphasis of this paper concerns depleted uranium. The legacy of radioactive waste, environmental and health hazards in the nuclear industry, and, more recently, the military use of depleted uranium in the tactical battlefield necessitates further insight into the toxicology of depleted uranium. The present controversy over the radiological and chemical toxicity of depleted uranium used in the Gulf War warrants further experimental and clinical investigations of its effects on the biosphere and human organisms.

  4. Production and analysis of ultradispersed uranium oxide powders

    Science.gov (United States)

    Zajogin, A. P.; Komyak, A. I.; Umreiko, D. S.; Umreiko, S. D.

    2010-05-01

    Spectroscopic studies are made of the laser plasma formed near the surface of a porous body containing nanoquantities of uranium compounds which is irradiated by two successive laser pulses. The feasibility of using laser chemical methods for obtaining nanoclusters of uranium oxide particles in the volume of a porous body and the simultaneous possibility of determining the uranium content with good sensitivity are demonstrated. The thermochemical and spectral characteristics of the analogs of their compounds with chlorine are determined and studied. The possibility of producing uranium dioxides under ordinary conditions and their analysis in the reaction products is demonstrated.

  5. The existence state of uranium(VI) in portland cement matrix material immobilization body

    International Nuclear Information System (INIS)

    Tan Hongbin; Li Yuxiang

    2005-01-01

    The basis of Portland cement material reaction with uranium, the corrosion of uranium minerals in nature and the state of study on immobilization of uranium by Portland cement matrix material are introduced, and some considerations are presented. (authors)

  6. Analysis of reaction cross-section production in neutron induced fission reactions on uranium isotope using computer code COMPLET.

    Science.gov (United States)

    Asres, Yihunie Hibstie; Mathuthu, Manny; Birhane, Marelgn Derso

    2018-04-22

    This study provides current evidence about cross-section production processes in the theoretical and experimental results of neutron induced reaction of uranium isotope on projectile energy range of 1-100 MeV in order to improve the reliability of nuclear stimulation. In such fission reactions of 235 U within nuclear reactors, much amount of energy would be released as a product that able to satisfy the needs of energy to the world wide without polluting processes as compared to other sources. The main objective of this work is to transform a related knowledge in the neutron-induced fission reactions on 235 U through describing, analyzing and interpreting the theoretical results of the cross sections obtained from computer code COMPLET by comparing with the experimental data obtained from EXFOR. The cross section value of 235 U(n,2n) 234 U, 235 U(n,3n) 233 U, 235 U(n,γ) 236 U, 235 U(n,f) are obtained using computer code COMPLET and the corresponding experimental values were browsed by EXFOR, IAEA. The theoretical results are compared with the experimental data taken from EXFOR Data Bank. Computer code COMPLET has been used for the analysis with the same set of input parameters and the graphs were plotted by the help of spreadsheet & Origin-8 software. The quantification of uncertainties stemming from both experimental data and computer code calculation plays a significant role in the final evaluated results. The calculated results for total cross sections were compared with the experimental data taken from EXFOR in the literature, and good agreement was found between the experimental and theoretical data. This comparison of the calculated data was analyzed and interpreted with tabulation and graphical descriptions, and the results were briefly discussed within the text of this research work. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

  7. Uranium in the Black Sea

    International Nuclear Information System (INIS)

    Babinets, A.E.; Zhorov, V.A.; Bezborodov, A.A.; Kobylyanskaya, A.G.; Solov'eva, L.V.; Urdenko, V.A.

    1975-01-01

    Water samples for uranium analysis have been collected over the entire Black Sea, from the surface to the sea floor. As distinct from the previously known facts, it has been established that the uranium content in different parts of the sea appears to vary both in extent and with depth. A behaviour of uranium is governed by redox conditions of the environment. A decrease in pH value of water to 7.5 and a change of Eh value from +0.4 to -0.2 v lead to reduction of U 6+ → U 4+ and ensure higher sorption properties of the solid phases. The reducing reaction is proved possible through the calculated data. It is shown that the rate of uranium isolation is increasing with depth and its content is going down. Using optical properties of water, a hydrogeochemical behaviour of organic matter and uranium in water thickness is explained. Role of organic matter and mineral components in the uranium deposition is described. Sorption of U 6+ ions on twelve components, which constitute a base of suspensions and floor sediments, has been also studied [ru

  8. Experimental Observation of Nuclear Reactions in Palladium and Uranium

    International Nuclear Information System (INIS)

    J. Dufour; D. Murat; X. Dufour; J. Foos

    2001-01-01

    By submitting various metals (Pd, U) containing hydrogen (from 2000 to 700 000 atoms of hydrogen for 1 000 000 atoms of the host metal) to the combined action of electrical currents and magnetic fields, we have observed a sizeable exothermal effect (from 0.1 to 8 W for 500 mg of metal used). This effect is beyond experimental errors, the energy output being typically 130 to 250% of the energy input and not of chemical origin (exothermal effect in the range of 7000 MJ/mol of metal in the case of palladium and of 60 MJ/mol in the case of uranium). New chemical species also appear in the processes metals. It has been shown by a QED calculation that resonances of long lifetime (s), nuclear dimensions (fm), and low energy of formation (eV) could exist. This concept seems to look like the 'shrunken hydrogen atoms' proposed by various authors. It is indeed very different in two ways (a) being a metastable state, it needs energy to be formed (a few eV) and reverts to normal hydrogen after a few seconds, liberating back its energy of formation (it is thus not the source of the energy observed); (b) its formation can be described as the electron spin/proton nuclear spin interaction becoming first order in the lattice environment (whereas it is third order in a normal hydrogen atom). Moreover, we consider that the hydrex cannot yield a neutron because this reaction is strongly endothermic. To explain our results, we put forward the following working hypothesis: In a metal lattice and under proper conditions, the formation of such resonances (metastable state) could be favored. We propose to call them HYDREX, and we assume that they are actually formed in cold fusion (CF) and low-energy nuclear reaction (LENR) experiments. Once formed, a number of HYDREX could gather around a nucleus of the lattice to form a cluster of nuclear size and of very long life time compared to nuclear time (10 -22 s). In this cluster, nuclear rearrangements could take place, yielding mainly 4 He

  9. Contribution to the study of the intermediate fluorides of uranium; Contribution a l'etude des fluorures intermediaires d'uranium

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen-Hoang, Nghi [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1961-10-15

    The reaction of gaseous uranium hexafluoride with solid uranium tetrafluoride has been studied between 20 and 300 deg. C. The intermediate fluorides resulting from this reaction were prepared and then identified by chemical analysis and Debye-Scherrer diagrams. Their magnetic susceptibility and action on various common solvents were determined. The kinetic study was carried out up to 45 deg. C at a constant gas pressure equal to 17,7 mm of mercury. The experimental results indicate that the reaction, limited by the diffusion process of ionic reactants, obeys the kinetic law: L (1 - C) = k{radical}t. The observed rate constant K and the diffusion coefficient D vary with the temperature according to the expressions: K min{sup -1/2} = - (1,88 {+-} 0,22) 10{sup 8} exp[-(14100 {+-} 1400 cal/mole)/(RT)]; D cm{sup 2} sec{sup -1} = (1,15 {+-} 0,51) 10{sup 6} exp[-(30200 {+-} 5700 cal/mole)/(RT)]. (author) [French] La reaction de l'hexafluorure d'uranium gazeux sur le tetrafluorure d'uranium solide a ete etudiee entre 20 et 300 deg. C. Les fluorures intermediaires resultant de cette reaction ont ete prepares, puis identifies par analyses chimiques et par diagrammes Debye-Scherrer. Leur susceptibilite magnetique et leur action sur divers solvants usuels ont ete determinees. L'etude cinetique a ete entreprise jusqu'a 45 deg. C, sous une pression de gaz constante et egale a 17,7 mm de mercure. Les resultats experimentaux obtenus indiquent que la reaction, limitee par le processus de diffusion de reactifs ioniques, suit la loi cinetique: L (1 - C) = k{radical}t. La constante de vitesse observee K et le coefficient de diffusion D varient avec la temperature selon les expressions: K min{sup -1/2} = - (1,88 {+-} 0,22) 10{sup 8} exp[-(14100 {+-} 1400 cal/mole)/(RT)]; D cm{sup 2} sec{sup -1} = (1,15 {+-} 0,51) 10{sup 6} exp[-(30200 {+-} 5700 cal/mole)/(RT)]. (auteur)

  10. Hydrolysis of uranium monocarbide

    International Nuclear Information System (INIS)

    Hajek, B.; Karen, P.; Brozek, V.

    1984-01-01

    The substoichiometric uranium monocarbide UCsub(0.95) was hydrolyzed in acid medium at 80 degC. The composition of the products of hydrolysis corresponds to published data but it correlates better with the stoichiometric composition of the hydrolyzable carbide. The mechanisms of the hydrolytic reaction are discussed and a modified radical mechanism is suggested based on the concept of initiation of the radical process by Hsup(.) radicals formed owing to the nonstoichiometry of the substance. A relation is proposed for calculating the content of free hydrogen in the hydrolysis products of carbides of metallic nature for which a radical mechanism of their reaction with water can be assumed. Some effects occurring during the hydrolysis of uranium carbide, as described in literature, are explained in terms of the concept suggested. The results obtained by the authors for carbides of manganese (Mn 7 C 3 ) and for rare earth elements are discussed. (author)

  11. Selective recovery of uranium from Ca-Mg uranates by chlorination

    Energy Technology Data Exchange (ETDEWEB)

    Pomiro, Federico J., E-mail: pomiro@cab.cnea.gov.ar [Departamento de Fisicoquímica y Control de Calidad, Complejo Tecnológico Pilcaniyeu, Centro Atómico Bariloche, Comisión Nacional de Energía Atómica, Av. Bustillo 9500, 8400 S.C. de Bariloche, Río Negro (Argentina); Gaviría, Juan P. [Departamento de Fisicoquímica y Control de Calidad, Complejo Tecnológico Pilcaniyeu, Centro Atómico Bariloche, Comisión Nacional de Energía Atómica, Av. Bustillo 9500, 8400 S.C. de Bariloche, Río Negro (Argentina); Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET) (Argentina); Quinteros, Raúl D. [Departamento de Fisicoquímica y Control de Calidad, Complejo Tecnológico Pilcaniyeu, Centro Atómico Bariloche, Comisión Nacional de Energía Atómica, Av. Bustillo 9500, 8400 S.C. de Bariloche, Río Negro (Argentina); and others

    2017-07-15

    A chlorination process is proposed for the uranium extraction and separation using Calcium−Magnesium uranates such as starting reactants which were obtained by precipitation from uranyl nitrate solutions with calcium hydroxide. The study is based on thermodynamic and reaction analysis using chlorine gas as chlorination agent. The results showed that the chlorination reaction of Ca uranate is more feasible to occur than the Mg uranate. The products obtained after chlorination reactions were washed with deionized water to remove the chlorides produced and analyzed. The XRD patterns of the washed products indicated that the chlorination between 400 and 500 °C result in a single phase of calcium uranate (CaUO{sub 4}) as reaction product. The formation of U{sub 3}O{sub 8} and MgU{sub 3}O{sub 10} was observed at temperatures between 600 °C and 700 °C for 8 hs. The optimal conditions to recover uranium were 3 l h{sup −1} of chlorine and 10 hs of reaction at 700 °C being U{sub 3}O{sub 8} the single uranium product obtained. - Highlights: •The chlorination is an effective method for the recovery uranium from Ca-Mg uranates. •The optimal conditions were: 10 hs of reaction time at 700 °C using 3 l/h of Cl{sub 2}(g). •U{sub 3}O{sub 8} is recovery by washing out the chlorination by-products.

  12. Redox reactivity and coordination chemistry of uranium

    International Nuclear Information System (INIS)

    Nocton, G.

    2009-09-01

    The study and the understanding of actinides chemistry have important implications in the nuclear field both for the development of new actinides materials and the retreatment of the nuclear wastes. One of the major issues in that chemistry is that the actinides elements are known to undergo redox reaction and to form assemblies of different size and different topologies. In that context uranium can be a good model of the heavier radioelement because it is much less radioactive. So, this work concerns the synthesis and the study of the spectroscopy and the magnetic properties of several uranium based polymetallic assemblies synthesized by taking advantage of the redox properties and the coordination chemistry of uranium. The hydrolysis reactivity of trivalent uranium has been studied in absence of sterically hindered ligands and led to the synthesis of oxo/hydroxo uranium assemblies with different sizes by changing the starting complex or the reaction conditions. By following the same strategy, the controlled oxidation of trivalent uranium complexes led to an original azido/nitrido uranium complex. The coordination chemistry of the pentavalent uranyl polymer {[UO 2 py 5 ][KI 2 py 3 ]} n has also been studied with different ligand and in different conditions and led to several cation-cation complexes for which the stability is sufficient for studying there dismutation by proton NMR. By changing the ancillary ligands stable monomeric complexes of pentavalent uranyl complexes were also obtained. The magnetic properties of all the complexes, monomers and polymetallic complexes were studied and an antiferromagnetic coupling was observed for the cation-cation pentavalent uranyl dimer [UO 2 (dbm) 2 (K 18 C 6 )] 2 . (author)

  13. The oxidation behaviour of uranium in air at 348-765 K

    International Nuclear Information System (INIS)

    Bennett, M.J.; Price, J.B.

    1981-01-01

    The oxidation behaviour of adjusted uranium has been examined in air, at atmospheric pressure, at 348-765 K. Particular emphasis has been directed to the role of swelling resulting from prior irradiation of the metal to a burn-up of 5600-9100 MWd/t and an addition of 2.5 x 10 4 vpm water vapour to the air. Pre-irradiation of uranium enhanced its attack by air at 348-523 K, the enhancement increasing progressively with percentage swelling. This effect resulted primarily from the break-up of the uranium surface during oxidation with the generation of a greater reaction surface area and was independent of the temperature of oxidation in dry air and also above 423 K in wet air. At lower temperatures, however, the water vapour addition increased the effective reaction rate, possibly by the transistory involvement of uranium hybride. The influence of the water vapour increased with swelling of the irradiated uranium and was greater than that exerted on the oxidation of unirradiated uranium at comparable temperatures. With increasing temperature above 623 K, swelling had a progressively decreasing influence upon the attack of irradiated uranium in both environments. (orig.)

  14. X-ray photoelectron spectroscopy study of CO2 reaction with polycrystalline uranium surface

    International Nuclear Information System (INIS)

    Liu Kezhao; Yu Yong; Zhou Juesheng; Wu Sheng; Wang Xiaolin; Fu Yibei

    1999-10-01

    The adsorption of CO 2 on 'clean' depleted polycrystalline uranium metal surface has been studied by X-ray photoelectron spectroscopy (XPS) at 300 K. The 'clean' surface were prepared by Ar + ion sputtering under ultra-high vacuum (UHV) condition with a base pressure 6.7 x 10 -8 Pa. The result s shows that adsorption of CO 2 on 'clean' uranium metal took place in total dissociation, and leads to the formation of uranium dioxide, uranium carbides and free carbon. The total dissociation of CO 2 produced carbon, oxygen species, CO 2 2- and CO 3 2- species. The diffusion tendency of carbon was much stronger than that of oxygen, and led to form a carbide in oxide-metal interface while the oxygen remained on their surface as an oxide

  15. MRE: a web tool to suggest foreign enzymes for the biosynthesis pathway design with competing endogenous reactions in mind

    KAUST Repository

    Kuwahara, Hiroyuki; Alazmi, Meshari; Cui, Xuefeng; Gao, Xin

    2016-01-01

    To rationally design a productive heterologous biosynthesis system, it is essential to consider the suitability of foreign reactions for the specific endogenous metabolic infrastructure of a host. We developed a novel web server, called MRE, which, for a given pair of starting and desired compounds in a given chassis organism, ranks biosynthesis routes from the perspective of the integration of new reactions into the endogenous metabolic system. For each promising heterologous biosynthesis pathway, MRE suggests actual enzymes for foreign metabolic reactions and generates information on competing endogenous reactions for the consumption of metabolites. These unique, chassis-centered features distinguish MRE from existing pathway design tools and allow synthetic biologists to evaluate the design of their biosynthesis systems from a different angle. By using biosynthesis of a range of high-value natural products as a case study, we show that MRE is an effective tool to guide the design and optimization of heterologous biosynthesis pathways. The URL of MRE is http://www.cbrc.kaust.edu.sa/mre/.

  16. MRE: a web tool to suggest foreign enzymes for the biosynthesis pathway design with competing endogenous reactions in mind

    KAUST Repository

    Kuwahara, Hiroyuki

    2016-04-29

    To rationally design a productive heterologous biosynthesis system, it is essential to consider the suitability of foreign reactions for the specific endogenous metabolic infrastructure of a host. We developed a novel web server, called MRE, which, for a given pair of starting and desired compounds in a given chassis organism, ranks biosynthesis routes from the perspective of the integration of new reactions into the endogenous metabolic system. For each promising heterologous biosynthesis pathway, MRE suggests actual enzymes for foreign metabolic reactions and generates information on competing endogenous reactions for the consumption of metabolites. These unique, chassis-centered features distinguish MRE from existing pathway design tools and allow synthetic biologists to evaluate the design of their biosynthesis systems from a different angle. By using biosynthesis of a range of high-value natural products as a case study, we show that MRE is an effective tool to guide the design and optimization of heterologous biosynthesis pathways. The URL of MRE is http://www.cbrc.kaust.edu.sa/mre/.

  17. Uranium Pyrophoricity Phenomena and Prediction (FAI/00-39)

    Energy Technology Data Exchange (ETDEWEB)

    PLYS, M.G.

    2000-10-10

    The purpose of this report is to provide a topical reference on the phenomena and prediction of uranium pyrophoricity for the Hanford Spent Nuclear Fuel (SNF) Project with specific applications to SNF Project processes and situations. Spent metallic uranium nuclear fuel is currently stored underwater at the K basins in the Hanford 100 area, and planned processing steps include: (1) At the basins, cleaning and placing fuel elements and scrap into stainless steel multi-canister overpacks (MCOs) holding about 6 MT of fuel apiece; (2) At nearby cold vacuum drying (CVD) stations, draining, vacuum drying, and mechanically sealing the MCOs; (3) Shipping the MCOs to the Canister Storage Building (CSB) on the 200 Area plateau; and (4) Welding shut and placing the MCOs for interim (40 year) dry storage in closed CSB storage tubes cooled by natural air circulation through the surrounding vault. Damaged fuel elements have exposed and corroded fuel surfaces, which can exothermically react with water vapor and oxygen during normal process steps and in off-normal situations, A key process safety concern is the rate of reaction of damaged fuel and the potential for self-sustaining or runaway reactions, also known as uranium fires or fuel ignition. Uranium metal and one of its corrosion products, uranium hydride, are potentially pyrophoric materials. Dangers of pyrophoricity of uranium and its hydride have long been known in the U.S. Department of Energy (Atomic Energy Commission/DOE) complex and will be discussed more below; it is sufficient here to note that there are numerous documented instances of uranium fires during normal operations. The motivation for this work is to place the safety of the present process in proper perspective given past operational experience. Steps in development of such a perspective are: (1) Description of underlying physical causes for runaway reactions, (2) Modeling physical processes to explain runaway reactions, (3) Validation of the method

  18. The role of grain boundaries and transient porosity increase as fluid pathways for reaction front propagation

    Science.gov (United States)

    Jonas, Laura; John, Timm; Geisler, Thorsten; Putnis, Andrew

    2013-04-01

    The pseudomorphic replacement of Carrara marble by calcium phosphates was studied as a model system to examine the influence of different fluid pathways for reaction front propagation induced by fluid-rock interaction. In this model system, the grain boundaries present in the rock and the transient porosity structures developing throughout the replacement reaction enable the reaction front to progress further into the rock as well as to the center of each single grain until complete transformation. Hydrothermal treatment of the marble using phosphate bearing solutions at temperature levels of 150° C and 200° C for different durations lead to the formation of two product phases which were identified as hydroxyapatite [Ca5(PO4)3OH] as well as β-tricalcium phosphate [β-Ca3(PO4)2] (β-TCP). The formation of β-TCP was probably favored by the presence of ~0.6wt.% of Mg in the parent phase. Completely transformed single grains show a distinctive zoning, both in composition and texture. Whereas areas next to the grain boundary consist of nearly pure hydroxyapatite and show a coarse porosity, areas close to the center of the single grains show a high amount of β-TCP and a very fine porous microstructure. If F was added as an additional solution component, the formation of β-TCP was avoided and up to 3wt.% of F were incorporated into the product apatite. The use of the isotope 18O as a chronometer for the replacement reaction makes it possible to reconstruct the chronological development of the calcium phosphate reaction front. Raman analysis revealed that the incorporation of 18O in the PO4 tetrahedron of hydroxyapatite results in the development of distinct profiles in the calcium phosphate reaction front perpendicular to the grain boundaries of the marble. Through the use of the 18O chronometer, it is possible to estimate and compare the time effectiveness of the different fluid pathways in this model system. The results show that the grain boundaries serve as a

  19. Re-examining uranium supply and demand: New insights

    International Nuclear Information System (INIS)

    Kahouli, Sondes

    2011-01-01

    In this paper, we derive a simultaneous system of equations which aims at analysing the uranium supply and demand. In addition to reviewing and updating previous studies dealing with the uranium market analysis, in particular , the contribution of the paper lies in putting attention to some questions which are still either controversial or unanswered. They are especially related to the controversial hypothesis of the interdependence between uranium market and other commodities markets, both, with respect to the demand side, i.e. oil and coal markets, and the supply side, i.e. gold market. The paper also casts lights on electricity and uranium price effects on uranium demand as well as on the simultaneous interdependencies that may exist between nuclear consumption and nuclear installed capacity. The model is estimated for three different time periods which takes into account the major events that have influenced the nuclear-uranium development, that is, that have constrained the growth rate of nuclear generating capacity, i.e. oil crisis and nuclear accidents. This permits to show if uranium market reaction is independent or it is correlated with specific events associated with each time periods. The model was estimated by using the 3SLS method that correct for the presence of contemporaneously error terms correlation and for the existence of simultaneity bias in the model. Main results give evidence of significant correlation between uranium price and competing fossil fuel prices. They also point-out that uranium price is significantly correlated with the supply forces where supply is significantly dependent on gold prices. Moreover, results show that the electricity prices have a significant effect on the uranium demand only in the post-1990 period, probably following the worldwide electricity prices increasing trend. Further, our estimations show that uranium demand is significantly correlated with uranium price only in the period of nuclear major expansion. As

  20. Re-examining uranium supply and demand: New insights

    Energy Technology Data Exchange (ETDEWEB)

    Kahouli, Sondes, E-mail: sondes.kahouli@univ-nantes.f [Universite de Nantes, Laboratoire d' Economie et de Management de Nantes Atlantique (LEMNA), Institut d' Economie et de Management de Nantes-I.A.E., Chemin de la Censive du Tertre-B.P. 52231, 44322 Nantes Cedex 3 (France)

    2011-01-15

    In this paper, we derive a simultaneous system of equations which aims at analysing the uranium supply and demand. In addition to reviewing and updating previous studies dealing with the uranium market analysis, in particular , the contribution of the paper lies in putting attention to some questions which are still either controversial or unanswered. They are especially related to the controversial hypothesis of the interdependence between uranium market and other commodities markets, both, with respect to the demand side, i.e. oil and coal markets, and the supply side, i.e. gold market. The paper also casts lights on electricity and uranium price effects on uranium demand as well as on the simultaneous interdependencies that may exist between nuclear consumption and nuclear installed capacity. The model is estimated for three different time periods which takes into account the major events that have influenced the nuclear-uranium development, that is, that have constrained the growth rate of nuclear generating capacity, i.e. oil crisis and nuclear accidents. This permits to show if uranium market reaction is independent or it is correlated with specific events associated with each time periods. The model was estimated by using the 3SLS method that correct for the presence of contemporaneously error terms correlation and for the existence of simultaneity bias in the model. Main results give evidence of significant correlation between uranium price and competing fossil fuel prices. They also point-out that uranium price is significantly correlated with the supply forces where supply is significantly dependent on gold prices. Moreover, results show that the electricity prices have a significant effect on the uranium demand only in the post-1990 period, probably following the worldwide electricity prices increasing trend. Further, our estimations show that uranium demand is significantly correlated with uranium price only in the period of nuclear major expansion. As

  1. Re-examining uranium supply and demand. New insights

    Energy Technology Data Exchange (ETDEWEB)

    Kahouli, Sondes [Universite de Nantes, Laboratoire d' Economie et de Management de Nantes Atlantique (LEMNA), Institut d' Economie et de Management de Nantes - I.A.E., Chemin de la Censive du Tertre - B.P. 52231, 44322 Nantes Cedex 3 (France)

    2011-01-15

    In this paper, we derive a simultaneous system of equations which aims at analysing the uranium supply and demand. In addition to reviewing and updating previous studies dealing with the uranium market analysis, in particular, the contribution of the paper lies in putting attention to some questions which are still either controversial or unanswered. They are especially related to the controversial hypothesis of the interdependence between uranium market and other commodities markets, both, with respect to the demand side, i.e. oil and coal markets, and the supply side, i.e. gold market. The paper also casts lights on electricity and uranium price effects on uranium demand as well as on the simultaneous interdependencies that may exist between nuclear consumption and nuclear installed capacity. The model is estimated for three different time periods which takes into account the major events that have influenced the nuclear-uranium development, that is, that have constrained the growth rate of nuclear generating capacity, i.e. oil crisis and nuclear accidents. This permits to show if uranium market reaction is independent or it is correlated with specific events associated with each time periods. The model was estimated by using the 3SLS method that correct for the presence of contemporaneously error terms correlation and for the existence of simultaneity bias in the model. Main results give evidence of significant correlation between uranium price and competing fossil fuel prices. They also point-out that uranium price is significantly correlated with the supply forces where supply is significantly dependent on gold prices. Moreover, results show that the electricity prices have a significant effect on the uranium demand only in the post-1990 period, probably following the worldwide electricity prices increasing trend. Further, our estimations show that uranium demand is significantly correlated with uranium price only in the period of nuclear major expansion. As

  2. Chemical and biological insights into uranium-induced apoptosis of rat hepatic cell line

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Fang; You, Yong [University of South China, College of Hunan Province, Key Laboratory of Tumor Cellular and Molecular Pathology, Hengyang (China); Du, Ke-Jie [University of South China, School of Chemistry and Chemical Engineering, Hengyang (China); Fang, Zhen [Anhui Normal University, College of Chemistry and Materials Science, Wuhu (China); Wen, Ge-Bo [University of South China, College of Hunan Province, Key Laboratory of Tumor Cellular and Molecular Pathology, Hengyang (China); University of South China, Laboratory of Protein Structure and Function, Hengyang (China); Lin, Ying-Wu [University of South China, School of Chemistry and Chemical Engineering, Hengyang (China); University of South China, Laboratory of Protein Structure and Function, Hengyang (China)

    2015-05-15

    Uranium release into the environment is a threat to human health, and the mechanisms of cytotoxicity caused by uranium are not well-understood. To improve our understanding in this respect, we herein evaluated the effects of uranium exposure on normal rat hepatic BRL cells. As revealed by scanning electron microscopy and transmission electron microscope analysis, uranyl nitrate was found to be transformed into uranyl phosphate particles in the medium and taken up by BRL cells in an endocytotic uptake manner, which presumably initiates apoptosis of the cell, although soluble uranyl ion may also be toxic. The apoptosis of BRL cells upon uranium exposure was also confirmed by both the acridine orange and ethidium bromide double staining assay and the Annexin V/propidium iodide double staining assay. Further studies revealed that uranium induced the loss of mitochondrial membrane potential in a dose-dependent manner. Moreover, the uranium-induced apoptosis was found to be associated with the activation of caspase-3, caspase-8 and caspase-9, indicating both a mitochondria-dependent signaling pathway and a death receptor pathway by a crosstalk. This study provides new chemical and biological insights into the mechanism of uranium toxicity toward hepatic cells, which will help seek approaches for biological remediation of uranium. (orig.)

  3. Analysis of Hazards Associated with a Process Involving Uranium Metal and Uranium Hydride Powders

    Energy Technology Data Exchange (ETDEWEB)

    Bullock, J.S.

    2000-05-01

    An analysis of the reaction chemistry and operational factors associated with processing uranium and uranium hydride powders is presented, focusing on a specific operation in the Development Division which was subjected to the Job Hazard Analysis (JHA) process. Primary emphasis is on the thermodynamic factors leading to pyrophoricity in common atmospheres. The discussion covers feed powders, cold-pressed and hot-pressed materials, and stray material resulting from the operations. The sensitivity of the various forms of material to pyrophoricity in common atmospheres is discussed. Operational recommendations for performing the work described are given.

  4. X-ray photoelectron and Auger electron spectroscopic study of the adsorption of molecular iodine on uranium metal and uranium dioxide

    International Nuclear Information System (INIS)

    Dillard, J.G.; Moers, H.; Klewe-Nebenius, H.; Kirch, G.; Pfennig, G.; Ache, H.J.

    1984-01-01

    The adsorption of molecular iodine on uranium metal and on uranium dioxide has been investigated at 25 0 C. Clean surfaces were prepared in an ultrahigh vacuum apparatus and were characterized by X-ray photoelectron (XPS) and X-ray and electron-induced Auger electron spectroscopies (AES). Adsorption of I 2 was studied for exposures up to 100 langmuirs (1 langmuir = 10 -6 torr s) on uranium metal and to 75 langmuirs on uranium dioxide. Above about 2-langmuir I 2 exposure on uranium, spectroscopic evidence is obtained to indicate the beginning of UI 3 formation. Saturation coverage for I 2 adsorption on uranium dioxide occurs at approximately 10-15 langmuirs. Analysis of the XPS and AES results as well as studies of spectra as a function of temperature lead to the conclusions that a dissociative chemisorption/reaction process occurs on uranium metal while nondissociative adsorption occurs on uranium dioxide. Variations in the iodine Auger kinetic energy and in the Auger parameter are interpreted in light of extra-atomic relaxation processes. 42 references, 10 figures, 1 table

  5. The neurotoxicology of uranium

    International Nuclear Information System (INIS)

    Dinocourt, Céline; Legrand, Marie; Dublineau, Isabelle; Lestaevel, Philippe

    2015-01-01

    The brain is a target of environmental toxic pollutants that impair cerebral functions. Uranium is present in the environment as a result of natural deposits and release by human applications. The first part of this review describes the passage of uranium into the brain, and its effects on neurological functions and cognitive abilities. Very few human studies have looked at its cognitive effects. Experimental studies show that after exposure, uranium can reach the brain and lead to neurobehavioral impairments, including increased locomotor activity, perturbation of the sleep-wake cycle, decreased memory, and increased anxiety. The mechanisms underlying these neurobehavioral disturbances are not clearly understood. It is evident that there must be more than one toxic mechanism and that it might include different targets in the brain. In the second part, we therefore review the principal mechanisms that have been investigated in experimental models: imbalance of the anti/pro-oxidant system and neurochemical and neurophysiological pathways. Uranium effects are clearly specific according to brain area, dose, and time. Nonetheless, this review demonstrates the paucity of data about its effects on developmental processes and the need for more attention to the consequences of exposure during development.

  6. Reaction pathways of model compounds of biomass-derived oxygenates on Fe/Ni bimetallic surfaces

    Science.gov (United States)

    Yu, Weiting; Chen, Jingguang G.

    2015-10-01

    Controlling the activity and selectivity of converting biomass-derivatives to fuels and valuable chemicals is critical for the utilization of biomass feedstocks. There are primarily three classes of non-food competing biomass, cellulose, hemicellulose and lignin. In the current work, glycolaldehyde, furfural and acetaldehyde are studied as model compounds of the three classes of biomass-derivatives. Monometallic Ni(111) and monolayer (ML) Fe/Ni(111) bimetallic surfaces are studied for the reaction pathways of the three biomass surrogates. The ML Fe/Ni(111) surface is identified as an efficient surface for the conversion of biomass-derivatives from the combined results of density functional theory (DFT) calculations and temperature programmed desorption (TPD) experiments. A correlation is also established between the optimized adsorption geometry and experimental reaction pathways. These results should provide helpful insights in catalyst design for the upgrading and conversion of biomass.

  7. Study of the dry processing of uranium ores; Etude des traitements de minerais d'uranium par voie seche

    Energy Technology Data Exchange (ETDEWEB)

    Guillet, H

    1959-02-01

    A description is given of direct fluorination of pre-concentrated uranium ores in order to obtain the hexafluoride. After normal sulfuric acid treatment of the ore to eliminate silica, the uranium is precipitated by a load of lime to obtain: either impure calcium uranate of medium grade, or containing around 10% of uranium. This concentrate is dried in an inert atmosphere and then treated with a current of elementary fluorine. The uranium hexafluoride formed is condensed at the outlet of the reaction vessel and may be used either for reduction to tetrafluoride and the subsequent manufacture of uranium metal or as the initial product in a diffusion plant. (author) [French] Il s'agit d'une description de fluoration directe de preconcentres de minerais d'uranium en vue d'obtention d'hexafluorure. Apres attaque sulfurique normale du minerai, afin d' eliminer la silice, l' uranium est precipite par un toit de chaux pour obtenir: ou uranate de chaux impur de titre moyen, ou uranium de la dizaine du pourcentage. Ce concentre seche en atmosphere inerte est soumis a un courant de fluor elementaire. L'hexafluorure d'uranium forme est condense a la sortie du reacteur et peut etre utilise soit apres reduction en tetrafluorure par l'elaboration d'uranium metal, soit comme produit de base dans le cadre d'une usine de diffusion. (auteur)

  8. Pyrophoricity of uranium in long-term storage environments

    International Nuclear Information System (INIS)

    Solbrig, C.W.; Krsul, J.R.; Olsen, D.N.

    1994-01-01

    A corrosion cycle for uranium is postulated which can be used to assess whether a given storage situation might produce fire hazards and/or continual uranium corrosion. A significant reaction rate of uranium and moisture occurs at room temperature which produces uranium oxide and hydrogen. If the hydrogen cannot escape, it will react slowly with uranium to form uranium hydride. The hydride is pyrophoric at room temperature when exposed to air. Either the hydrogen or the hydride can produce a dangerous situation as demonstrated by two different incidents described here. Long-term corrosion will occur even if the normal precautions are taken as is demonstrated by the long-term storage of stainless steel clad uranium fuel plates. The major initiator of these problems is attributed to any moisture condensed on the metal or any brought in by the cover gas. The postulated corrosion cycle is used to suggest ways to circumvent these problems

  9. Metabolic control analysis of biochemical pathways based on a thermokinetic description of reaction rates

    DEFF Research Database (Denmark)

    Nielsen, Jens Bredal

    1997-01-01

    Metabolic control analysis is a powerful technique for the evaluation of flux control within biochemical pathways. Its foundation is the elasticity coefficients and the flux control coefficients (FCCs). On the basis of a thermokinetic description of reaction rates it is here shown...... that the elasticity coefficients can be calculated directly from the pool levels of metabolites at steady state. The only requirement is that one thermodynamic parameter be known, namely the reaction affinity at the intercept of the tangent in the inflection point of the curve of reaction rate against reaction...... of the thermokinetic description of reaction rates to include the influence of effecters. Here the reaction rate is written as a linear function of the logarithm of the metabolite concentrations. With this type of rate function it is shown that the approach of Delgado and Liao [Biochem. J. (1992) 282, 919-927] can...

  10. Metabolomics identifies a biological response to chronic low-dose natural uranium contamination in urine samples.

    Science.gov (United States)

    Grison, Stéphane; Favé, Gaëlle; Maillot, Matthieu; Manens, Line; Delissen, Olivia; Blanchardon, Eric; Banzet, Nathalie; Defoort, Catherine; Bott, Romain; Dublineau, Isabelle; Aigueperse, Jocelyne; Gourmelon, Patrick; Martin, Jean-Charles; Souidi, Maâmar

    2013-01-01

    Because uranium is a natural element present in the earth's crust, the population may be chronically exposed to low doses of it through drinking water. Additionally, the military and civil uses of uranium can also lead to environmental dispersion that can result in high or low doses of acute or chronic exposure. Recent experimental data suggest this might lead to relatively innocuous biological reactions. The aim of this study was to assess the biological changes in rats caused by ingestion of natural uranium in drinking water with a mean daily intake of 2.7 mg/kg for 9 months and to identify potential biomarkers related to such a contamination. Subsequently, we observed no pathology and standard clinical tests were unable to distinguish between treated and untreated animals. Conversely, LC-MS metabolomics identified urine as an appropriate biofluid for discriminating the experimental groups. Of the 1,376 features detected in urine, the most discriminant were metabolites involved in tryptophan, nicotinate, and nicotinamide metabolic pathways. In particular, N -methylnicotinamide, which was found at a level seven times higher in untreated than in contaminated rats, had the greatest discriminating power. These novel results establish a proof of principle for using metabolomics to address chronic low-dose uranium contamination. They open interesting perspectives for understanding the underlying biological mechanisms and designing a diagnostic test of exposure.

  11. Preliminary study of the preparation of uranium 232 by irradiation of protactinium 231

    International Nuclear Information System (INIS)

    Guillot, Ph.

    1965-01-01

    A bibliography about preparation of uranium 232 is done. This even-even isotope of uranium is suitable for radioactive tracer, neutron source through α,n reaction and heat source applications. The irradiation of protactinium 231, the chemical separation and the purification of uranium are studied. (author) [fr

  12. Mitigation of Hydrogen Gas Generation from the Reaction of Uranium Metal with Water in K Basin Sludge and Sludge Waste Forms

    Energy Technology Data Exchange (ETDEWEB)

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2011-06-08

    Prior laboratory testing identified sodium nitrate and nitrite to be the most promising agents to minimize hydrogen generation from uranium metal aqueous corrosion in Hanford Site K Basin sludge. Of the two, nitrate was determined to be better because of higher chemical capacity, lower toxicity, more reliable efficacy, and fewer side reactions than nitrite. The present lab tests were run to determine if nitrate’s beneficial effects to lower H2 generation in simulated and genuine sludge continued for simulated sludge mixed with agents to immobilize water to help meet the Waste Isolation Pilot Plant (WIPP) waste acceptance drainable liquid criterion. Tests were run at ~60°C, 80°C, and 95°C using near spherical high-purity uranium metal beads and simulated sludge to emulate uranium-rich KW containerized sludge currently residing in engineered containers KW-210 and KW-220. Immobilization agents tested were Portland cement (PC), a commercial blend of PC with sepiolite clay (Aquaset II H), granulated sepiolite clay (Aquaset II G), and sepiolite clay powder (Aquaset II). In all cases except tests with Aquaset II G, the simulated sludge was mixed intimately with the immobilization agent before testing commenced. For the granulated Aquaset II G clay was added to the top of the settled sludge/solution mixture according to manufacturer application directions. The gas volumes and compositions, uranium metal corrosion mass losses, and nitrite, ammonia, and hydroxide concentrations in the interstitial solutions were measured. Uranium metal corrosion rates were compared with rates forecast from the known uranium metal anoxic water corrosion rate law. The ratios of the forecast to the observed rates were calculated to find the corrosion rate attenuation factors. Hydrogen quantities also were measured and compared with quantities expected based on non-attenuated H2 generation at the full forecast anoxic corrosion rate to arrive at H2 attenuation factors. The uranium metal

  13. Mitigation of Hydrogen Gas Generation from the Reaction of Uranium Metal with Water in K Basin Sludge and Sludge Waste Forms

    International Nuclear Information System (INIS)

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2011-01-01

    Prior laboratory testing identified sodium nitrate and nitrite to be the most promising agents to minimize hydrogen generation from uranium metal aqueous corrosion in Hanford Site K Basin sludge. Of the two, nitrate was determined to be better because of higher chemical capacity, lower toxicity, more reliable efficacy, and fewer side reactions than nitrite. The present lab tests were run to determine if nitrate's beneficial effects to lower H2 generation in simulated and genuine sludge continued for simulated sludge mixed with agents to immobilize water to help meet the Waste Isolation Pilot Plant (WIPP) waste acceptance drainable liquid criterion. Tests were run at ∼60 C, 80 C, and 95 C using near spherical high-purity uranium metal beads and simulated sludge to emulate uranium-rich KW containerized sludge currently residing in engineered containers KW-210 and KW-220. Immobilization agents tested were Portland cement (PC), a commercial blend of PC with sepiolite clay (Aquaset II H), granulated sepiolite clay (Aquaset II G), and sepiolite clay powder (Aquaset II). In all cases except tests with Aquaset II G, the simulated sludge was mixed intimately with the immobilization agent before testing commenced. For the granulated Aquaset II G clay was added to the top of the settled sludge/solution mixture according to manufacturer application directions. The gas volumes and compositions, uranium metal corrosion mass losses, and nitrite, ammonia, and hydroxide concentrations in the interstitial solutions were measured. Uranium metal corrosion rates were compared with rates forecast from the known uranium metal anoxic water corrosion rate law. The ratios of the forecast to the observed rates were calculated to find the corrosion rate attenuation factors. Hydrogen quantities also were measured and compared with quantities expected based on non-attenuated H2 generation at the full forecast anoxic corrosion rate to arrive at H2 attenuation factors. The uranium metal

  14. Study and development of refractory coatings for metallic uranium fusion and evaporation

    International Nuclear Information System (INIS)

    Vasconcelos, Getulio de

    2004-01-01

    In melting process or evaporation of metallic uranium, the reaction with the crucible and the possible contamination of the molten metal should be avoided. This effect can be reduced using an inert and protective coating on the crucible walls. The selection of the coating should be based on the chemical inertia and the kinetic of the reaction products. By avoiding chemical reactions, the amount of impurities in the molten metal can be reduced, leading to an increased crucible lifetime. This work presents a comparative study among different crucible coatings used in the melting process of metallic uranium, at temperatures above its melting point. Samples of metallic uranium are melted in contact with different materials in a vacuum furnace. The reactions occur at a given temperature during a certain time interval; samples are then cooled down to room temperature. Finally, samples are characterized by optical and electronic microscopy, dispersive X-ray spectroscopy, surface roughness and X-ray diffraction. Samples preparation consists of polishing selected areas, and milling the reaction products originated from the corroded interfaces. The extent of the reactions is determined as a function of the temperature by optical microscopy and roughness analyses. The compositions of the reacted products are determined by Energy Dispersive Spectroscopy, and the phase changes by X-ray diffraction. The results indicate that alumina presented higher activation energy (39 kcal.mol -1 ) than magnesia (12 kcal.mol -1 ), otherwise, it is corroded faster. On the other hand, the alumina could be protected by a thick coating of titanium nitride, because no rection between titanium nitride and uranium was observed at temperatures near to 1700 K. After cooling to the room temperature, there is stress concentration between the graphite and the TiN layer, generating a compressive stress of 0,5 GPa. When uranium is deposited on the TiN, a tensile stress is generated in this new layer, which

  15. Kinetics of the glucose/glycine Maillard reaction pathways: influences of pH and reactant initial concentrations

    NARCIS (Netherlands)

    Martins, S.I.F.S.; Boekel, van M.A.J.S.

    2005-01-01

    A previously proposed kinetic model for the glucose/glycine Maillard reaction pathways has been validated by changing the initial pH (4.8, 5.5, 6.0, 6.8 and 7.5) of the reaction and reactant initial concentrations (1:2 and 2:1 molar ratios were compared to the 1:1 ratio). The model consists of 10

  16. Behaviour of uranium dioxide in liquid nitrogen tetraoxide

    International Nuclear Information System (INIS)

    Kobets, L.V.; Klavsut', G.N.; Dolgov, V.M.

    1983-01-01

    Interaction kinetics of uranium dioxide with liquid nitrogen tetroxide at 25-150 deg C has been studied. It is shown that in the temperature range studied NO[UO 2 (NO 3 ) 3 ] is the final product of the reaction. With the increase of specific surface of uranium dioxide and with the temperature increase the degree of oxide transformation increases. Uranium dioxide-liquid N 2 O 4 interaction proceeds in the diffusion region. Seeming activation energies and rate constants of the mentioned processes are calculated. Effect of nitrogen trioxide additions on transformation kinetics is considered

  17. Environmental radiological impact of some Portuguese uranium mines

    International Nuclear Information System (INIS)

    Galvao, J.P.; Bettencourt, A.O.; Teixeira, M.M.G.R.; Elias, M.D.T.

    1988-01-01

    An environmental radiological surveillance programme has been in progress around the most significant Portuguese uranium mines, from 1976 to 1983. A short description is given of the mines of Urgeirica (including uranium milling), Freixiosa, Pinhal de Souto and Bica. The results of the surveillance programme developed in the vicinity of these facilities are presented and the identified critical pathways are discussed. One of these pathways is the consumption of cabbage, which is an important component in the diet of the Portuguese population. The exposure of the critical groups, due to the intake of 226 Ra through the diet, calculated from the results of this monitoring programme, range from 0.02 to 1.5 mSv.y -1 for the different mines under study. (author)

  18. Synthesis of resorcinol resin as a polymer adsorbent, and study of its usability in uranium sorption process

    International Nuclear Information System (INIS)

    Aslani, M. A. A.; Yusan, S.; Goek, C.; Akyil, S.; Aytas, S.

    2009-01-01

    Uranium is one of the most important elements in nuclear fuel technology. In order to obtain purified of this element at uranium mining and processing the use of synthetic resins is significant at column and/or batch process. The synthesis of resorcinol resin polymer was carried out with a modified microwave oven instead of the conventional heater due to the some advantage properties such as very rapid reaction, rapid bulk heat, short reaction duration and high yield etc. To characterization of synthesized resin FT-IR, TG-DTA and SEM techniques were used. In order to obtain the optimum uranium adsorption conditions the effective sorption parameters such as solution pH, uranium concentration, reaction time and temperature were investigated.

  19. Contribution to Yttria corrosion study by liquid uranium; Contribution a l`etude de la corrosion de l`yttria par l`uranium liquide

    Energy Technology Data Exchange (ETDEWEB)

    Tournier, C

    1995-02-01

    We are studying liquid uranium and polycrystalline Yttria interactions under secondary vacuum. The type, morphology and thickness of interfacial reaction products between U and Y{sub 2}O{sub 3} are examined by optical and confocal microscopy, SEM, X ray diffraction, X analysis and XPS. The most important parameters are the stoechiometry and microstructure of the Yttria, the oxygen partial pressure of the furnace atmosphere, pO{sub 2}, and the duration and temperature of experiments. In the thermodynamic modelization, we take into account exchanges at the ceramic/metal interface and exchanges between the molten metal and the furnace atmosphere. Liquid uranium reacts with Yttria to form UO{sub 2} at the interface which gradually changes into a solid solution UO{sub 2}-Y{sub 2}O{sub 3}. The total thickness of reaction products results from two opposing reactions: (i) oxidation of uranium by Yttria (low pO{sub 2}) or by the atmosphere (high pO{sub 2}), controlled by migration of oxygen vacancies at Yttria grain boundaries. (ii) deoxidation caused by the formation of volatile uranium monoxide. On the other hand, we observed a transition of the type ``non-wettability {yields} wettability `` which occurs subsequent to an increase of the stoichiometric variation x in Y{sub 2}O{sub 3-x}. (author). 69 refs., 76 figs., 30 tabs.

  20. Kinetics of the reduction of uranium oxide catalysts

    International Nuclear Information System (INIS)

    Heynen, H.W.G.; Camp-van Berkel, M.M.; Bann, H.S. van der

    1977-01-01

    The reduction of uranium oxide and uranium oxide on alumina catalysts by ethylbenzene and by hydrogen has been studied in a thermobalance. Ethylbenzene mole fractions between 0.0026 and 0.052 and hydrogen mole fractions between 0.1 and 0.6 were applied at temperatures of 425--530 0 C. During the reduction the uranium oxides are converted into UO 2 . The rate of reduction of pure uranium oxide appears to be constant in the composition region UO/sub 2.6/-UO/sub 2.25/. The extent of this region is independent of the concentration of the reducing agents and of the reaction temperature. The constant rate is explained in terms of a constant oxygen pressure which is in equilibrium with the two solid phases, U 3 O/sub 8-x/ and U 4 O 9 . The reduction rate is first order in hydrogen and zero order in ethylbenzene with activation energies of 120 and 190 kJ mol -1 , respectively. Oxygen diffusion through the lattice is probably not rate limiting. The reduction behavior of uranium oxide on alumina is different from that of pure uranium oxide; the rate of reduction continuously decreases with increasing degree of reduction. An explanation for this behavior has been given by visualizing this catalyst as a set of isolated uranium oxide crystallites with a relative wide variation of diameters, in an alumina matrix. At the beginning of the reduction, carbon dioxide and water are the only reaction products. Thereafter, benzene is found as well and, finally, at U/O ratios below 2.25, styrene also appears in the reactor outlet

  1. Preparation and Purification of natural uranium metal by Iodine method

    International Nuclear Information System (INIS)

    Taies, J.A.

    2008-01-01

    In this work ,glass-metal apparatus was designed and manufactured which used for preparing a high purity uranium.The reaction is simply take place between iodine vapour and uranium metal at 500C in closed system to form uranium tetra iodide which is decomposed on hot wire at high temperature around 1100C.Also another apparatus was made from Glass and used for preparing a high purity of UI 4 more than 99.9%purity

  2. Criticality safety concerns of uranium deposits in cascade equipment

    International Nuclear Information System (INIS)

    Plaster, M.J.

    1996-01-01

    The Paducah and Portsmouth Gaseous Diffusion Plants enrich uranium in the 235 U isotope by diffusing gaseous uranium hexafluoride (UF 6 ) through a porous barrier. The UF 6 gaseous diffusion cascade utilized several thousand open-quotes stagesclose quotes of barrier to produce highly enriched uranium (HEU). Historically, Portsmouth has enriched the Paducah Gaseous Diffusion Plant's product (typically 1.8 wt% 235 U) as well as natural enrichment feed stock up to 97 wt%. Due to the chemical reactivity of UF 6 , particularly with water, the formation of solid uranium deposits occur at a gaseous diffusion plant. Much of the equipment operates below atmospheric pressure, and deposits are formed when atmospheric air enters the cascade. Deposits may also be formed from UF 6 reactions with oil, UF 6 reactions with the metallic surfaces of equipment, and desublimation of UF 6 . The major deposits form as a result of moist air in leakage due to failure of compressor casing flanges, blow-off plates, seals, expansion joint convolutions, and instrument lines. This report describes criticality concerns and deposit disposition

  3. Influence of diffusion on extraction kinetics in porous bodies. The case of uranium oxides; Influence de la diffusion sur la cinetique d'extraction dans un corps poreux. Cas des oxydes de l'uranium

    Energy Technology Data Exchange (ETDEWEB)

    Tinturier, B [Commissariat a l' Energie Atomique, Fontenay-Aux-Roses (France). Centre d' Etudes Nucleaires

    1966-12-01

    The study of the leaching of heaped uranium ore can be considered theoretically as the problem of the diffusion of liquids in porous bodies and in particular as that of its influence on the chemical reaction rates of conventional uranium oxides. Below a certain value of the pore diameter, it is diffusion which is responsible for mass transfer. The porous structure can be characterized by various physical constants which modify the free diffusion equation and, as long as the pores have a diameter greater than a few microns, it can be shown that the pore walls have a negligible effect on the diffusion. The diffusion coefficients for the nitrate, the sulfate, the chloride, the acetate and the perchlorate of uranium have been determined. In the case of the reaction of uranium trioxide with acids in a porous body, the reaction kinetics are governed by the arrival of the reagent by diffusion. The attack of uranium dioxide by an acid ferric iron solution has been studied under the same conditions and it has been found that the diffusion modifies the influence of the ferrous and ferric iron concentrations on the reaction kinetics. The same is true for the oxide U{sub 3}O{sub 8}. All the results concerning these reactions studied in the absence of the influence of diffusion should be modified to take this factor into account when it intervenes in an extraction process. (authors) [French] L'etude de la lixiviation en tas d'un minerai d'uranium peut se ramener theoriquement au probleme de la diffusion des liquides dans les corps poreux et en particulier a celui de son influence sur les vitesses de reaction chimique des oxydes classiques de l'uranium. En dessous d'une certaine limite de diametre des pores la diffusion est responsable du transfert de masse. La structure poreuse peut se caracteriser par differentes constantes physiques qui modifient l'equation de la diffusion libre et tant que les pores ont un diametre superieur a quelques microns, on a montre que l

  4. Investigation of (n, 2n) reaction and fission rates in iron-shielded uranium samples bombarded by 14.9 MeV neutrons

    International Nuclear Information System (INIS)

    Shani, G.

    1976-01-01

    The effect of the thickness of iron shielding on the (n, 2n) reaction rate in a fusion reactor (hybrid) blanket is investigated. The results are compared with the fission rate-dependence. Samples of natural uranium are irradiated with 14 MeV neutrons, with iron slabs of various thickness between the neutron generator target and the samples. Both reactions are threshold reactions but the fact that the 238 U (n, 2n) reaction threshold is at 6 MeV and that of fission is at 2 MeV makes the ratio between the two very much geometry-dependent. Two geometrical effects take place, the 1/r 2 and the build-up. While the build-up affects the (n, 2n) reaction rate, the fission rate is affected more by the 1/r 2 effect. The reason is that both elastic and inelastic scattering end up with neutrons with energy above fission threshold, while only elastic scattering brings high energy neutrons to the sample and causes (n, 2n) reaction. A comparison is made with calculated results where the geometrical effects do not exist. (author)

  5. Bicarbonate Elution of Uranium from Amidoxime-Based Polymer Adsorbents for Sequestering Uranium from Seawater

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Horng-Bin [Department of Chemistry, University of Idaho, Moscow, Idaho 83844 USA; Wai, Chien M. [Department of Chemistry, University of Idaho, Moscow, Idaho 83844 USA; Kuo, Li-Jung [Pacific Northwest National Laboratory, Marine Sciences Laboratory, Sequim, Washington 98382 USA; Gill, Gary [Pacific Northwest National Laboratory, Marine Sciences Laboratory, Sequim, Washington 98382 USA; Tian, Guoxin [Lawrence Berkeley National Laboratory, Berkeley, California 94720 USA; Rao, Linfeng [Lawrence Berkeley National Laboratory, Berkeley, California 94720 USA; Das, Sadananda [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 USA; Mayes, Richard T. [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 USA; Janke, Christopher J. [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 USA

    2017-05-02

    Uranium adsorbed on amidoxime-based polyethylene fibers in simulated seawater can be quantitatively eluted using 3 M KHCO3 at 40°C. Thermodynamic calculations are in agreement with the experimental observation that at high bicarbonate concentrations (3 M) uranyl ions bound to amidoxime molecules are converted to uranyl tris-carbonato complex in the aqueous solution. The elution process is basically the reverse reaction of the uranium adsorption process which occurs at a very low bicarbonate concentration (~10-3 M) in seawater. In real seawater experiments, the bicarbonate elution is followed by a NaOH treatment to remove natural organic matter adsorbed on the polymer adsorbent. Using the sequential bicarbonate and NaOH elution, the adsorbent is reusable after rinsing with deionized water and the recycled adsorbent shows no loss of uranium loading capacity based on real seawater experiments.

  6. Exposure pathways and health effects associated with chemical and radiological toxicity of natural uranium: a review.

    Science.gov (United States)

    Brugge, Doug; de Lemos, Jamie L; Oldmixon, Beth

    2005-01-01

    Natural uranium exposure derives from the mining, milling, and processing of uranium ore, as well as from ingestion of groundwater that is naturally contaminated with uranium. Ingestion and inhalation are the primary routes of entry into the body. Absorption of uranium from the lungs or digestive track is typically low but can vary depending on compound specific solubility. From the blood, two-thirds of the uranium is excreted in urine over the first 24 hours and up to 80% to 90% of uranium deposited in the bone leaves the body within 1.5 years. The primary health outcomes of concern documented with respect to uranium are renal, developmental, reproductive, diminished bone growth, and DNA damage. The reported health effects derive from experimental animal studies and human epidemiology. The Lowest Observed Adverse Effect Level (LOAEL) derived from animal studies is 50 microg/m3 for inhalation and 60 ug/kg body weight/day for ingestion. The current respiratory standard of the Occupational Safety and Health Administration (OSHA), 50 microg/m3, affords no margin of safety. Considering the safety factors for species and individual variation, the ingestion LOAEL corresponds to the daily consumption set by the World Health Organization Drinking Water Standard at 2 microg/L. Based on economic considerations, the United States Environmental Protection Agency maximum contaminant level is 30 microg/L. Further research is needed, with particular attention on the impact of uranium on indigenous populations, on routes of exposure in communities near uranium sites, on the combined exposures present at many uranium sites, on human developmental defects, and on health effects at or below established exposure standards.

  7. Degradation of ibuprofen by hydrodynamic cavitation: Reaction pathways and effect of operational parameters.

    Science.gov (United States)

    Musmarra, Dino; Prisciandaro, Marina; Capocelli, Mauro; Karatza, Despina; Iovino, Pasquale; Canzano, Silvana; Lancia, Amedeo

    2016-03-01

    Ibuprofen (IBP) is an anti-inflammatory drug whose residues can be found worldwide in natural water bodies resulting in harmful effects to aquatic species even at low concentrations. This paper deals with the degradation of IBP in water by hydrodynamic cavitation in a convergent-divergent nozzle. Over 60% of ibuprofen was degraded in 60 min with an electrical energy per order (EEO) of 10.77 kWh m(-3) at an initial concentration of 200 μg L(-1) and a relative inlet pressure pin=0.35 MPa. Five intermediates generated from different hydroxylation reactions were identified; the potential mechanisms of degradation were sketched and discussed. The reaction pathways recognized are in line with the relevant literature, both experimental and theoretical. By varying the pressure upstream the constriction, different degradation rates were observed. This effect was discussed according to a numerical simulation of the hydroxyl radical production identifying a clear correspondence between the maximum kinetic constant kOH and the maximum calculated OH production. Furthermore, in the investigated experimental conditions, the pH parameter was found not to affect the extent of degradation; this peculiar feature agrees with a recently published kinetic insight and has been explained in the light of the intermediates of the different reaction pathways. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Photothermal deflection spectroscopy investigations of uranium electrochemistry

    International Nuclear Information System (INIS)

    Russo, R.E.; Rudnicki, J.D.

    1993-01-01

    Photothermal Deflection Spectroscopy (PDS) has been successfully applied to the study of uranium oxide electrochemistry. A brief description of PDS and preliminary results that demonstrate the technique are presented. Concentration gradients formed at the electrode surface are measured by this technique. The gradients give insight into the reaction mechanisms. There is some evidence of the initiation of non-electrochemical dissolution of the uranium oxide. Optical absorption by the uranium oxide is measured by PDS and the first results indicate that the absorption of the surface does not change during electrochemical experiments. This result is contrary to literature measurements of bulk samples that indicate that the optical absorption should be strongly changing

  9. Kinetic study of the thermal decomposition of uranium metaphosphate, U(PO{sub 3}){sub 4}, into uranium pyrophosphate, UP{sub 2}O{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Hee-Chul, E-mail: nhcyang@kaeri.re.kr; Kim, Hyung-Ju; Lee, Si-Young; Yang, In-Hwan; Chung, Dong-Yong

    2017-06-15

    The thermochemical properties of uranium compounds have attracted much interest in relation to thermochemical treatments and the safe disposal of radioactive waste bearing uranium compounds. The characteristics of the thermal decomposition of uranium metaphosphate, U(PO{sub 3}){sub 4}, into uranium pyrophosphate, UP{sub 2}O{sub 7}, have been studied from the view point of reaction kinetics and acting mechanisms. A mixture of U(PO{sub 3}){sub 4} and UP{sub 2}O{sub 7} was prepared from the pyrolysis residue of uranium-bearing spent TBP. A kinetic analysis of the reaction of U(PO{sub 3}){sub 4} into UP{sub 2}O{sub 7} was conducted using an isoconversional method and a master plot method on the basis of data from a non-isothermal thermogravimetric analysis. The thermal decomposition of U(PO{sub 3}){sub 4} into UP{sub 2}O{sub 7} followed a single-step reaction with an activation energy of 175.29 ± 1.58 kJ mol{sup −1}. The most probable kinetic model was determined as a type of nucleation and nuclei-growth models, the Avrami-Erofeev model (A3), which describes that there are certain restrictions on nuclei growth of UP{sub 2}O{sub 7} during the solid-state decomposition of U(PO{sub 3}){sub 4}. - Highlights: •Thermal decomposition kinetics of U(PO{sub 3}){sub 4} into UP{sub 2}O{sub 7} was investigated. •The thermal decomposition followed a single-step reaction with an activation energy of 175.3 ± 1.6 kJ mol{sup −1}. •The most probable kinetic model was determined as a type of nucleation and nuclei-growth models, the Avrami-Erofeev (A3).

  10. Study of ammonia synthesis over uranium catalysts

    International Nuclear Information System (INIS)

    Spitsyn, V.I.; Erofeev, B.V.; Mikhajlenko, I.E.; Gorelkin, I.I.; Ivanov, L.S.

    1980-01-01

    The effect of induced radiactivity and chemical composition of uranium catalysts on their catalytic activity in the ammonia synthesis reaction has been studied. The catalyst samples comprise pieces of metal uranium and chip irradiated in nuclear reactor by the 4.3x10 16 n/cm 2 integral flux of slow neutrons. Studies of catalytic activity was carried out at 1 atm and 340-510 deg C when stoichiometric nitrogen-hydrogen mixture passed through the following installation. At different temperatures uranium nitrides of different composition are shown to be formed. Uranium nitrides with the composition close to UN 2 are the samples with the highest catalYtic activity. The reduction of catalytic activity of uranium catalysts with the increased temperature of their formation above 400 deg C is explained by low catalytic activity of forming UNsub(1.7) in comparison with UN 2 . Catalytic properties of irradiated and nonirradiated samples do not differ from one another

  11. Study of the Formation of Eutectic Melt of Uranium and Thermal Analysis for the Salt Distillation of Uranium Deposits

    International Nuclear Information System (INIS)

    Park, Sung Bin; Hwang, Sung Chan; Kang, Young Ho; Park, Ki Min; Jun, Wan Gi; Lee, Han Soo; Cho, Dong Wook

    2010-01-01

    Uranium deposits from an electrorefining process contain about 30% salt. In order to recover pure uranium and transform it into an ingot, the salts have to be removed from the uranium deposits. Major process variables for the salt distillation process of the uranium deposits are hold temperature and vacuum pressure. Effects of the variables on the salt removal efficiency were studied in the previous study 1. By applying the Hertz-Langmuir relation to the salt evaporation of the uranium deposits, the evaporation coefficients were obtained at the various conditions. The operational conditions for achieving above 99% salt removal were deduced. The salt distilled uranium deposits tend to form the eutectic melt with iron, nickel, chromium for structural material of salt evaporator. In this study, we investigated the hold temperature limitation in order to prevent the formation of the eutectic melt between uranium and other metals. The reactions between the uranium metal and stainless steel were tested at various conditions. And for enhancing the evaporation rate of the salt and the efficient recovery of the distilled salt, the thermal analysis of the salt distiller was conducted by using commercial CFX software. From the thermal analysis, the effect of Ar gas flow on the evaporation of the salt was studied.

  12. Detection of uranium extraction zone by axial temperature profiles in a pulsed column for Purex process

    International Nuclear Information System (INIS)

    Tsukada, T.; Takahashi, K.

    1991-01-01

    A new method was presented for detecting uranium extraction zone in a pulsed column by means of measuring axial temperature profile originated from reaction heat during uranium extraction. Key parameters of the temperature profiles were estimated with a code developed for calculating temperature profiles in a direct-contact heat exchanger such as a pulsed column, and were verified using data from a small pulsed column simulating reaction heat with injecting hot water. Finally, the results were compared with those from an actual uranium extraction tests, indicating that the method presented was promising for detecting uranium extraction zone in a pulsed column. (author)

  13. Reaction of H2 with O2 in Excited Electronic States: Reaction Pathways and Rate Constants.

    Science.gov (United States)

    Pelevkin, Alexey V; Loukhovitski, Boris I; Sharipov, Alexander S

    2017-12-21

    Comprehensive quantum chemical analysis with the use of the multireference state-averaged complete active space self-consistent field approach was carried out to study the reactions of H 2 with O 2 in a 1 Δ g , b 1 Σ g + , c 1 Σ u - , and A' 3 Δ u electronically excited states. The energetically favorable reaction pathways and possible intersystem crossings have been revealed. The energy barriers were refined employing the extended multiconfiguration quasi-degenerate second-order perturbation theory. It has been shown that the interaction of O 2 (a 1 Δ g ) and O 2 (A' 3 Δ u ) with H 2 occurs through the H-abstraction process with relatively low activation barriers that resulted in the formation of the HO 2 molecule in A″ and A' electronic states, respectively. Meanwhile, molecular oxygen in singlet sigma states (b 1 Σ g + and c 1 Σ u - ) was proved to be nonreactive with respect to the molecular hydrogen. Appropriate rate constants for revealed reaction and quenching channels have been estimated using variational transition-state theory including corrections for the tunneling effect, possible nonadiabatic transitions, and anharmonicity of vibrations for transition states and reactants. It was demonstrated that the calculated reaction rate constant for the H 2 + O 2 (a 1 Δ g ) process is in reasonable agreement with known experimental data. The Arrhenius approximations for these processes have been proposed for the temperature range T = 300-3000 K.

  14. Laccase-catalyzed removal of the antimicrobials chlorophene and dichlorophen from water: Reaction kinetics, pathway and toxicity evaluation.

    Science.gov (United States)

    Shi, Huanhuan; Peng, Jianbiao; Li, Jianhua; Mao, Liang; Wang, Zunyao; Gao, Shixiang

    2016-11-05

    As active agents in cleaning and disinfecting products, antimicrobials have been widely spread in the environment and have drawn extensive attention as potential threats to the ecological system and human health. In this study, the laccase-catalyzed removal of two emerging antimicrobials, chlorophene (CP) and dichlorophen (DCP), was investigated under simulated environmental conditions. Intrinsic reaction kinetics showed that the removal of CP and DCP followed second-order reaction kinetics, first-order with respect to both the enzyme and the substrate concentration. It was also found that fulvic acid could suppress the transformation of CP and DCP by reversing the oxidation reactions through its action as a scavenger of the free radical intermediates produced from reactions between laccase and the substrates. Several reaction products were identified by a quadrupole time-of-flight mass spectrometer, and detailed reaction pathways were proposed. For both CP and DCP, direct polymerization was the principal pathway, and the coupling patterns were further corroborated based on molecular modeling. The nucleophilic substitution of chlorine by the hydroxyl group was observed, and further oxidation products capable of coupling with each other were also found. Additionally, toxicity evaluation tests using Scenedesmus obliquus confirmed that the toxicity of CP and DCP was effectively eliminated during the reaction processes. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. A mechanistic study on the reaction pathways leading to benzene and naphthalene in cellulose vapor phase cracking

    International Nuclear Information System (INIS)

    Norinaga, Koyo; Yang, Huamei; Tanaka, Ryota; Appari, Srinivas; Iwanaga, Keita; Takashima, Yuka; Kudo, Shinji; Shoji, Tetsuya; Hayashi, Jun-ichiro

    2014-01-01

    The reaction pathways leading to aromatic hydrocarbons such as benzene and naphthalene in gas-phase reactions of multi-component mixtures derived from cellulose fast pyrolysis were studied both experimentally and numerically. A two-stage tubular reactor was used for evaluating the reaction kinetics of secondary vapor phase cracking of the nascent pyrolysates at temperature ranging from 400 to 900 °C, residence time from 0.2 to 4.3 s, and at 241 kPa. The products of alkyne and diene were identified from the primary pyrolysis of cellulose even at low temperature range 500–600 °C. These products include acetylene, propyne, propadiene, vinylacetylene, and cyclopentadiene. Experiments were also numerically validated by a detailed chemical kinetic model consisting of more than 8000 elementary step-like reactions with over 500 chemical species. Acceptable capabilities of the kinetic model in predicting concentration profiles of the products enabled us to assess reaction pathways leading to benzene and naphthalene via the alkyne and diene from primary pyrolysates of cellulose. C 3 alkyne and diene are primary precursors of benzene at 650 °C, while combination of ethylene and vinylacetylene produces benzene dominantly at 850 °C. Cyclopentadiene is a prominent precursor of naphthalene. Combination of acetylene with propyne or allyl radical leads to the formation of cyclopentadiene. Furan and acrolein are likely important alkyne precursors in cellulose pyrolysis at low temperature, whereas dehydrogenations of olefins are major route to alkyne at high temperatures. - Highlights: • Analytical pyrolysis experiments provided data for kinetic modeling. • Detailed chemical kinetic model was used and evaluated. • Alkyne and diene were important intermediates for aromatic hydrocarbon formation. • Reaction pathways leading to aromatic hydrocarbons were proposed

  16. Behavior of radioactive elements (uranium and thorium) in Bayer process

    International Nuclear Information System (INIS)

    Sato, C.; Kazama, S.; Sakamoto, A.; Hirayanagi, K.

    1986-01-01

    It is essential that alumina used for manufacturing electronic devices should contain an extremely low level of alpha-radiation. The principal source of alpha-radiation in alumina is uranium, a minor source being thorium. Uranium in bauxite dissolves into the liquor in the digestion process and is fixed to the red mud as the desilication reaction progresses. A part of uranium remaining in the liquor precipitates together with aluminum hydroxide in the precipitation process. The uranium content of aluminum hydroxide becomes lower as the precipitation velocity per unit surface area of the seed becomes slower. Organic matters in the Bayer liquor has an extremely significant impact on the uranium content of aluminum hydroxide. Aluminum hydroxide free of uranium is obtainable from the liquor that does not contain organic matters

  17. Study of the dry processing of uranium ores; Etude des traitements de minerais d'uranium par voie seche

    Energy Technology Data Exchange (ETDEWEB)

    Guillet, H

    1959-02-01

    A description is given of direct fluorination of pre-concentrated uranium ores in order to obtain the hexafluoride. After normal sulfuric acid treatment of the ore to eliminate silica, the uranium is precipitated by a load of lime to obtain: either impure calcium uranate of medium grade, or containing around 10% of uranium. This concentrate is dried in an inert atmosphere and then treated with a current of elementary fluorine. The uranium hexafluoride formed is condensed at the outlet of the reaction vessel and may be used either for reduction to tetrafluoride and the subsequent manufacture of uranium metal or as the initial product in a diffusion plant. (author) [French] Il s'agit d'une description de fluoration directe de preconcentres de minerais d'uranium en vue d'obtention d'hexafluorure. Apres attaque sulfurique normale du minerai, afin d' eliminer la silice, l' uranium est precipite par un toit de chaux pour obtenir: ou uranate de chaux impur de titre moyen, ou uranium de la dizaine du pourcentage. Ce concentre seche en atmosphere inerte est soumis a un courant de fluor elementaire. L'hexafluorure d'uranium forme est condense a la sortie du reacteur et peut etre utilise soit apres reduction en tetrafluorure par l'elaboration d'uranium metal, soit comme produit de base dans le cadre d'une usine de diffusion. (auteur)

  18. Study of the optimal reaction conditions for assay of the mouse alternative complement pathway

    NARCIS (Netherlands)

    Dijk, H. van; Rademaker, P.M.; Klerx, J.P.A.M.; Willers, J.M.M.

    1985-01-01

    The optimal reaction conditions for hemolytic assay of alternative complement pathway activity in mouse serum were investigated. A microtiter system was used, in which a number of 7.5×106 rabbit erythrocytes per test well appeared to be optimal. Rabbit erythrocytes were superior as target cells over

  19. Speciation of uranium with respect to hydrogeological aspects

    International Nuclear Information System (INIS)

    Meinrath, G.

    1997-01-01

    Until 1991, eastern Germany has been third largest uranium producer in the world. After the cease of uranium production, larger areas remained contaminated by uranium mining debris, mill-tailings and mining areas. Since 1991 these areas are in the process of remediation by intervention. In Germany, legal stipulations require the prognosis of the likely mid-term impact of an intervention. The benefit of a planned remediation procedure must be evident against the Zero option (doing nothing) and alternative actions. Thermodynamic data of geochemically relevant reactions for uranium under conditions of natural aqueous solution serve as important input data into geochemical reactive transport codes. Especially hydrolysis and carbonato complexation of hexavalent uranium influence the geochemical behaviour of uranium. The first part of the report report summarizes the fundamental chemical facts on mineralogy, electronic structure, UV-Vis and emission spectroscopy of hexavalent uranium. A second part reports in depth the experimental and numerical procedures to study the hydrolytic and carbonate complexation behaviour of hexavalent uranium. The evaluation of single component spectra of the relevant uranium species is discussed. Spectral curves are quantitatively deconcoluted into single components. In all cases the associated uncertainties are given. Thermodynamic data on hydrolysis and carbonato species derived from these experiments are compared to existing data in the literature. (orig.)

  20. Thermal reactions of uranium metal, UO 2, U 3O 8, UF 4, and UO 2F 2 with NF 3 to produce UF 6

    Science.gov (United States)

    McNamara, Bruce; Scheele, Randall; Kozelisky, Anne; Edwards, Matthew

    2009-11-01

    This paper demonstrates that NF 3 fluorinates uranium metal, UO 2, UF 4, UO 3, U 3O 8, and UO 2F 2·2H 2O to produce the volatile UF 6 at temperatures between 100 and 550 °C. Thermogravimetric and differential thermal analysis reaction profiles are described that reflect changes in the uranium fluorination/oxidation state, physiochemical effects, and instances of discrete chemical speciation. Large differences in the onset temperatures for each system investigated implicate changes in mode of the NF 3 gas-solid surface interaction. These studies also demonstrate that NF 3 is a potential replacement fluorinating agent in the existing nuclear fuel cycle and in actinide volatility reprocessing.

  1. A gravimetric method for the determination of oxygen in uranium oxides and ternary uranium oxides by addition of alkaline earth compounds

    International Nuclear Information System (INIS)

    Fujino, Takeo; Tagawa, Hiroaki; Adachi, Takeo; Hashitani, Hiroshi

    1978-01-01

    A simple gravimetric determination of oxygen in uranium oxides and ternary uranium oxides is described. In alkaline earth uranates which are formed by heating in air at 800-1100 0 C, uranium is in the hexavalent state over certain continuous ranges of alkaline earth-to-uranium ratios. Thus, if an alkaline earth uranate or a compound containing an alkaline earth element, e.g. MgO, is mixed with the oxide sample and heated in air under suitable conditions, oxygen can be determined from the weight change before and after the reaction. The standard deviation of the O:U ratio for a UOsub(2+x) test sample is +-0.0008-0.001, if a correction is applied for atmospheric moisture absorbed during mixing. (Auth.)

  2. Acid Dissolution of Depleted Uranium from Catalyst using Microwave

    Energy Technology Data Exchange (ETDEWEB)

    Sung, Jin Hyun; Jeong, Seong Gi; Park, Kwang Heon [Kyunghee University, Yongin (Korea, Republic of)

    2011-05-15

    The separation process of uranium is one of the most important fields in nuclear industry because uranium is used primary in nuclear power plants. Uranium ores are treated by either acid or alkaline reagents. Uranium can be dissolved by acid or alkaline solutions. There are two oxidation states in which the hexavalent form, the oxide of which is UO{sub 3}, and the tetravalent form, the oxide of which is UO{sub 2}. However, depleted uranium(DU) has also been used as a catalyst in specialized chemical reaction such as ammoxidation. The preferred catalyst for propylene oxidation with ammonia was a uranium oxide-antimony oxide composition. The active phase of catalyst was known as USbO{sub 5} and USb{sub 3}O{sub 10}. There is pentavalent form. Waste catalyst containing DU was generated and stored in chemical industry. In this work, we removed DU from catalyst by acid dissolution

  3. Government policy uncertainty and stock prices: The case of Australia's uranium industry

    International Nuclear Information System (INIS)

    Ferguson, Andrew; Lam, Peter

    2016-01-01

    We investigate effects of government policy uncertainty on stock prices, reflecting tension between ‘private interest’ (economic benefits) and ‘public interest’ arguments over uranium mining. Using a sample of Australian-listed uranium firms from January 2005 through June 2008, we document a positive contemporaneous correlation between stock returns and volatility and two measures of government policy uncertainty, proxied by the spread in voters' opinion polls between the two major political parties and a news-based sentiment index. Event-study results show significant stock price reactions to key uranium-related policy events, with cross-sectional variation in event returns predicted by models incorporating firm- and project-level characteristics. Our research design and findings may inform future research on the capital market effects of government policy uncertainty in other regulated industries. - Highlights: • Government policy uncertainty has direct effects on stock prices of uranium explorers. • Stock returns are positively related to the spread in two-party-preferred voting intention. • Stock volatility is positively related to a uranium news-based sentiment index. • Event-study results show significant market reaction to key uranium policy events.

  4. Evidence for single metal two electron oxidative addition and reductive elimination at uranium.

    Science.gov (United States)

    Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; McInnes, Eric J L; Tuna, Floriana; Wooles, Ashley J; Maron, Laurent; Liddle, Stephen T

    2017-12-01

    Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido complex in a reaction that satisfies all criteria of a single-metal two-electron oxidative addition. Thermolysis of this complex promotes extrusion of azobenzene, where H-/D-isotopic labelling finds no isotopomer cross-over and the non-reactivity of a nitrene-trap suggests that nitrenes are not generated and thus a reductive elimination has occurred. Though not optimally balanced in this case, this work presents evidence that classical d-block redox chemistry can be performed reversibly by f-block metals, and that uranium can thus mimic elementary transition metal reactivity, which may lead to the discovery of new f-block catalysis.

  5. High temperature behavior of metallic inclusions in uranium dioxide

    International Nuclear Information System (INIS)

    Yang, R.L.

    1980-08-01

    The object of this thesis was to construct a temperature gradient furnace to simulate the thermal conditions in the reactor fuel and to study the migration of metallic inclusions in uranium oxide under the influence of temperature gradient. No thermal migration of molybdenum and tungsten inclusions was observed under the experimental conditions. Ruthenium inclusions, however, dissolved and diffused atomically through grain boundaries in slightly reduced uranium oxide. An intermetallic compound (probably URu 3 ) was formed by reaction of Ru and UO/sub 2-x/. The diffusivity and solubility of ruthenium in uranium oxide were measured

  6. Subsurface Conditions Controlling Uranium Incorporation in Iron Oxides: A Redox Stable Sink

    International Nuclear Information System (INIS)

    Fendorf, Scott

    2016-01-01

    Toxic metals and radionuclides throughout the U.S. Department of Energy Complex pose a serious threat to ecosystems and to human health. Of particular concern is the redox-sensitive radionuclide uranium, which is classified as a priority pollutant in soils and groundwaters at most DOE sites owing to its large inventory, its health risks, and its mobility with respect to primary waste sources. The goal of this research was to contribute to the long-term mission of the Subsurface Biogeochemistry Program by determining reactions of uranium with iron (hydr)oxides that lead to long-term stabilization of this pervasive contaminant. The research objectives of this project were thus to (1) identify the (bio)geochemical conditions, including those of the solid-phase, promoting uranium incorporation in Fe (hydr)oxides, (2) determine the magnitude of uranium incorporation under a variety of relevant subsurface conditions in order to quantify the importance of this pathway when in competition with reduction or adsorption; (3) identify the mechanism(s) of U(VI/V) incorporation in Fe (hydr)oxides; and (4) determine the stability of these phases under different biogeochemical (inclusive of redox) conditions. Our research demonstrates that redox transformations are capable of achieving U incorporation into goethite at ambient temperatures, and that this transformation occurs within days at U and Fe(II) concentrations that are common in subsurface geochemical environments with natural ferrihydrites - inclusive of those with natural impurities. Increasing Fe(II) or U concentration, or initial pH, made U(VI) reduction to U(IV) a more competitive sequestration pathway in this system, presumably by increasing the relative rate of U reduction. Uranium concentrations commonly found in contaminated subsurface environments are often on the order of 1-10 μM, and groundwater Fe(II) concentrations can reach exceed 1 mM in reduced zones of the subsurface. The redox-driven U(V) incorporation

  7. Subsurface Conditions Controlling Uranium Incorporation in Iron Oxides: A Redox Stable Sink

    Energy Technology Data Exchange (ETDEWEB)

    Fendorf, Scott [Stanford Univ., CA (United States)

    2016-04-05

    Toxic metals and radionuclides throughout the U.S. Department of Energy Complex pose a serious threat to ecosystems and to human health. Of particular concern is the redox-sensitive radionuclide uranium, which is classified as a priority pollutant in soils and groundwaters at most DOE sites owing to its large inventory, its health risks, and its mobility with respect to primary waste sources. The goal of this research was to contribute to the long-term mission of the Subsurface Biogeochemistry Program by determining reactions of uranium with iron (hydr)oxides that lead to long-term stabilization of this pervasive contaminant. The research objectives of this project were thus to (1) identify the (bio)geochemical conditions, including those of the solid-phase, promoting uranium incorporation in Fe (hydr)oxides, (2) determine the magnitude of uranium incorporation under a variety of relevant subsurface conditions in order to quantify the importance of this pathway when in competition with reduction or adsorption; (3) identify the mechanism(s) of U(VI/V) incorporation in Fe (hydr)oxides; and (4) determine the stability of these phases under different biogeochemical (inclusive of redox) conditions. Our research demonstrates that redox transformations are capable of achieving U incorporation into goethite at ambient temperatures, and that this transformation occurs within days at U and Fe(II) concentrations that are common in subsurface geochemical environments with natural ferrihydrites—inclusive of those with natural impurities. Increasing Fe(II) or U concentration, or initial pH, made U(VI) reduction to U(IV) a more competitive sequestration pathway in this system, presumably by increasing the relative rate of U reduction. Uranium concentrations commonly found in contaminated subsurface environments are often on the order of 1-10 μM, and groundwater Fe(II) concentrations can reach exceed 1 mM in reduced zones of the subsurface. The redox-driven U(V) incorporation

  8. Thermogravimetric studies on the silicothermic reduction of uranium tetrafluoride under nitrogen

    International Nuclear Information System (INIS)

    Venkataramani, R.; Bhatt, Y.J.; Krishnamurthy, N.; Garg, S.P.

    1986-01-01

    This paper presents details of the experimental procedure and results obtained by thermogravimetric studies on the preparation of uranium nitrides by silicothermic reduction of uranium tetrafluoride under a nitrogen atmosphere. The folowing sequential steps are involved during the reaction: 4UF 4 +Si->4UF 3 +SiF 4 (g), 2UF 3 +Si+N 2 ->2UNF+SiF 4 (g), 4UNF+Si+N 2 ->2U 2 N 3 +SiF 4 (g), the uranium sesquintride U 2 N 3 obtained in the above process then decomposed at 1370 K under a dynamic vacuum of less than 10 -2 Tor to yield uranium mononitride of purity better than 99.9%, according to reaction 2U 2 N 3 ->4UN+N 2 (g). The chemical composition of the intermediate products formed during the sequential steps of the process, assessed by thermogravimetric and differential thermogravimetric studies, were further confirmed by chemical and X-ray analysis

  9. Position-specific isotope modeling of organic micropollutants transformations through different reaction pathways

    Science.gov (United States)

    Jin, Biao; Rolle, Massimo

    2016-04-01

    Organic compounds are produced in vast quantities for industrial and agricultural use, as well as for human and animal healthcare [1]. These chemicals and their metabolites are frequently detected at trace levels in fresh water environments where they undergo degradation via different reaction pathways. Compound specific stable isotope analysis (CSIA) is a valuable tool to identify such degradation pathways in different environmental systems. Recent advances in analytical techniques have promoted the fast development and implementation of multi-element CSIA. However, quantitative frameworks to evaluate multi-element stable isotope data and incorporating mechanistic information on the degradation processes [2,3] are still lacking. In this study we propose a mechanism-based modeling approach to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. We validate the proposed approach with the concentration and multi-element isotope data of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model precisely captures the dual element isotope trends characteristic of different reaction pathways and their range of variation consistent with observed multi-element (C, N) bulk isotope fractionation. The proposed approach can also be used as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available. [1] Schwarzenbach, R.P., Egli, T., Hofstetter, T.B., von Gunten, U., Wehrli, B., 2010. Global Water Pollution and Human Health. Annu. Rev. Environ. Resour. doi:10.1146/annurev-environ-100809-125342. [2] Jin, B., Haderlein, S.B., Rolle, M

  10. LiCl-KCl-UCl3 Salt production and Transfer for the Uranium Electrorefining

    International Nuclear Information System (INIS)

    Woo, Moon Sik; Kang, Hee Suk; Lee, Han Soo

    2009-01-01

    A pyrometallurgical partitioning technology to recover uranium from an uranium-TRU mixture which is the product material of electroreduction system is being developed at KAERI since 1997. In the process, the reactor of an electrorefiner consists of the electrodes and the molten chloride salt which is LiCl-KCl-UCl 3 . The role of uranium chloride salt (UCl 3 ) is to stabilize the initial cell voltage between electrodes in the electrorefining reactor. The process to produce a uranium chloride salt includes two steps: a reaction process of gaseous chlorine with liquid cadmium to form the CdCl 2 occurring in a Cd layer, followed by a process to produce UCl 3 by the reaction of U in the LiCl-KCl eutectic salt and CdCl 2 . The apparatus for producing UCl 3 consists of a chlorine gas generator, a chlorinator, and a off-gas wet scrubber. The temperature of the reactants are maintained at about 600 .deg. C . After the reaction is completed, the product salt is transferred from the vessel to the electrorefiner by a transfer system

  11. Reducing emissions from uranium dissolving

    International Nuclear Information System (INIS)

    Griffith, W.L.; Compere, A.L.; Huxtable, W.P.; Googin, J.M.

    1992-10-01

    This study was designed to assess the feasibility of decreasing NO x emissions from the current uranium alloy scrap tray dissolving facility. In the current process, uranium scrap is dissolved in boiling nitric acid in shallow stainless-steel trays. As scrap dissolves, more metal and more nitric acid are added to the tray by operating personnel. Safe geometry is assured by keeping liquid level at or below 5 cm, the depth of a safe infinite slab. The accountability batch control system provides additional protection against criticality. Both uranium and uranium alloys are dissolved. Nitric acid is recovered from the vapors for reuse. Metal nitrates are sent to uranium recovery. Brown NO x fumes evolved during dissolving have occasionally resulted in a visible plume from the trays. The fuming is most noticeable during startup and after addition of fresh acid to a tray. Present environmental regulations are expected to require control of brown NO x emissions. A detailed review of the literature, indicated the feasibility of slightly altering process chemistry to favor the production of NO 2 which can be scrubbed and recycled as nitric acid. Methods for controlling the process to manage offgas product distribution and to minimize chemical reaction hazards were also considered

  12. The oxidative corrosion of carbide inclusions at the surface of uranium metal during exposure to water vapour

    International Nuclear Information System (INIS)

    Scott, T.B.; Petherbridge, J.R.; Harker, N.J.; Ball, R.J.; Heard, P.J.; Glascott, J.; Allen, G.C.

    2011-01-01

    Highlights: → High resolution imagery (FIB, SEM and SIMS) of carbide inclusions in uranium metal. → Real time images following the reaction of the carbide inclusions with water vapour. → Shown preferential consumption of carbide over that of the bulk metal. → Quantity of impurities in the metal therefore seriously influence reaction rate. → Metal purity must be considered when storing uranium in air or moist conditions. - Abstract: The reaction between uranium and water vapour has been well investigated, however discrepancies exist between the described kinetic laws, pressure dependence of the reaction rate constant and activation energies. Here this problem is looked at by examining the influence of impurities in the form of carbide inclusions on the reaction. Samples of uranium containing 600 ppm carbon were analysed during and after exposure to water vapour at 19 mbar pressure, in an environmental scanning electron microscope (ESEM) system. After water exposure, samples were analysed using secondary ion mass spectrometry (SIMS), focused ion beam (FIB) imaging and sectioning and transmission electron microscopy (TEM) with X-ray diffraction (micro-XRD). The results of the current study indicate that carbide particles on the surface of uranium readily react with water vapour to form voluminous UO 3 .xH 2 O growths at rates significantly faster than that of the metal. The observation may also have implications for previous experimental studies of uranium-water interactions, where the presence of differing levels of undetected carbide may partly account for the discrepancies observed between datasets.

  13. Chlorination of uranium oxides with CCl4 using a mechanochemical method

    Science.gov (United States)

    Kitawaki, Shinichi; Nagai, Takayuki; Sato, Nobuaki

    2013-08-01

    A chlorination method for uranium oxides at low temperature was investigated by using a mechanochemical method. In particular, the possibility of the chlorination of uranium oxides, such as UO2 and U3O8, via mechanochemical reaction with CCl4 was studied using a planetary ball mill. Mechanochemical experiments were conducted to evaluate the effect of milling time, CCl4/uranium oxide molar ratio, and revolution speed on the reaction. The synthesized products were then subjected to X-ray diffraction analysis, and it was found that the chlorination of U3O8 with CCl4 to UOCl2, UCl4, and U2O2Cl5 proceeded. However, the chlorination reaction could not be observed when using UO2 powder as the raw material. The chlorination reaction could not be observed when using UO2 powder as the raw material. The chlorination of U3O8 with CCl4 to form UOCl2, UCl4, and U2O2Cl5 via mechanochemical reaction occurs at room temperature. The ratio of chlorination increases with milling time when the appropriate amount of CCl4 is employed. However, the use of excess liquid CCl4 decreases the mechanochemical effect.

  14. Design of polymetallic uranium assemblies for the development of single molecule magnets

    International Nuclear Information System (INIS)

    Chatelain, Lucile

    2016-01-01

    The study of actinide chemistry is not only essential for the development of nuclear fuel, nuclear fuel reprocessing or environmental clean up, but also for the understanding of fundamental actinide/ligand interactions and multiple bounding. The magnetic properties of polynuclear actinide molecules are of significant interest to investigate the magnetic communication between the metallic centres. Furthermore, they are highly promising for the design of molecular magnets. Uranium undergoes redox reactions due to a wide range of available oxidation states and easily forms polynuclear assemblies. However, only a few controlled synthetic routes towards these polynuclear uranium assemblies are described in the literature. In this context, the first part of this work was dedicated to the synthesis of oxo/hydroxo uranium clusters from the controlled hydrolysis of tetravalent uranium in the presence of an environmentally relevant ligand. This led to the synthesis of clusters with novel topologies, for which size could be varied as a function of the reaction conditions employed. However, the obtained clusters do not behave as SMM. In order to gain a stronger interaction between metallic centres, the cation-cation interaction was used to rationally design polynuclear uranyl(V) complexes. The isolation of uranyl(V) complexes had been limited in the past by its disproportionation, however, a fine tuning of the organic ligand and reaction conditions finally allowed to stabilise uranyl(V). We used stable uranyl(V) units as building block to form heteronuclear complexes with 3d and 4f metals with polymeric or discrete structures. The study of the magnetic properties of the uranium polynuclear assemblies was carried out and revealed single molecule or chain magnet behaviours with high energy barriers. The uranyl(V) unit was also used as a structural model for the more radioactive neptunium element, allowing the isolation of an isostructural trinuclear neptunyl(V) assembly in

  15. Reactivity of uranium(IV) bridged chalcogenido complexes UIV–E–UIV (E = S, Se) with elemental sulfur and selenium: synthesis of polychalcogenido-bridged uranium complexes

    OpenAIRE

    Franke, Sebastian M.; Heinemann, Frank W.; Meyer, Karsten

    2014-01-01

    We report the syntheses, electronic properties, and molecular structures of a series of polychalcogenido-bridged dinuclear uranium species. These complexes are supported by the sterically encumbering but highly flexible, single N-anchored tris(aryloxide) chelator (AdArO)3N3−. Reaction of an appropriate uranium precursor, either the U(III) starting material, [((AdArO)3N)U(DME)], or the dinuclear mono-chalcogenido-bridged uranium(IV/IV) compounds [{((AdArO)3N)U(DME)}2(μ-E)] (E = S, Se), with el...

  16. Preparation and thermochemical stability of uranium-zirconium-carbonitrides

    International Nuclear Information System (INIS)

    Kouhsen, C.

    1975-08-01

    This investigation deals with the preparation and the thermochemical stability of uranium-zirconium-carbonitrides as well as with the mechanism of (U,Zr) (C,N)-preparation by carbothermic reduction of uranium-zirconium-oxide. Single-phase (U,Zr) (C,N)-solid solutions with U:Zr-propertions of 3:1, 1:1, and 1:3 were prepared from oxide powder. The thermochemical stability of the (U,Zr) (C,N)-solid solutions against carbon was measured for varying Zr- and N-contents and for several temperatures; the results indicate an increase of the uranium carbide stability potential by the formation of (U,Zr) (C,N)-solid solutions. The thermodynamic properties ΔG 0 , ΔH 0 , and ΔS 0 were calculated and the correlation between the M(C,N)-lattice constant and the N-content was evaluated. Through an intensive investigation of the reaction mechanism, several different reaction paths were found; for each of them the characteristical diffusion of matter was explained by means of the microsections. It was shown that the Zr-concentration of the oxide reactant and the heating rate during the carbothermic reduction influence the species of the reaction product, especially the homogeneity of the (U,Zr) (C,N)-solid solution. (orig.) [de

  17. Radiological impacts of uranium recovery in the phosphate industry

    International Nuclear Information System (INIS)

    Ryan, M.T.

    1981-01-01

    This article characterizes the occupational and public radiological health impacts associated with phosphate mining and milling. These impacts are related to the phosphate industry's uranium production potential and are compared with those associated with conventional uranium mining and milling. The radiological impacts resulting from occupational and nonoccupational exposures are assessed. Occupational exposures in phosphate facilities are compared to background exposures and radiological population dose assessments, which characterize important radionuclides and exposure pathways. The following conclusions were reached: (1) public consequences of phosphate mining will occur whether or not uranium is recovered as a by-product, (2) radiological consequences of phosphate mining may be comparable to those associated with uranium mining and milling per unit uranium production, (3) radiological impacts via surface waterways and crops fertilized with uranium-bearing phosphates are of minor consequence, and (4) major radiological public health problems associated with phosphate mining are related to radon and radon progeny exposures in structures built on reclaimed lands or with phosphate mining residues, although the magnitudes of these impacts are difficult to evaluate with current data

  18. Immobilization of uranium in contaminated soil by natural apatite addition

    International Nuclear Information System (INIS)

    Mrdakovic Popic, Jelena; Stojanovic, Mirjana; Milosevic, Sinisa; Iles, Deana; Zildzovic, Snezana

    2007-01-01

    Available in abstract form only. Full text of publication follows: The goal of this study was to evaluate the effectiveness of Serbian natural mineral apatite as soil additive for reducing the migration of uranium from contaminated sediments. In laboratory study we investigated the sorption properties of domestic apatite upon different experimental conditions, such as pH, adsorbent mass, reaction period, concentration of P 2 O 5 in apatite, solid/liquid ratio. In second part of study, we did the quantification of uranium in soil samples, taken from uranium mine site 'Kalna', by sequential extraction method. The same procedure was, also, used for uranium determination in contaminated soil samples after apatite addition, in order to determine the changes in U distribution in soil fraction. The obtained results showed the significant level of immobilization (96.7%) upon certain conditions. Increase of %P 2 O 5 in apatite and process of mechano-chemical activation led to increase of immobilization capacity from 17.50% till 91.64%. The best results for uranium binding were obtained at pH 5.5 and reaction period 60 days (98.04%) The sequential extraction showed the presence of uranium (48.2%) in potentially available soil fractions, but with the apatite addition uranium content in these fractions decreased (30.64%), what is considering environmental aspect significant fact. In situ immobilization of radionuclide using inexpensive sequestering agents, such as apatite, is very adequate for big contaminated areas of soil with low level of contamination. This investigation study on natural apatite from deposit 'Lisina' Serbia was the first one of this type in our country. Key words: apatite, uranium, immobilization, soil, contamination. (authors)

  19. Polynuclear compounds of uranium: structure, reactivity and properties

    International Nuclear Information System (INIS)

    Mougel, V.

    2012-01-01

    The study and comprehension of actinide's fundamental chemistry have important implications both for the development of new nuclear fuel and for the nuclear fuel reprocessing. One of the major issues in these processes is the ease of uranium to undergo redox reactions and to form polynuclear assemblies, which largely perturb these processes. However, despite their relevance, only few synthetic routes towards polynuclear uranium assemblies are described in the literature, and most of the polynuclear complexes reported are formed by serendipity rather than by rational design. Moreover, polynuclear uranium compounds are highly promising for the design of magnetic materials with improved properties and for reactivity studies. The aim of this work is the synthesis of polynuclear uranium complexes and the study of their reactivity and coordination properties. New synthetic routes to uranium polynuclear assemblies were developed and the study of their physico-chemical properties was carried out. The first approach investigated was based on pentavalent uranyl chemistry. Uranyl(V) is known to form aggregates via an interaction between uranyl moieties often named cation-cation interaction, but the isolation of uranyl(V) complexes had been largely limited by its ease of disproportionation. We isolated the first stable uranyl(V) polynuclear assembly using Salen-type Schiff base ligand. Based on this result, a fine tuning of the ligand and counter-ion properties resulted in the isolation of a large family of uranyl(V) polynuclear assemblies and in a better understanding of the parameters ruling their stability. Moreover, rare examples of clear antiferromagnetic couplings were observed with these complexes. In addition, this synthetic path was used to build the first 5f-3d cluster presenting single molecule magnet properties. The second approach used in this thesis consisted in the synthesis of oxo/hydroxo uranium clusters. The controlled hydrolysis of trivalent uranium in

  20. Filtration and Hydrogen Reaction Modeling in a Depleted Uranium Bed

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Kwang Jin; Kim, Yean Jin; Ahn, Do Hee; Chung, Hong Suk [UST, Daejeon (Korea, Republic of); Kang, Hee Seok [KAERI, Daejeon (Korea, Republic of); Yun, Sei Hun [NFRI, Daejeon (Korea, Republic of)

    2016-05-15

    The storage and delivery system (SDS) stores the hydrogen isotopes and delivers them to the fuel injection system. Depleted uranium (DU) was chosen as a hydrogen isotope storage material. The hydrogen isotopes stored in the SDS are in the form of DU hydride confined in the primary and secondary containment within a glove box with an argon atmosphere. In this study, we performed a modeling study of the SDS. A modeling study is practically important because an experimental study requires comparatively more money and time. We estimated the hydrogen atomic ratio in DU hydride by two empirical equations we formulated. Two empirical equations are used to determine Pressure-Composition-Temperature (PCT) curves and the hydrogen atomic ratio in DU hydride. In addition, we present the effect of pressure and temperature in the hydriding and dehydriding. A modeling study of the SDS was performed in this study. It is practically important to save more money and time. The hydrogen atomic ratio in the DU hydride was estimated using two empirical equations. The two empirical equations are modified and reformulated to determine PCT curves and the hydrogen atomic ratio in DU hydride. All parameters that are required to solve two empirical equations are obtained from the experimental data. The derived parameters are utilized for the numerical simulations. In the numerical simulations, the effects of pressure and temperature on both the hydriding and dehydriding reaction rates are confirmed.

  1. Trends in exploration and exploration equipment for uranium

    International Nuclear Information System (INIS)

    Raitz, C.H.

    1976-01-01

    Uranium exploration once again is in a ''boom'' cycle. The energy needs of the OPEC and non-OPEC countries alike have created a demand for uranium which appears certain to increase in future years. In turn, this demand has stimulated a dramatic rise in both the price of uranium and the exploration activity necessary to discover new reserves. One immediate reaction to the sudden increase in uranium exploration activity has been the evaluation of old exploration methods and equipment. This paper briefly reviews some of the traditional equipment and techniques which currently are being refined and updated. Undoubtedly this equipment, complemented with good exploration planning and judgment, will continue to be relied upon for many years and will lead to the discovery of many new deposits. The paper also covers in greater detail some of the newer, less conventional techniques and equipment now being introduced for uranium exploration. These new methods may be expected to keep this country in the forefront among the uranium producers of the world

  2. Research of the Mass Spectra of the Fission Products and Yields of (n, gamma) and (n, 2n) Reactions in a Model Subcritical Uranium Blanket of the Electronuclear System "Energy Plus Transmutation" on Proton Beam of the Dubna Synchrophasotron at 1.5 Ge

    CERN Document Server

    Chultem, D; Krivopustov, M I; Gerbish, S; Tumendemberel, B; Pavlyuk, A B; Zaveryukha, O S

    2002-01-01

    This paper is devoted to the research of the spatial distributions of the yields of (n, f), (n, gamma) and (n, 2n) reactions in a two-section model of the uranium blanket electronuclear installation constructed at the Laboratory of High Energies, JINR (Dubna) for experiments according to the program "Research of physical aspects of the electronuclear method of energy production and of radioactive waste transmutation in atomic power-engineering on beams of the synchrophasotron and nuclotron" - project "Energy plus Transmutation". The mass spectrum of the fission products and yields of above reactions in uranium activation detectors placed on the radii of the so-called detector plates is determined. The experimental results testify that the fission of nuclei in the uranium blanket is made by fast neutrons. This conclusion coincides with the result obtained with track integrators of uranium fission.

  3. Method of converting uranium fluoride to intermediate product for uranium oxide manufacture with recycling or reusing valuable materials

    International Nuclear Information System (INIS)

    Baran, V.; Moltasova, J.

    1982-01-01

    Uranium fluoride is acted upon by water with nitrate containing a cation capable of binding fluoride ions. The uranium is extracted, for instance, with tributyl phosphate with the generated organic phase containing the prevalent proportion of uranium and representing the required intermediate product and the aqueous phase from which is isolated the fluorine component which may be used within the fuel cycle. The nitrate component of the aqueous phase is recycled following treatment. It is also possible to act on uranium fluoride directly with an aqueous solution. Here the cations of nitrate form with the fluorides soluble nondissociated complexes and reduce the concentration of free fluoride ions. The nitrate +s mostly used in an amount corresponding to its solubility in the system prior to the introduction of UF 6 . The uranium from the solution with the reduced concentration of free fluoride ions is extracted into the reaction system under such conditions as to make the prevalent majority of fluorides and an amount of uranium smaller than 5x10 -2 mol/l remain in the aqueous phase and that such an amount of fluorides should remain in the organic phase which is smaller than corresponds to the fluorine/uranium molar ratio in the organic phase. Uranium contained in the organic phase is processed into uranium oxide, with advantage into UO 2 . From the isolated compounds of fluorine and the cation of the nitrate gaseous HF is released which is used either inside or outside of the fuel cycle. (J.P.)

  4. Uranium accumulation in CTF and ETF-II rotors

    International Nuclear Information System (INIS)

    1987-06-01

    In the expanding technology of uranium enrichment by gas centrifuge, efforts are being made to become more and more familar with the reactions taking place inside the rotor tube while the machine is operational. Inspection of the rotor after shutdown shows where uranium containing compounds are deposited. A study of these deposits from several ETF, CTF and CPL rotors has provided insight as to accumulation amounts, its composition and deposition parameters involved

  5. X-ray photoelectron spectroscopy of the uranium/oxygen system: Part 13

    International Nuclear Information System (INIS)

    Allen, G.C.; Stevens, J.C.H.

    1987-02-01

    The reaction between commercial H 2 and uranium metal leads to the formation of UO 2 due to traces of water vapour or oxygen. When extremely pure H 2 is used uranium hydride may be formed but, even with 99.9999% H 2 , uranium dioxide forms preferentially. The present work identifies the presence of UH 3 in the X-ray photoelectron spectrum of a uranium sample which has been exposed to ∼ 5 mbar H 2 at ∼ 200 0 C for 1 hour. This spectrum indicates that the hydride possesses a high degree of covalency, since the oxidation state of uranium in UH 3 appears to be ∼ 1.4. (U.K.)

  6. Methane coupling reaction in an oxy-steam stream through an OH radical pathway by using supported alkali metal catalysts

    KAUST Repository

    Liang, Yin

    2014-03-24

    A universal reaction mechanism involved in the oxidative coupling of methane (OCM) is demonstrated under oxy-steam conditions using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from a H 2O-O2 reaction followed by C-H activation in CH 4 with an OH radical. Thus, the presence of water enhances both the CH4 conversion rate and the C2 selectivity. This OH radical pathway that is selective for the OCM was observed for the catalyst without Mn, which suggests clearly that Mn is not the essential component in a selective OCM catalyst. The experiments with different catalyst compositions revealed that the OH.-mediated pathway proceeded in the presence of catalysts with different alkali metals (Na, K) and different oxo anions (W, Mo). This difference in catalytic activity for OH radical generation accounts for the different OCM selectivities. As a result, a high C2 yield is achievable by using Na2WO4/SiO2, which catalyzes the OH.-mediated pathway selectively. Make it methane: A universal reaction mechanism involved in the oxidative coupling of methane is demonstrated under oxy-stream conditions by using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from an H2O-O2 reaction, followed by C-H activation in CH4 with an OH radical. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. The measurement of metallic uranium solubility in lithium chloride molten salt

    International Nuclear Information System (INIS)

    Park, K. K.; Choi, I. K.; Yeon, J. W.; Choi, K. S.; Park, Y. J.

    2002-01-01

    For the purpose of more precise solubility measurement of metallic uranium in lithium chloride melt, the effect of lithium chloride on uranium determination and and the change of oxidation state of metallic uranium in the media were investigated. Uranium of higher than 10 μg/g could be directly determined by ICP-AES. In the case of the lower concentration, the separation and concentration of uranium by anion exchanger was followed by ICP-AES, thereby extending the measurable concentration to 0.1 μg/g. The effects of lithium oxide, uranium oxides(UO 2 or U 3 O 8 ) and metallic lithium on the solubility of metallic uranium were individually investigated in glassy carbon or stainless steel crucibles under argon gas atmosphere. Since metallic uranium is oxidized to uranium(III) in the absence of metallic lithium, causing an increase in the solubility, metallic lithium as reducing agent should be present in the reaction media to obtain the more precise solubility. The metallic uranium solubilities measured at 660 and 690 .deg. C were both lower than 10 μg/g

  8. Conferring specificity in redox pathways by enzymatic thiol/disulfide exchange reactions.

    Science.gov (United States)

    Netto, Luis Eduardo S; de Oliveira, Marcos Antonio; Tairum, Carlos A; da Silva Neto, José Freire

    2016-01-01

    Thiol-disulfide exchange reactions are highly reversible, displaying nucleophilic substitutions mechanism (S(N)2 type). For aliphatic, low molecular thiols, these reactions are slow, but can attain million times faster rates in enzymatic processes. Thioredoxin (Trx) proteins were the first enzymes described to accelerate thiol-disulfide exchange reactions and their high reactivity is related to the high nucleophilicity of the attacking thiol. Substrate specificity in Trx is achieved by several factors, including polar, hydrophobic, and topological interactions through a groove in the active site. Glutaredoxin (Grx) enzymes also contain the Trx fold, but they do not share amino acid sequence similarity with Trx. A conserved glutathione binding site is a typical feature of Grx that can reduce substrates by two mechanisms (mono and dithiol). The high reactivity of Grx enzymes is related to the very acid pK(a) values of reactive Cys that plays roles as good leaving groups. Therefore, although distinct oxidoreductases catalyze similar thiol–disulfide exchange reactions, their enzymatic mechanisms vary. PDI and DsbA are two other oxidoreductases, but they are involved in disulfide bond formation, instead of disulfide reduction, which is related to the oxidative environment where they are found. PDI enzymes and DsbC are endowed with disulfide isomerase activity, which is related with their tetra-domain architecture. As illustrative description of specificity in thiol-disulfide exchange, redox aspects of transcription activation in bacteria, yeast, and mammals are presented in an evolutionary perspective. Therefore, thiol-disulfide exchange reactions play important roles in conferring specificity to pathways, a required feature for signaling.

  9. Following the electroreduction of uranium dioxide to uranium in LiCl–KCl eutectic in situ using synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Brown, L.D.; Abdulaziz, R.; Jervis, R.; Bharath, V.J. [Electrochemical Innovation Lab, Dept. Chemical Engineering, UCL, London WC1E 7JE (United Kingdom); Atwood, R.C.; Reinhard, C.; Connor, L.D. [Diamond Light Source, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE (United Kingdom); Simons, S.J.R.; Inman, D.; Brett, D.J.L. [Electrochemical Innovation Lab, Dept. Chemical Engineering, UCL, London WC1E 7JE (United Kingdom); Shearing, P.R., E-mail: p.shearing@ucl.ac.uk [Electrochemical Innovation Lab, Dept. Chemical Engineering, UCL, London WC1E 7JE (United Kingdom)

    2015-09-15

    Highlights: • We investigated the electroreduction of UO{sub 2} to U in LiCl/KCL eutectic molten salt. • Combined electrochemical measurement and in situ XRD is utilised. • The electroreduction appears to occur in a single, 4-electron-step, process. • No intermediate compounds were observed. - Abstract: The electrochemical reduction of uranium dioxide to metallic uranium has been investigated in lithium chloride–potassium chloride eutectic molten salt. Laboratory based electrochemical studies have been coupled with in situ energy dispersive X-ray diffraction, for the first time, to deduce the reduction pathway. No intermediate phases were identified using the X-ray diffraction before, during or after electroreduction to form α-uranium. This suggests that the electrochemical reduction occurs via a single, 4-electron-step, process. The rate of formation of α-uranium is seen to decrease during electrolysis and could be a result of a build-up of oxygen anions in the molten salt. Slow transport of O{sup 2−} ions away from the UO{sub 2} working electrode could impede the electrochemical reduction.

  10. Depleted uranium residual radiological risk assessment for Kosovo sites

    International Nuclear Information System (INIS)

    Durante, Marco; Pugliese, Mariagabriella

    2003-01-01

    During the recent conflict in Yugoslavia, depleted uranium rounds were employed and were left in the battlefield. Health concern is related to the risk arising from contamination of areas in Kosovo with depleted uranium penetrators and dust. Although chemical toxicity is the most significant health risk related to uranium, radiation exposure has been allegedly related to cancers among veterans of the Balkan conflict. Uranium munitions are considered to be a source of radiological contamination of the environment. Based on measurements and estimates from the recent Balkan Task Force UNEP mission in Kosovo, we have estimated effective doses to resident populations using a well-established food-web mathematical model (RESRAD code). The UNEP mission did not find any evidence of widespread contamination in Kosovo. Rather than the actual measurements, we elected to use a desk assessment scenario (Reference Case) proposed by the UNEP group as the source term for computer simulations. Specific applications to two Kosovo sites (Planeja village and Vranovac hill) are described. Results of the simulations suggest that radiation doses from water-independent pathways are negligible (annual doses below 30 μSv). A small radiological risk is expected from contamination of the groundwater in conditions of effective leaching and low distribution coefficient of uranium metal. Under the assumptions of the Reference Case, significant radiological doses (>1 mSv/year) might be achieved after many years from the conflict through water-dependent pathways. Even in this worst-case scenario, DU radiological risk would be far overshadowed by its chemical toxicity

  11. Heterogeneous reaction of particulate chlorpyrifos with NO3 radicals: Products, pathways, and kinetics

    Science.gov (United States)

    Li, Nana; Zhang, Peng; Yang, Bo; Shu, Jinian; Wang, Youfeng; Sun, Wanqi

    2014-08-01

    Chlorpyrifos is a typical chlorinated organophosphorus pesticide. The heterogeneous reaction of chlorpyrifos particles with NO3 radicals was investigated using a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) and a real-time atmospheric gas analysis mass spectrometer. Chlorpyrifos oxon, 3,5,6-trichloro-2-pyridinol, O,O-diethyl O-hydrogen phosphorothioate, O,O-diethyl ester thiophosphoric acid, diethyl hydrogen phosphate and a phosphinyl disulfide compound were identified as the main degradation products. The heterogeneous reaction pathways were proposed and their kinetic processes were investigated via a mixed-phase relative rate method. The observed effective rate constant is 3.4 ± 0.2 × 10-12 cm3 molecule-1 s-1.

  12. Catalytic Hydrotreatment of Fast Pyrolysis Oil : Model Studies on Reaction Pathways for the Carbohydrate Fraction

    NARCIS (Netherlands)

    Wildschut, J.; Arentz, J.; Rasrendra, C. B.; Venderbosch, R. H.; Heeres, H. J.

    2009-01-01

    Fast pyrolysis oil can be upgraded by a catalytic hydrotreatment (250-400 degrees C, 100-200 bar) using heterogeneous catalysts such as Ru/C to hydrocarbon-like products that can serve as liquid transportation fuels. Insight into the complex reaction pathways of the various component fractions

  13. Roles of different initial Maillard intermediates and pathways in meat flavor formation for cysteine-xylose-glycine model reaction systems.

    Science.gov (United States)

    Hou, Li; Xie, Jianchun; Zhao, Jian; Zhao, Mengyao; Fan, Mengdie; Xiao, Qunfei; Liang, Jingjing; Chen, Feng

    2017-10-01

    To explore initial Maillard reaction pathways and mechanisms for maximal formation of meaty flavors in heated cysteine-xylose-glycine systems, model reactions with synthesized initial Maillard intermediates, Gly-Amadori, TTCA (2-threityl-thiazolidine-4-carboxylic acids) and Cys-Amadori, were investigated. Relative relativities were characterized by spectrophotometrically monitoring the development of colorless degradation intermediates and browning reaction products. Aroma compounds formed were determined by solid-phase microextraction combined with GC-MS and GC-olfactometry. Gly-Amadori showed the fastest reaction followed by Cys-Amadori then TTCA. Free glycine accelerated reaction of TTCA, whereas cysteine inhibited that of Gly-Amadori due to association forming relatively stable thiazolidines. Cys-Amadori/Gly had the highest reactivity in development of both meaty flavors and brown products. TTCA/Gly favored yielding meaty flavors, whereas Gly-Amadori/Cys favored generation of brown products. Conclusively, initial formation of TTCA and pathway involving TTCA with glycine were more applicable to efficiently produce processed-meat flavorings in a cysteine-xylose-glycine system. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Risk assessment applications for determining cleanup limits for uranium in treated and untreated soils

    International Nuclear Information System (INIS)

    Armstrong, A.Q.; Layton, D.W.; Rutz, E.E.

    1994-01-01

    Uranium-contaminated soils are present at various locations across the US where uranium was processed for nuclear fuels or atomic weapons. Important issues relative to such contamination include the assessment of potential health risks associated with human exposures to the residual uranium and the determination of safe levels of uranium in soils that have been treated by a given technology. This paper discusses various risk assessment considerations that must be dealt with when developing cleanup limits for uranium in treated and untreated soils. Key issues addressed include alternative land use scenarios, potential exposure pathways, characterization of the bioavailability of uranium compounds in food and water, a brief overview of health risks associated with uranium and its daughter products as well as a summary of considerations for development of risk-based cleanup limits for uranium in soils

  15. Potential health and environmental hazards of uranium mine wastes. Volume 3. Appendixes. Report to the congress

    International Nuclear Information System (INIS)

    1983-01-01

    Contents include: summary of federal laws potentially affecting uranium mining; federal water programs and right activities; congressionally approved compacts that apportion water; state laws, regulations, and guides for uranium mining; active uranium mines in the United States; inactive uranium mines in the United States; general observations of uranium mine sites in Colorado, New Mexico, Texas, and Wyoming; influence of mine drainage on seepage to groundwater and surface water outflow; computation of mass emission factors for wind erosion; aquatic dosimetry and health effects models and parameter values; Airborne pathway modeling; and health risk assessment methodology

  16. Cross Sections for the Production of Residual Nuclides by Proton-Induced Reactions with Uranium at Medium Energies

    International Nuclear Information System (INIS)

    Issa, S.A.M.; Michel, R.; Uosif, M.A.M.; Issa, S.A.M.; Flamentc, J.L.; David, J.C.; Leray, S.

    2009-01-01

    The production of residual nuclides by proton-induced reactions on uranium is investigated using activated targets from irradiation experiments at Saturne II synchrocyclotron at the Laboratory National Saturne/Saclay. These investigations contribute to the European research project NUDATRA within the IP EUROTRANS in which the feasibility of accelerator-driven transmutation of nuclear waste is evaluated. Experimental cross sections are derived from gamma-spectrometric measurements. A total of 1894 cross-section was deter-mined covering 44 residual nuclides in the energy range from 211 MeV to 2530 MeV. The experimental data together with those of earlier work of our group are discussed in the context of theoretical excitation functions calculated by the newly developed INCL4 + ABLA and the TALYS codes

  17. The hydrolysis of thorium dicarbide and of mixed uranium-thorium dicarbides

    International Nuclear Information System (INIS)

    Del Litto, B.

    1966-09-01

    The hydrolysis of thorium dicarbide leads to the formation of a complex mixture of gaseous and condensed carbon hydrides. The temperature, between 25 and 100 deg. C, has no influence on the nature and composition of the gas phase. The reaction kinetics, however, are strongly temperature dependent. In a hydrochloric medium, an enrichment in hydrogen of the gas mixture is observed. On the other hand a decrease in hydrogen and an increase in acetylene content take place in an oxidizing medium. The general results can be satisfactorily interpreted through a reaction mechanism involving C-C radical groups. In the same way, the hydrolysis of uranium-thorium-carbon ternary alloys leads to the formation of gaseous and condensed carbon hydrides. The variation of the composition of the gas phase versus uranium content in the alloy suggests an hypothesis about the carbon-carbon distance in the alloy crystal lattice. The variation of methane content, on the other hand, has lead us to discuss the nature of the various phases present in uranium-carbon alloys and carbon-rich uranium-thorium-carbon alloys. We have reached the conclusion that these alloys include a proportion of monocarbide which is dependent upon the ratio. Th/(Th + U). We put forward a diagram of the system uranium-carbon with features proper to explain some phenomena which have been observed in the uranium-thorium-carbon ternary diagram. (author) [fr

  18. Uranium

    International Nuclear Information System (INIS)

    Hamdoun, N.A.

    2007-01-01

    The article includes a historical preface about uranium, discovery of portability of sequential fission of uranium, uranium existence, basic raw materials, secondary raw materials, uranium's physical and chemical properties, uranium extraction, nuclear fuel cycle, logistics and estimation of the amount of uranium reserves, producing countries of concentrated uranium oxides and percentage of the world's total production, civilian and military uses of uranium. The use of depleted uranium in the Gulf War, the Balkans and Iraq has caused political and environmental effects which are complex, raising problems and questions about the effects that nuclear compounds left on human health and environment.

  19. A density functional theory study on redox reaction of uranium

    International Nuclear Information System (INIS)

    Toraishi, T.; Kawaguchi, M.; Tsuneda, T.; Tanaka, S.; Nagasaki, S.

    2005-01-01

    Full text of publication follows: Redox reactions are key issues for predicting the migration behavior of actinides in the geosphere, and therefore the chemical processes have to be profoundly understood. However, redox reactions basically involve several elemental processes, and in many cases only limited chemical information can be obtained experimentally. A theoretical approach gives further information which never can be obtained by experiments, such as precise thermodynamic data or reaction pathways of very rapid charge transfer reactions. For this reason, ab initio MO calculations have been applied in the last 5-6 years to the elucidation of redox processes in the U(VI)-Fe(II) or U(VI)-U(IV) system [1- 3]. Those studies provided extremely important chemical information. Nevertheless, the 'huge' calculation costs of ab initio MO techniques now interfere with the extension of the calculation to the 'real' size system: In order to deal with the practically important chemical reactions such as the reduction of actinides at solid surfaces, a large chemical system involving many atoms (electrons) has to be treated. Present ab initio MO techniques at CASSCF, CASPT2 or MRCI level, however, do not allow to handle such a large systems because of the high calculation costs. Density functional theory (DFT) calculations should be also feasible for such systems. Nevertheless, there are very few reports on redox processes of actinides calculated by DFT. This fact was based on the argument that DFT could not treat charge transfer phenomena accurately since the two-electron exchange integral term is not explicitly involved [1-3]. However this is no longer correct: the long-range corrected (LC) energy function was recently developed, and now the charge transfer reaction can safely be calculated by DFT [4]. In the present work, we employ the DFT technique to treat the reduction of U(VI) to U(V) by Fe(II) via the bi-nuclear complex system, and confirm the applicability of the

  20. Reactivity of hydrogen with uranium in the presence of Pt

    International Nuclear Information System (INIS)

    Balooch, M.; Siekhaus, W.J.

    1997-07-01

    The surface-reaction of di-hydrogen with uranium in the presence of Pt clusters has been studied using scanning tunneling microscopy (STM). Uranium was deposited on highly oriented pyrolytic graphite (HOPG) and annealed at temperatures up to 1200 degrees C to obtain atomically pyrolytic flat surfaces. Pt clusters were then formed using evaporation from a Pt source onto the surface and subsequent annealing. Hydrogen mainly attacked uranium in the vicinity of Pt clusters and formed hydride. The hydride formation probability is almost constant at 2.3x10 -4 over the range of exposures studied

  1. Uranium extraction from gold-uranium ores

    Energy Technology Data Exchange (ETDEWEB)

    Laskorin, B.N.; Golynko, Z.Sh.

    1981-01-01

    The process of uranium extraction from gold-uranium ores in the South Africa is considered. Flowsheets of reprocessing gold-uranium conglomerates, pile processing and uranium extraction from the ores are presented. Continuous counter flow ion-exchange process of uranium extraction using strong-active or weak-active resins is noted to be the most perspective and economical one. The ion-exchange uranium separation with the succeeding extraction is also the perspective one.

  2. Validation of the WATEQ4 geochemical model for uranium

    International Nuclear Information System (INIS)

    Krupka, K.M.; Jenne, E.A.; Deutsch, W.J.

    1983-09-01

    As part of the Geochemical Modeling and Nuclide/Rock/Groundwater Interactions Studies Program, a study was conducted to partially validate the WATEQ4 aqueous speciation-solubility geochemical model for uranium. The solubility controls determined with the WATEQ4 geochemical model were in excellent agreement with those laboratory studies in which the solids schoepite [UO 2 (OH) 2 . H 2 O], UO 2 (OH) 2 , and rutherfordine ((UO 2 CO 3 ) were identified as actual solubility controls for uranium. The results of modeling solution analyses from laboratory studies of uranyl phosphate solids, however, identified possible errors in the characterization of solids in the original solubility experiments. As part of this study, significant deficiencies in the WATEQ4 thermodynamic data base for uranium solutes and solids were corrected. Revisions included recalculation of selected uranium reactions. Additionally, thermodynamic data for the hydroxyl complexes of U(VI), including anionic (VI) species, were evaluated (to the extent permitted by the available data). Vanadium reactions were also added to the thermodynamic data base because uranium-vanadium solids can exist in natural ground-water systems. This study is only a partial validation of the WATEQ4 geochemical model because the available laboratory solubility studies do not cover the range of solid phases, alkaline pH values, and concentrations of inorganic complexing ligands needed to evaluate the potential solubility of uranium in ground waters associated with various proposed nuclear waste repositories. Further validation of this or other geochemical models for uranium will require careful determinations of uraninite solubility over the pH range of 7 to 10 under highly reducing conditions and of uranyl hydroxide and phosphate solubilities over the pH range of 7 to 10 under oxygenated conditions

  3. Spectrophotometric determination of uranium using quercetin

    International Nuclear Information System (INIS)

    Barros, A.R.

    1972-10-01

    A spectrophotometric method for quantitative determination of uranium, using a flavone (quercetin) as complexing agent, is described. The method is based on the reaction between uranyl ion and alcoholic solution of quercetin with a complex formation of intense yellow color. (M.C.L.) [pt

  4. Heterogeneous catalysis in fluoride melts - reduction of uranium(V) by hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Kelmers, A D; Bennett, M R [Oak Ridge National Lab., Tenn. (USA)

    1976-01-01

    A necessary step in fuel reprocessing for the Molten-Salt Breeder Reactor is the reduction of pentavalent uranium to tetravalent uranium by hydrogen gas. The pentavalent uranium is dissolved in a mixed fluoride melt. Results are presented which show that the hydrogen reduction is rate limited, possibly due to the dissociation of hydrogen molecules to yield active hydrogen atoms; and that by the application of platinum catalysts a 10- to 100-fold increase in the reaction rate can be achieved.

  5. Reaction Pathways in Catechol/Primary Amine Mixtures: A Window on Crosslinking Chemistry.

    Directory of Open Access Journals (Sweden)

    Juan Yang

    Full Text Available Catechol chemistry is used as a crosslinking tool abundantly in both natural organisms (e.g. mussels, sandcastle worms and synthetic systems to achieve the desired mechanical properties. Despite this abundance and success, the crosslinking chemistry is still poorly understood. In this study, to simplify the system, yet to capture the essential chemistry, model compounds 4-methyl catechol and propylamine are used. The reaction of 4-methyl catechol (2 mM with propylamine (6 mM is carried out in the presence of NaIO4 (2 mM in 10 mM Na2CO3 aqueous solution. A variety of spectroscopic/spectrometric and chromatographic methods such as 1H NMR, LC-MS, and UV-VIS are used to track the reaction and identify the products/intermediates. It is found that the crosslinking chemistry of a catechol and an amine is both fast and complicated. Within five minutes, more than 60 products are formed. These products encompass 19 different masses ranging from molecular weight of 179 to 704. By combining time-dependent data, it is inferred that the dominant reaction pathways: the majority is formed via aryloxyl-phenol coupling and Michael-type addition, whereas a small fraction of products is formed via Schiff base reactions.

  6. Biotechnology based opportunities for environmental protection in the uranium mining industry

    International Nuclear Information System (INIS)

    Glombitza, F.; Iske, U.; Bullmann, M.; Ondruschka, J.

    1992-01-01

    Fluorides and a sodium paraffin sulfonate were used as biocidial substances for blocking microbial oxidation reactions due to chemolithoautotrophic microorganisms and tested in a laboratory and pilot plant scale. A treatment of uranium containing effluents by means of a biosorption process for reducing the uranium concentration was demonstrated in a pilot plant scale too. (orig.)

  7. Method for converting uranium oxides to uranium metal

    International Nuclear Information System (INIS)

    Duerksen, W.K.

    1988-01-01

    A method for converting uranium oxide to uranium metal is described comprising the steps of heating uranium oxide in the presence of a reducing agent to a temperature sufficient to reduce the uranium oxide to uranium metal and form a heterogeneous mixture of a uranium metal product and oxide by-products, heating the mixture in a hydrogen atmosphere at a temperature sufficient to convert uranium metal in the mixture to uranium hydride, cooling the resulting uranium hydride-containing mixture to a temperature sufficient to produce a ferromagnetic transition in the uranium hydride, magnetically separating the cooled uranium hydride from the mixture, and thereafter heating the separated uranium hydride in an inert atmosphere to a temperature sufficient to convert the uranium hydride to uranium metal

  8. Uranium bed oxidation vacuum process system

    International Nuclear Information System (INIS)

    McLeland, H.L.

    1977-01-01

    Deuterium and tritium gases are occluded in uranium powder for release into neutron generator tubes. The uranium powder is contained in stainless steel bottles, termed ''beds.'' If these beds become damaged, the gases must be removed and the uranium oxidized in order not to be flammable before shipment to ERDA disposal grounds. This paper describes the system and methods designed for the controlled degassing and oxidation process. The system utilizes sputter-ion, cryo-sorption and bellows pumps for removing the gases from the heated source bed. Removing the tritium gas is complicated by the shielding effect of helium-3, a byproduct of tritium decay. This effect is minimized by incremental pressure changes, or ''batch'' processing. To prevent runaway exothermic reaction, oxidation of the uranium bed is also done incrementally, or by ''batch'' processing, rather than by continuous flow. The paper discusses in detail the helium-3 shielding effect, leak checks that must be made during processing, bed oxidation, degree of gas depletion, purity of gases sorbed from beds, radioactivity of beds, bed disposal and system renovation

  9. Study the oxidation kinetics of uranium using XRD and Rietveld method

    Science.gov (United States)

    Zhang, Yanzhi; Guan, Weijun; Wang, Qinguo; Wang, Xiaolin; Lai, Xinchun; Shuai, Maobing

    2010-03-01

    The surface oxidation of uranium metal has been studied by X-ray diffraction (XRD) and Rietveld method in the range of 50~300°C in air. The oxidation processes are analyzed by XRD to determine the extent of surface oxidation and the oxide structure. The dynamics expression for the formation of UO2 was derived. At the beginning, the dynamic expression was nonlinear, but switched to linear subsequently for uranium in air and humid oxygen. That is, the growth kinetics of UO2 can be divided into two stages: nonlinear portion and linear portion. Using the kinetic data of linear portion, the activation energy of reaction between uranium and air was calculated about 46.0 kJ/mol. However the content of oxide as a function of time was linear in humid helium ambience. Contrast the dynamics results, it prove that the absence of oxygen would accelerate the corrosion rate of uranium in the humid gas. We can find that the XRD and Rietveld method are a useful convenient method to estimate the kinetics and thermodynamics of solid-gas reaction.

  10. Uranium(VI) speciation by spectroscopy

    International Nuclear Information System (INIS)

    Meinrath, G.

    1997-01-01

    The application of UV-Vis and time-resolved laser-induced fluorescence (TRLF) spectroscopies to direct of uranium(VI) in environmental samples offers various prospects that have, however, serious limitations. While UV-Vis spectroscopy is probably not sensitive enough to detect uranium(VI) species in the majority of environmental samples, TRLFS is principially able to speciate uranium(VI) at very low concentration levels in the nanomol range. Speciation by TRLFS can be based on three parameters: excitation spectrum, emission spectrum and lifetime of the fluorescence emission process. Due to quenching effects, the lifetime may not be expected to be as characteristics as, e.g., the emission spectrum. Quenching of U(VI) fluorescence by reaction with organic substances, inorganic ions and formation of carbonate radicals is one important limiting factor in the application of U(VI) fluorescence spectroscopy. Fundamental photophysical criteria are illustrated using UV-Vis and fluorescence spectra of U(VI) hydrolysis and carbonato species as examples. (author)

  11. Processing of uranium-containing coal

    International Nuclear Information System (INIS)

    Cordero Alvarez, M.

    1987-01-01

    A direct storage of uranium-bearing coal requires the processing of large amounts of raw materials while lacking guarantee of troublefree process cycles. With the example of an uranium-bearing bituminous coal from Stockheim, it was aimed at the production of an uranium ore concentrate by means of mechanical, thermal and chemical investigations. Above all, amorphous pitch blende was detected as a uranium mineralization which occurs homogeneously distributed in the grain size classes of the comminuted raw material with particle diameters of a few μm and, after the combustion, enriches in the field of finest grain of the axis. Heterogeneous and solid-state reactions in the thermal decarburization above 700deg C result in the development of hardly soluble uranium oxides and and calcium uranates as well as in enclosures in mineral glass. Thus, the pre-enrichment has to take place in a temperature range below 600deg C. By means of a sorting classification of the ash at ± 2.0 mm, it is possible to achieve an enrichment of up to factor 15 for a mineral of a mainly low carbonate content and, for a mineral of a rich carbonate content, up to the factor 4. The separation of the uranium from the concentrates produced is possible with a yield of 95% by means of leaching with sulphuric acid at a temperature of 20deg C. As far as their reproducibility was concerned, the laboratory tests were verified on a semi-industrial scale. A processing method is suggested on the basis of the data obtained. (orig.) [de

  12. Ligand influences on properties of uranium coordination complexes. Structure, reactivity, and spectroscopy

    International Nuclear Information System (INIS)

    Kosog, Boris

    2012-01-01

    example of a uranium(IV) μ-trithiocarbonate was synthesized and characterized. Reaction of the μ-sulfide complex [{(( Ad ArO) 3 N)U IV } 2 (μ-S)], which is obtained by reaction of the uranium(III) complex with triphenylphosphine sulfide, with CS 2 leads to the formation of the [{(( Ad ArO) 3 N)U IV } 2 (μ-κ 2 :κ 2 -CS 3 )]. The coordination mode of the trithicarbonate differes from that of the respective carbonate, obtained previously from a similar reaction of the μ-oxo complex with CO 2 . With the help of detailed DFT calculations, the different reactivity of uranium(III) towards CO 2 and CS 2 is rationalized. Finally, a series of the first uranium vinyl complexes is presented. These are obtained through inter- and intramolecular C-C-coupling reactions of terminal mono- or bisalkynes on a uranium(III) complex. Detailed mechanistic DFT calculations show that a bimetallic mechanism is energetically most likely. This mechanism can be transferred to the catalytic alkyne coupling using both uranium(III), as reported by Eisen in the late 90's, and also transition metal catalyzed C-C-coupling, where a bimetallic mechanism should be taken into account.

  13. Bioremediation of Uranium-Contaminated Groundwater using Engineered Injection and Extraction

    Science.gov (United States)

    Greene, J. A.; Neupauer, R.; Ye, M.; Kasprzyk, J. R.; Mays, D. C.; Curtis, G. P.

    2017-12-01

    During in-situ remediation of contaminated groundwater, a treatment chemical is injected into the contaminated groundwater to react with and degrade the contaminant, with reactions occurring where the treatment chemical contacts the contaminant. Traditional in-situ groundwater remediation relies on background groundwater flow for spreading of treatment chemicals into contaminant plumes. Engineered Injection and Extraction (EIE), in which time-varying induced flow fields are used to actively spread the treatment chemical into the contaminant plume, has been developed to increase contact between the contaminant and treatment chemical, thereby enhancing contaminant degradation. EIE has been investigated for contaminants that degrade through irreversible bimolecular reaction with a treatment chemical, but has not been investigated for a contaminant governed by reversible reactions. Uranium primarily occurs in its aqueous, mobile form, U(VI), in the environment but can be bioreduced to its sparingly soluble, immobile form, U(IV), by iron reducing bacteria stimulated by an acetate amendment. In this study, we investigate the ability of EIE to facilitate and sustain favorable conditions to immobilize uranium during remediation, and to prevent re-mobilization of uranium into the aqueous phase after active remediation has ended. Simulations in this investigation are conducted using a semi-synthetic model based on physical and chemical conditions at the Naturita Uranium Mill Tailings Remedial Action (UMTRA) site in southwestern Colorado and the Old Rifle UMTRA site in western Colorado. The EIE design is optimized for the synthetic model using the Borg multi-objective evolutionary algorithm.

  14. Absorption, accumulation and biological effects of depleted uranium in Peyer's patches of rats

    International Nuclear Information System (INIS)

    Dublineau, I.; Grison, S.; Grandcolas, L.; Baudelin, C.; Tessier, C.; Suhard, D.; Frelon, S.; Cossonnet, C.; Claraz, M.; Ritt, J.; Paquet, P.; Voisin, P.; Gourmelon, P.

    2006-01-01

    The digestive tract is the entry route for radionuclides following the ingestion of contaminated food and/or water wells. It was recently characterized that the small intestine was the main area of uranium absorption throughout the gastrointestinal tract. This study was designed to determine the role played by the Peyer's patches in the intestinal absorption of uranium, as well as the possible accumulation of this radionuclide in lymphoid follicles and the toxicological or pathological consequences on the Peyer's patch function subsequent to the passage and/or accumulation of uranium. Results of experiments performed in Ussing chambers indicate that the apparent permeability to uranium in the intestine was higher (10-fold) in the mucosa than in Peyer's patches ((6.21 ± 1.21 to 0.55 ± 0.35) x 10 -6 cm/s, respectively), demonstrating that the small intestinal epithelium was the preferential pathway for the transmucosal passage of uranium. A quantitative analysis of uranium by ICP-MS following chronic contamination with depleted uranium during 3 or 9 months showed a preferential accumulation of uranium in Peyer's patches (1355% and 1266%, respectively, at 3 and 9 months) as compared with epithelium (890% and 747%, respectively, at 3 and 9 months). Uranium was also detected in the mesenteric lymph nodes (∼5-fold after contamination with DU). The biological effects of this accumulation of depleted uranium after chronic contamination were investigated in Peyer's patches. There was no induction of the apoptosis pathway after chronic DU contamination in Peyer's patches. The results indicate no change in the cytokine expression (Il-10, TGF-β, IFN-γ, TNF-α, MCP-1) in Peyer's patches and in mesenteric lymph nodes, and no modification in the uptake of yeast cells by Peyer's patches. In conclusion, this study shows that the Peyer's patches were a site of retention for uranium following the chronic ingestion of this radionuclide, without any biological consequences of

  15. Uranium Release from Acidic Weathered Hanford Sediments: Single-Pass Flow-Through and Column Experiments.

    Science.gov (United States)

    Wang, Guohui; Um, Wooyong; Wang, Zheming; Reinoso-Maset, Estela; Washton, Nancy M; Mueller, Karl T; Perdrial, Nicolas; O'Day, Peggy A; Chorover, Jon

    2017-10-03

    The reaction of acidic radioactive waste with sediments can induce mineral transformation reactions that, in turn, control contaminant fate. Here, sediment weathering by synthetic uranium-containing acid solutions was investigated using bench-scale experiments to simulate waste disposal conditions at Hanford's cribs (Hanford, WA). During acid weathering, the presence of phosphate exerted a strong influence over uranium mineralogy and a rapidly precipitated, crystalline uranium phosphate phase (meta-ankoleite [K(UO 2 )(PO 4 )·3H 2 O]) was identified using spectroscopic and diffraction-based techniques. In phosphate-free system, uranium oxyhydroxide minerals such as K-compreignacite [K 2 (UO 2 ) 6 O 4 (OH) 6 ·7H 2 O] were formed. Single-pass flow-through (SPFT) and column leaching experiments using synthetic Hanford pore water showed that uranium precipitated as meta-ankoleite during acid weathering was strongly retained in the sediments, with an average release rate of 2.67 × 10 -12 mol g -1 s -1 . In the absence of phosphate, uranium release was controlled by dissolution of uranium oxyhydroxide (compreignacite-type) mineral with a release rate of 1.05-2.42 × 10 -10 mol g -1 s -1 . The uranium mineralogy and release rates determined for both systems in this study support the development of accurate U-release models for the prediction of contaminant transport. These results suggest that phosphate minerals may be a good candidate for uranium remediation approaches at contaminated sites.

  16. Uranium Release from Acidic Weathered Hanford Sediments: Single-Pass Flow-Through and Column Experiments

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Guohui [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Um, Wooyong [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Pohang University of Science and Technology (POSTECH), Pohang, South Korea; Wang, Zheming [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Reinoso-Maset, Estela [Sierra; Washton, Nancy M. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Mueller, Karl T. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Perdrial, Nicolas [Department; Department; O’Day, Peggy A. [Sierra; Chorover, Jon [Department

    2017-09-21

    The reaction of acidic radioactive waste with sediments can induce mineral transformation reactions that, in turn, control contaminant fate. Here, sediment weathering by synthetic uranium-containing acid solutions was investigated using bench-scale experiments to simulate waste disposal conditions at Hanford’s cribs, USA. During acid weathering, the presence of phosphate exerted a strong influence over uranium mineralogy and a rapidly precipitated, crystalline uranium phosphate phase (meta-ankoleite [K(UO2)(PO4)·3H2O]) was identified using spectroscopic and diffraction-based techniques. In phosphate-free system, uranium oxyhydroxide minerals such as K-compreignacite [K2(UO2)6O4(OH)6·7H2O] were formed. Single-pass flow-through (SPFT) and column leaching experiments using synthetic Hanford pore water showed that uranium precipitated as meta-ankoleite during acid weathering was strongly retained in the sediments, with an average release rate of 2.67E-12 mol g-1 s-1. In the absence of phosphate, uranium release was controlled by dissolution of uranium oxyhydroxide (compreignacite-type) mineral with a release rate of 1.05-2.42E-10 mol g-1 s-1. The uranium mineralogy and release rates determined for both systems in this study support the development of accurate U-release models for prediction of contaminant transport. These results suggest that phosphate minerals may be a good candidate for uranium remediation approaches at contaminated sites.

  17. A melt refining method for uranium-contaminated aluminum

    International Nuclear Information System (INIS)

    Uda, T.; Iba, H.; Hanawa, K.

    1986-01-01

    Melt refining of uranium-contaminated aluminum which has been difficult to decontaminate because of the high reactivity of aluminum, was experimentally studied. Samples of contaminated aluminum and its alloys were melted after adding various halide fluxes at various melting temperatures and various melting times. Uranium concentration in the resulting ingots was determined. Effective flux compositions were mixtures of chlorides and fluorides, such as LiF, KCl, and BaCl 2 , at a fluoride/chloride mole ratio of 1 to 1.5. The removal of uranium from aluminum (the ''decontamination effect'') increased with decreasing melting temperature, but the time allowed for reaction had little influence. Pure aluminum was difficult to decontaminate from uranium; however, uranium could be removed from alloys containing magnesium. This was because the activity of the aluminum was decreased by formation of the intermetallic compound Al-Mg. With a flux of LiF-KCl-BaCl 2 and a temperature of 800 0 C, uranium added to give an initial concentration of 500 ppm was removed from a commercial alloy of aluminum, A5056, which contains 5% magnesium, to a final concentration of 0.6 ppm, which is near that in the initial aluminum alloy

  18. Uranium mineralization and unconformities: how do they correlate? - A look beyond the classic unconformity-type deposit model?

    Science.gov (United States)

    Markwitz, Vanessa; Porwal, Alok; Campbell McCuaig, T.; Kreuzer, Oliver P.

    2010-05-01

    Uranium deposits are usually classified based on the characteristics of their host rocks and geological environments (Dahlkamp, 1993; OECD/NEA Red Book and IAEA, 2000; Cuney, 2009). The traditional unconformity-related deposit types are the most economical deposits in the world, with the highest grades amongst all uranium deposit types. In order to predict undiscovered uranium deposits, there is a need to understand the spatial association of uranium mineralization with structures and unconformities. Hydrothermal uranium deposits develop by uranium enriched fluids from source rocks, transported along permeable pathways to their depositional environment. Unconformities are not only separating competent from incompetent sequences, but provide the physico-chemical gradient in the depositional environment. They acted as important fluid flow pathways for uranium to migrate not only for surface-derived oxygenated fluids, but also for high oxidized metamorphic and magmatic fluids, dominated by their geological environment in which the unconformities occur. We have carried out comprehensive empirical spatial analyses of various types of uranium deposits in Australia, and first results indicate that there is a strong spatial correlation between unconformities and uranium deposits, not only for traditional unconformity-related deposits but also for other styles. As a start we analysed uranium deposits in Queensland and in particular Proterozoic metasomatic-related deposits in the Mount Isa Inlier and Late Carboniferous to Early Permian volcanic-hosted uranium occurrences in Georgetown and Charters Towers Regions show strong spatial associations with contemporary and older unconformities. The Georgetown Inlier in northern Queensland consists of a diverse range of rocks, including Proterozoic and early Palaeozoic metamorphic rocks and granites and late Palaeozoic volcanic rocks and related granites. Uranium-molybdenum (+/- fluorine) mineralization in the Georgetown inlier

  19. Estimating the threshold levels of uranium and fluorine for the development of pulmonitis and toxic lung edema resultant from accidents involving uranium hexafluoride release

    International Nuclear Information System (INIS)

    Gasteva, G.N.; Antipin, E.B.; Bad'in, V.I.; Molokanov, A.A.; Mordasheva, V.V.; Mirkhajdarov, A.Kh.; Sorokin, A.V.; Savinova, I.A.

    1999-01-01

    Threshold doses of uranium and fluorine for the development of pulmonitis and toxic edema of the lung with lethal outcome are estimated. The levels of UF 6 entry under emergency conditions are evaluated and bronchopulmonary disease is described in subjects involved in three accidents with UF 6 release which occurred in the seventies and eighties, as shown by records. The results deny the previous assumption on the leading role of uranium in a single exposure to uranium hexafluoride. Fluorine ion triggering the mechanism of reactions in systems which determine the disease outcome is vitally important [ru

  20. Criticality analyses of regions containing uranium in the earth history

    International Nuclear Information System (INIS)

    Ravnik, M.

    2005-01-01

    Investigations of necessary conditions for a self-sustained chain reaction in the Earth inner regions hypothetically containing uranium is presented for the time interval from Earth formation to present time. It is determined that criticality was theoretically possible up to 2.5 Ga before present if uranium concentrated in pure form. In the early geological history (4 Ga before present) the self-sustained criticality could occur even if uranium was diluted up to 1:20 by the average core material or 1:60 by the average mantle material. If other metallic materials of similar density as uranium (e.g., Au, W) or similar atomic weight (e.g., Th) concentrated from the primordial mixture in equal proportion as uranium, criticality was not possible for any period in Earth history provided that the basic material contained no light nuclides (H, C). Criticality in the Earth inner regions could have established only if uranium concentrated from the basic material more effectively than elements of similar density or atomic number. (orig.)

  1. Isolation and characterization of a uranium(VI)-nitride triple bond

    Science.gov (United States)

    King, David M.; Tuna, Floriana; McInnes, Eric J. L.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

    2013-06-01

    The nature and extent of covalency in uranium bonding is still unclear compared with that of transition metals, and there is great interest in studying uranium-ligand multiple bonds. Although U=O and U=NR double bonds (where R is an alkyl group) are well-known analogues to transition-metal oxo and imido complexes, the uranium(VI)-nitride triple bond has long remained a synthetic target in actinide chemistry. Here, we report the preparation of a uranium(VI)-nitride triple bond. We highlight the importance of (1) ancillary ligand design, (2) employing mild redox reactions instead of harsh photochemical methods that decompose transiently formed uranium(VI) nitrides, (3) an electrostatically stabilizing sodium ion during nitride installation, (4) selecting the right sodium sequestering reagent, (5) inner versus outer sphere oxidation and (6) stability with respect to the uranium oxidation state. Computational analyses suggest covalent contributions to U≡N triple bonds that are surprisingly comparable to those of their group 6 transition-metal nitride counterparts.

  2. Method for converting uranium oxides to uranium metal

    Science.gov (United States)

    Duerksen, Walter K.

    1988-01-01

    A process is described for converting scrap and waste uranium oxide to uranium metal. The uranium oxide is sequentially reduced with a suitable reducing agent to a mixture of uranium metal and oxide products. The uranium metal is then converted to uranium hydride and the uranium hydride-containing mixture is then cooled to a temperature less than -100.degree. C. in an inert liquid which renders the uranium hydride ferromagnetic. The uranium hydride is then magnetically separated from the cooled mixture. The separated uranium hydride is readily converted to uranium metal by heating in an inert atmosphere. This process is environmentally acceptable and eliminates the use of hydrogen fluoride as well as the explosive conditions encountered in the previously employed bomb-reduction processes utilized for converting uranium oxides to uranium metal.

  3. Radioactive wastes of uranium mining and milling: Radiological consequences for human population and natural environment

    International Nuclear Information System (INIS)

    Sazykina, T.G.; Kryshev, I.I.

    2002-01-01

    The sources of wastes and levels of radioactive contamination are considered in the areas of uranium ore mining and milling. Assessments of doses to the population are made using the methodology of multiple sources and pathways of exposure, including calculations of inhalation dose and doses from consumption of contaminated agricultural and natural products, as well as external exposure from the radioactive cloud and soil. On the local (0-100 km) spatial scale, the dose from uranium mining and processing is, on average, about 0.7 man Sv (GWa) -1 . The most significant pathway of the population exposure is inhalation of radon. The impact of uranium ore mining and processing on natural flora and fauna is determined by specific characteristics of the production at uranium mining enterprises and has both radiation and non-radiation components. The estimates of external and internal exposures to the natural biota in the vicinity of hydro-metallurgical works and tailing dumps are presented. (author)

  4. Isotope exchange between gaseous hydrogen and uranium hydride powder

    International Nuclear Information System (INIS)

    Shugard, Andrew D.; Buffleben, George M.; Johnson, Terry A.; Robinson, David B.

    2014-01-01

    Highlights: • Isotope exchange between hydrogen gas and uranium hydride powder can be rapid and reversible. • Gas–solid exchange rate is controlled by transport within ∼0.7 μm hydride particles. • Gas chromatographic separation of hydrogen isotopes using uranium hydride is feasible. - Abstract: Isotope exchange between gaseous hydrogen and solid uranium hydride has been studied by flowing hydrogen (deuterium) gas through packed powder beds of uranium deuteride (hydride). We used a residual gas analyzer system to perform real-time analysis of the effluent gas composition. We also developed an exchange and transport model and, by fitting it to the experimental data, extracted kinetic parameters for the isotope exchange reaction. Our results suggest that, from approximately 70 to 700 kPa and 25 to 400 °C, the gas-to-solid exchange rate is controlled by hydrogen and deuterium transport within the ∼0.7 μm diameter uranium hydride particles. We use our kinetic parameters to show that gas chromatographic separation of hydrogen and deuterium using uranium hydride could be feasible

  5. Conceptual Model of Uranium in the Vadose Zone for Acidic and Alkaline Wastes Discharged at the Hanford Site Central Plateau

    Energy Technology Data Exchange (ETDEWEB)

    Truex, Michael J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Szecsody, James E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Qafoku, Nikolla [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Serne, R. Jeffrey [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2014-09-01

    Historically, uranium was disposed in waste solutions of varying waste chemistry at the Hanford Site Central Plateau. The character of how uranium was distributed in the vadose zone during disposal, how it has continued to migrate through the vadose zone, and the magnitude of potential impacts on groundwater are strongly influenced by geochemical reactions in the vadose zone. These geochemical reactions can be significantly influenced by the disposed-waste chemistry near the disposal location. This report provides conceptual models and supporting information to describe uranium fate and transport in the vadose zone for both acidic and alkaline wastes discharged at a substantial number of waste sites in the Hanford Site Central Plateau. The conceptual models include consideration of how co-disposed acidic or alkaline fluids influence uranium mobility in terms of induced dissolution/precipitation reactions and changes in uranium sorption with a focus on the conditions near the disposal site. This information, when combined with the extensive information describing uranium fate and transport at near background pH conditions, enables focused characterization to support effective fate and transport estimates for uranium in the subsurface.

  6. On the radiology of thorium-uranium electro breeding

    International Nuclear Information System (INIS)

    Gai, E.V.; Rabotnov, N.S.; Shubin, Y.N.

    1995-01-01

    Radiological problems arising in thorium-uranium electro-breeding with thorium accelerator target are discussed. Following radiological problems are discussed and evaluated in simplified model calculations: U-232 formation, accumulation of light Th isotopes in (n, xn) reactions on thorium target: accumulation of the same nuclides in final repository after alpha-decay of uranium isotopes. The qualitative comparison of U-Pu and U-Th fuel cycles is performed. The problems seem to be serious enough to justify detailed quantitative investigation. (authors)

  7. Molybdenum from uranium solutions

    International Nuclear Information System (INIS)

    Gardner, H.E.

    1981-01-01

    A method of removing molybdenum from a uranium bearing solution is claimed. It comprises adding sufficient reactive lead compound to supply at least 90 percent of the stoichiometric quantity of lead ion required to fully react with the molybdenum present to form insoluble lead molybdate and continuing the reaction with agitation until the desired percentage of the molybdenum present has reacted with the lead ion

  8. Uranium sesqui nitride synthesis and its use as catalyst for the thermo decomposition of ammonia

    International Nuclear Information System (INIS)

    Rocha, Soraya Maria Rizzo da

    1996-01-01

    The preoccupation to have a secure destination for metallic uranium scraps and wastes and to search new non-nuclear uses for the huge amount of depleted metal uranium accumulated at the nuclear industry encouraged the study of the uranium sesqui nitride synthesis and its use. The use of uranium sesqui nitride as a catalyst for the thermo decomposition of ammonia for the hydrogen production has enormous significance. One of the most important nuclear cycle step is the reduction of the higher uranium oxides for the production of uranium dioxide and its conversion to uranium tetrafluoride. The reduction of the UO 3 and U 3 O 8 oxides is accomplished by the gas-solid reaction with elementary hydrogen. For economical purposes and for the safety concern the nuclear industry prefers to manufacture the hydrogen gas at the local and at the moment of use, exploring the catalytic decomposition of ammonia vapor. Using metallic uranium scraps as the raw material the obtention of its nitride was achieved by the reaction with ammonia. The results of the chemical and physical characterization of the prepared uranium sesqui nitride and its behavior as a catalyst for the cracking of ammonia are commented. A lower ammonia cracking temperature (550 deg C) using the uranium sesqui nitride compared with recommended industrial catalysts iron nitride (650 deg C) and manganese nitride (700 deg C) sounds reliable and economically advantageous. (author)

  9. Preliminary study of the preparation of uranium 232 by irradiation of protactinium 231; Etude preliminaire a la preparation d'uranium 232 par irradiation de protactinium 231

    Energy Technology Data Exchange (ETDEWEB)

    Guillot, Ph. [Commissariat a l' Energie Atomique, Fontenay aux Roses (France). Centre d' Etudes Nucleaires

    1965-07-01

    A bibliography about preparation of uranium 232 is done. This even-even isotope of uranium is suitable for radioactive tracer, neutron source through {alpha},n reaction and heat source applications. The irradiation of protactinium 231, the chemical separation and the purification of uranium are studied. (author) [French] Une etude bibliographique de la preparation d'uranium 232 a ete effectuee. Cet isotope pair-pair de l'uranium peut etre utilise en tant que traceur, source d'energie et source de neutrons, lorsqu'il est melange a un element leger tel le beryllium. Une etude du taux de formation des isotopes produits, lors de l'irradiation du protactinium 231 - une des manieres d'obtenir l'uranium 232 - a ete faite a l'aide d'un programme passe sur ordinateur. Les problemes poses par la separation chimique et la purification de l'uranium ont ete egalement envisages dans ce rapport. (auteur)

  10. Phase equilibrium study on system uranium-plutonium-tungsten-carbon

    International Nuclear Information System (INIS)

    Ugajin, Mitsuhiro

    1976-11-01

    Metallurgical properties of the U-Pu-W-C system have been studied with emphasis on phases and reactions. Free energy of compound formation, carbon activity and U/Pu segregation in the W-doped carbide fuel are estimated using phase diagram data. The results indicate that tungsten metal is useful as a thermochemical stabilizer of the carbide fuel. Tungsten has high temperature stability in contact with uranium carbide and mixed uranium-plutonium carbide. (auth.)

  11. Effect of CO on surface oxidation of uranium metal

    International Nuclear Information System (INIS)

    Wang, X.; Fu, Y.; Xie, R.

    1997-01-01

    The surface reactions of uranium metal with carbon monoxide at 25 and 200 deg C have been studied by X-ray photoelectron spectroscopy (XPS);respectively. Adsorption of carbon monoxide on the surface layer of uranium metal leads to partial reduction of surface oxide and results in U4f photoelectron peak shifting to the lower binding energy. The content of oxygen in the surface oxide is decreased and O1s/O4f ratio decreases with increasing the exposure of carbon monoxide. The investigation indicates the surface layer of uranium metal has resistance to further oxidation in the atmosphere of carbon monoxide. (author)

  12. Kinetics study of the fluorination of uranium tetrafluoride in a fluidized bed reactor

    International Nuclear Information System (INIS)

    Khani, M.H.; Pahlavanzadeh, H.; Ghannadi, M.

    2008-01-01

    The kinetics of reaction of the uranium tetrafluoride conversion to the uranium hexafluoride with fluorine gas taking place in a fluidized bed reactor operating in industrial conditions have been studied. The external and internal diffusion effects are investigated by Mears and Weisz-Prater criterions. The kinetic equation for the fluorination of uranium tetrafluoride is developed in the absence of diffusional limitation using an integral method by assuming that the gas flow is of plug or perfectly mixed type. A good agreement is observed between the experimental data and a first-order model with respect to fluorine in the CSTR system. The activation energy of the reaction and the pre-exponential factor are obtained using analytical results from a better model

  13. Fixation and reduction of uranium by natural organic matter: reaction mechanisms and kinetics

    International Nuclear Information System (INIS)

    Nakashima, S.; Perruchot, A.; Trichet, J.; Disnar, J.R.

    1987-01-01

    The reactivity of lignite towards soluble uranyl species in an aqueous medium is experimentally investigated as a function of temperature (between 20 0 C and 400 0 C). The fixation process starts near 45 0 C, with reduction beginning around 120 0 C. The fixation process leads to the formation of chemically and thermally stable organo-uranyl species. The reduction of free uranyl species is accompanied by a stoichiometric (2:1) liberation of protons into the medium. These protons originate from the organic matter which thus undergoes dehydrogenation. The general evolution of the carbonaceous residue in the course of this reaction shows that alcoholic and aliphatic hydrocarbon groups are responsible for the reduction. This chemical dehydrogenation could explain the low hydrogen content of natural organic materials associated with uraniferous deposits. The kinetics of the reduction step have been studied at 180 0 C, 190 0 C and 200 0 C. The kinetic parameters determined over this temperature range, and the extrapolation made to 20 0 C, show that reduction can be a crucial process in the geochemical behaviour of uranium especially in the thermal conditions in which sedimentary basins evolve [fr

  14. Uranium

    International Nuclear Information System (INIS)

    Cuney, M.; Pagel, M.; Leroy, J.

    1992-01-01

    First, this book presents the physico-chemical properties of Uranium and the consequences which can be deduced from the study of numerous geological process. The authors describe natural distribution of Uranium at different scales and on different supports, and main Uranium minerals. A great place in the book is assigned to description and classification of uranium deposits. The book gives also notions on prospection and exploitation of uranium deposits. Historical aspects of Uranium economical development (Uranium resources, production, supply and demand, operating costs) are given in the last chapter. 7 refs., 17 figs

  15. Uranium

    International Nuclear Information System (INIS)

    Poty, B.; Cuney, M.; Bruneton, P.; Virlogeux, D.; Capus, G.

    2010-01-01

    With the worldwide revival of nuclear energy comes the question of uranium reserves. For more than 20 years, nuclear energy has been neglected and uranium prospecting has been practically abandoned. Therefore, present day production covers only 70% of needs and stocks are decreasing. Production is to double by 2030 which represents a huge industrial challenge. The FBR-type reactors technology, which allows to consume the whole uranium content of the fuel, is developing in several countries and will ensure the long-term development of nuclear fission. However, the implementation of these reactors (the generation 4) will be progressive during the second half of the 21. century. For this reason an active search for uranium ores will be necessary during the whole 21. century to ensure the fueling of light water reactors which are huge uranium consumers. This dossier covers all the aspects of natural uranium production: mineralogy, geochemistry, types of deposits, world distribution of deposits with a particular attention given to French deposits, the exploitation of which is abandoned today. Finally, exploitation, ore processing and the economical aspects are presented. Contents: 1 - the uranium element and its minerals: from uranium discovery to its industrial utilization, the main uranium minerals (minerals with tetravalent uranium, minerals with hexavalent uranium); 2 - uranium in the Earth's crust and its geochemical properties: distribution (in sedimentary rocks, in magmatic rocks, in metamorphic rocks, in soils and vegetation), geochemistry (uranium solubility and valence in magmas, uranium speciation in aqueous solution, solubility of the main uranium minerals in aqueous solution, uranium mobilization and precipitation); 3 - geology of the main types of uranium deposits: economical criteria for a deposit, structural diversity of deposits, classification, world distribution of deposits, distribution of deposits with time, superficial deposits, uranium

  16. Pump-shaped dump optimal control reveals the nuclear reaction pathway of isomerization of a photoexcited cyanine dye.

    Science.gov (United States)

    Dietzek, Benjamin; Brüggemann, Ben; Pascher, Torbjörn; Yartsev, Arkady

    2007-10-31

    Using optimal control as a spectroscopic tool we decipher the details of the molecular dynamics of the essential multidimensional excited-state photoisomerization - a fundamental chemical reaction of key importance in biology. Two distinct nuclear motions are identified in addition to the overall bond-twisting motion: Initially, the reaction is dominated by motion perpendicular to the torsion coordinate. At later times, a second optically active vibration drives the system along the reaction path to the bottom of the excited-state potential. The time scales of the wavepacket motion on a different part of the excited-state potential are detailed by pump-shaped dump optimal control. This technique offers new means to control a chemical reaction far from the Franck-Condon point of absorption and to map details of excited-state reaction pathways revealing unique insights into the underlying reaction mechanism.

  17. Heterogeneous-catalytic redox reactions in nitrate - formate systems

    International Nuclear Information System (INIS)

    Ananiev, A.V.; Shilov, V.P.; Tananaev, I.G.; Brossard, Ph.; Broudic, J.Ch.

    2000-01-01

    It was found that an intensive destruction of various organic and mineral substances - usual components of aqueous waste solutions (oxalic acid, complexones, urea, hydrazine, ammonium nitrate, etc.) takes place under the conditions of catalytic denitration. Kinetics and mechanisms of urea and ammonium nitrate decomposition in the system HNO 3 - HCOOH - Pt/SiO 2 are comprehensively investigated. The behaviour of uranium, neptunium and plutonium under the conditions of catalytic denitration is studied. It is shown, that under the certain conditions the formic acid is an effective reducer of the uranium (VI), neptunium (VI, V) and plutonium (VI, IV) ions. Kinetics of heterogeneous-catalytic red-ox reactions of uranium (VI), neptunium (VI, V) and plutonium (VI, IV) with formic acid are investigated. The mechanisms of the appropriate reactions are evaluated. (authors)

  18. Oxidizing attack process of uranium ore by a carbonated liquor

    International Nuclear Information System (INIS)

    Maurel, Pierre; Nicolas, Francois.

    1981-01-01

    A continuous process for digesting a uraniferous ore by oxidation with a recycling aqueous liquor containing alkaline carbonates and bicarbonates in solution as well as uranium in a concentration close to its solubility limit at digestion temperature, and of recuperation of the precipitated uranium within the solid phase remaining after digestion. The digestion is carried out by spraying oxygen into the hot reactional medium in order not only to permit oxidation of the uranium and its solubilization but also to ensure that the sulphides of impurities and organic substances present in the ore are oxidized [fr

  19. Nuclear energy - Uranium dioxide powder and sintered pellets - Determination of oxygen/uranium atomic ratio by the amperometric method. 2. ed.

    International Nuclear Information System (INIS)

    2007-01-01

    This International Standard specifies an analytical method for the determination of the oxygen/uranium atomic ratio in uranium dioxide powder and sintered pellets. The method is applicable to reactor grade samples of hyper-stoichiometric uranium dioxide powder and pellets. The presence of reducing agents or residual organic additives invalidates the procedure. The test sample is dissolved in orthophosphoric acid, which does not oxidize the uranium(IV) from UO 2 molecules. Thus, the uranium(VI) that is present in the dissolved solution is from UO 3 and/or U 3 O 8 molecules only, and is proportional to the excess oxygen in these molecules. The uranium(VI) content of the solution is determined by titration with a previously standardized solution of ammonium iron(II) sulfate hexahydrate in orthophosphoric acid. The end-point of the titration is determined amperometrically using a pair of polarized platinum electrodes. The oxygen/uranium ratio is calculated from the uranium(VI) content. A portion, weighing about 1 g, of the test sample is dissolved in orthophosphoric acid. The dissolution is performed in an atmosphere of nitrogen or carbon dioxide when sintered material is being analysed. When highly sintered material is being analysed, the dissolution is performed at a higher temperature in purified phosphoric acid from which the water has been partly removed. The cooled solution is titrated with an orthophosphoric acid solution of ammonium iron(II) sulfate, which has previously been standardized against potassium dichromate. The end-point of the titration is detected by the sudden increase of current between a pair of polarized platinum electrodes on the addition of an excess of ammonium iron(II) sulfate solution. The paper provides information about scope, principle, reactions, reagents, apparatus, preparation of test sample, procedure (uranium dioxide powder, sintered pellets of uranium dioxide, highly sintered pellets of uranium dioxide and determination

  20. A new method for alkaline dissolution of uranium metal foil

    International Nuclear Information System (INIS)

    Mondino, A.V.; Wilkinson, M.V.; Manzini, A.C.

    2001-01-01

    In order to develop a production process of 99 Mo by fission of low-enriched uranium, the first purification step, which consists of dissolution of a uranium metal foil target, was studied. It was found that alkaline NaClO gave good results, reaching the dissolution of up to 300 μm of uranium foil. The different conditions for the dissolution were studied and the optimum ones were found. The influence of NaClO and NaOH concentration, temperature, dissolving solution volume per unit of surface and dissolution time were investigated. During this step, a gas identified as H 2 , was generated, and a precipitate characterized as Na 2 U 2 O 7 was observed. A stoichiometric reaction for this uranium dissolution is proposed. (author)

  1. Analytical and numerical models of uranium ignition assisted by hydride formation

    International Nuclear Information System (INIS)

    Totemeier, T.C.; Hayes, S.L.

    1996-01-01

    Analytical and numerical models of uranium ignition assisted by the oxidation of uranium hydride are described. The models were developed to demonstrate that ignition of large uranium ingots could not occur as a result of possible hydride formation during storage. The thermodynamics-based analytical model predicted an overall 17 C temperature rise of the ingot due to hydride oxidation upon opening of the storage can in air. The numerical model predicted locally higher temperature increases at the surface; the transient temperature increase quickly dissipated. The numerical model was further used to determine conditions for which hydride oxidation does lead to ignition of uranium metal. Room temperature ignition only occurs for high hydride fractions in the nominally oxide reaction product and high specific surface areas of the uranium metal

  2. Preparation of electrodeless discharge lamps for emission studies of uranium isotopes at trace level

    International Nuclear Information System (INIS)

    Bhowmick, G.K.; Verma, R.; Verma, M.K.; Raman, V.A.; Joshi, A.R.; Deo, M.N.; Gantayet, L.M.; Tiwari, A.K.; Ramakumar, K.L.; Kumar, Navin

    2010-01-01

    A simplified method for preparation of electrodeless discharge lamp for uranium isotopes with specific concerns for 232 U is described. Micro-gram quantities of solid uranium oxides and aqueous solution of uranium nitrate have been used as a starting material for in situ synthesis of uranium tetraiodide. High temperature iodination reaction is carried out in the presence of inert gas neon. By careful design, the preparation time and surface area of quartz reaction tubes have been reduced considerably. The latter decreases the level of contamination which has a direct bearing on the operational lifetime of the lamps. Incorporation of steps to purify the product from an unwanted material improved the stability of the lamps. The procedure provides a safe and convenient way of handling 232 U in particular but can be extended in general to any actinides having radioactivity similar to that of freshly separated 232 U. Characteristic emission of uranium isotopes have been recorded by Fourier Transform Spectrometer to show the satisfactory operation of the lamps as well as their usage for studying emission spectra of the specific isotope.

  3. Estimating contaminant discharge rates from stabilized uranium tailings embankments

    International Nuclear Information System (INIS)

    Weber, M.F.

    1986-01-01

    Estimates of contaminant discharge rates from stabilized uranium tailings embankments are essential in evaluating long-term impacts of tailings disposal on groundwater resources. Contaminant discharge rates are a function of water flux through tailings covers, the mass and distribution of tailings, and the concentrations of contaminants in percolating pore fluids. Simple calculations, laboratory and field testing, and analytical and numerical modeling may be used to estimate water flux through variably-saturated tailings under steady-state conditions, which develop after consolidation and dewatering have essentially ceased. Contaminant concentrations in water discharging from the tailings depend on tailings composition, leachability and solubility of contaminants, geochemical conditions within the embankment, tailings-water interactions, and flux of water through the embankment. These concentrations may be estimated based on maximum reported concentrations, pore water concentrations, extrapolations of column leaching data, or geochemical equilibria and reaction pathway modeling. Attempts to estimate contaminant discharge rates should begin with simple, conservative calculations and progress to more-complicated approaches, as necessary

  4. Thermodynamic isotope effects of D2 and T2 reaction with uranium

    International Nuclear Information System (INIS)

    Huang Gang; Long Xinggui; Liang Jianhua; Yang Benfu; Liu Wenke

    2010-01-01

    The p-c-T curves of deuterium and tritium absorption by uranium and p-t curves of desorption were measured. The balance pressure of absorption and desorption on different temperatures were got and then the thermodynamic parameters were determined according to the Van't Hoff equation. It shows that the balance pressure of deuterium absorption is lower than that of tritium absorption on the same temperature and atom ratio. It has the same phenomena for desorption but there are obvious hysteresis effect for reversible process of absorption and desorption. There are a little thermodynamic isotope effects when deuterium and tritium absorption and desorption by uranium estimating from enthalpy and entropy values. (authors)

  5. DEVELOPMENT OF HIGH-DENSITY U/AL DISPERSION PLATES FOR MO-99 PRODUCTION USING ATOMIZED URANIUM POWDER

    Directory of Open Access Journals (Sweden)

    HO JIN RYU

    2013-12-01

    Full Text Available Uranium metal particle dispersion plates have been proposed as targets for Molybdenum-99 (Mo-99 production to improve the radioisotope production efficiency of conventional low enriched uranium targets. In this study, uranium powder was produced by centrifugal atomization, and miniature target plates containing uranium particles in an aluminum matrix with uranium densities up to 9 g-U/cm3 were fabricated. Additional heat treatment was applied to convert the uranium particles into UAlx compounds by a chemical reaction of the uranium particles and aluminum matrix. Thus, these target plates can be treated with the same alkaline dissolution process that is used for conventional UAlx dispersion targets, while increasing the uranium density in the target plates

  6. Chemical separation of Th-230 from uranium ore

    International Nuclear Information System (INIS)

    Kikunaga, H.; Nakanishi, T.; Mitsugashira, T.; Hara, M.

    2001-01-01

    We are studying the decay processes of low energy nuclear isomer of Th-229. Our approach to produce Th-229m is (γ, n) reaction on Th-230, hence, about 100 μg of Th-230 is necessary as a target. However, our stock of Th-230 has run out during several experiments, thus, we tried to separate Th-230 from uranium ore. In this paper, the detail of a chemical separation procedure for Th-230 from uranium ore and the results are reported. (author)

  7. The discovery of uranium fission

    International Nuclear Information System (INIS)

    Brix, P.

    1990-01-01

    Uranium was discovered 200 years ago. Its radioactive character was first demonstrated in 1896 and two years later radium was extracted from uranium minerals. In 1911 studies with alpha rays from radioactive decay led to the unexpected discovery of the atomic nucleus. Exposure of beryllium to alpha rays yielded neutrons, first detected in 1932. Starting in 1934, neutron irradiation of uranium produced radioactive substances erroneously attributed to transuranium elements but with confusing properties. Painstaking experiments by chemists left no doubt on 17 December 1938 that barium was produced by these irradiations: the neutrons had split some uranium nuclei. The physics of the fission process was understood two weeks later; after a few months, neutron multiplication was found to be probable. This review deals with the eminent scientists involved, their successes, errors and disappointments, and the unexpected insights which occurred on the paths and detours of scientific research. It is, therefore, instructive also to discuss how fission was not discovered. The momentous discovery must be considered inevitable; the great tragedy was that Germany started World War II just at the time when the possibility of nuclear chain reactions and bombs became known. The consequences and anxieties that remain after 50 years of nuclear fission demand that mankind act with reason and conscience to maintain peace. (author)

  8. Nuclear waste viewed in a new light; a synchrotron study of uranium encapsulated in grout

    Energy Technology Data Exchange (ETDEWEB)

    Stitt, C.A., E-mail: Camilla.stitt@bristol.ac.uk [Interface Analysis Centre, H. H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL (United Kingdom); Hart, M., E-mail: oxford.mike@gmail.com [Diamond Light Source Limited, Harwell Science and Innovation Campus, Fermi Avenue, Didcot, Oxfordshire OX11 0QX (United Kingdom); Harker, N.J., E-mail: nicholas.harker@esrf.fr [Interface Analysis Centre, H. H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL (United Kingdom); Hallam, K.R., E-mail: k.r.hallam@bristol.ac.uk [Interface Analysis Centre, H. H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL (United Kingdom); MacFarlane, J., E-mail: james.macfarlane@bristol.ac.uk [Interface Analysis Centre, H. H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL (United Kingdom); Banos, A., E-mail: antonis.banos@bristol.ac.uk [Interface Analysis Centre, H. H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL (United Kingdom); Paraskevoulakos, C., E-mail: cp13846@bristol.ac.uk [Interface Analysis Centre, H. H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL (United Kingdom); Butcher, E., E-mail: ed.j.butcher@nnl.co.uk [National Nuclear Laboratory, Seascale, Cumbria CA20 1 PG (United Kingdom); Padovani, C., E-mail: cristiano.padovani@nda.gov.uk [Radioactive Waste Management Limited (formerly the Radioactive Waste Management Directorate of the UK Nuclear Decommissioning Authority), Curie Avenue, Didcot, Oxfordshire OX11 0RH (United Kingdom); Scott, T.B., E-mail: t.b.scott@bristol.ac.uk [Interface Analysis Centre, H. H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL (United Kingdom)

    2015-03-21

    Highlights: • Unirradiated Magnox uranium was encapsulated in grout and exposed to hydrogen. • Synchrotron X-ray tomography imaged the uranium corrosion before and after exposure. • Synchrotron X-ray powder diffraction identified the corrosion products; UH{sub 3} and UO{sub 2}. • Uranium encapsulated in grout oxidised via the anoxic U + H{sub 2}O regime. • Successful in-situ, non-invasive examination of pyrophoric and radioactive material - Abstract: How do you characterise the contents of a sealed nuclear waste package without breaking it open? This question is important when the contained corrosion products are potentially reactive with air and radioactive. Synchrotron X-rays have been used to perform micro-scale in-situ observation and characterisation of uranium encapsulated in grout; a simulation for a typical intermediate level waste storage packet. X-ray tomography and X-ray powder diffraction generated both qualitative and quantitative data from a grout-encapsulated uranium sample before, and after, deliberately constrained H{sub 2} corrosion. Tomographic reconstructions provided a means of assessing the extent, rates and character of the corrosion reactions by comparing the relative densities between the materials and the volume of reaction products. The oxidation of uranium in grout was found to follow the anoxic U + H{sub 2}O oxidation regime, and the pore network within the grout was observed to influence the growth of uranium hydride sites across the metal surface. Powder diffraction analysis identified the corrosion products as UO{sub 2} and UH{sub 3}, and permitted measurement of corrosion-induced strain. Together, X-ray tomography and diffraction provide means of accurately determining the types and extent of uranium corrosion occurring, thereby offering a future tool for isolating and studying the reactions occurring in real full-scale waste package systems.

  9. Elucidating Bioreductive Transformations within Physically Complex Media: Impact on the Fate and Transport of Uranium and Chromium

    International Nuclear Information System (INIS)

    Fendorf, Scott; Francis, Chris; Jardine, Phil; Benner, Shawn

    2009-01-01

    In situ stabilization (inclusive of natural attenuation) of toxic metals and radionuclides is an attractive approach for remediating many contaminated DOE sites. By immobilizing toxic metals and radionuclides in place, the removal of contaminated water to the surface for treatment as well as the associated disposal costs are avoided. To enhance in situ remediaton, microbiological reductive stabilization of contaminant metals has been, and continues to be, actively explored. It is likely that surface and subsurface microbial activity can alter the redox state of toxic metals and radionuclides, either directly or indirectly, so they are rendered immobile. Furthermore, anaerobic bacterial metabolic products will help to buffer pulses of oxidation, typically from fluxes of nitrate or molecular oxygen, and thus may stabilize reduced contaminants from oxidative mobilization. Uranium and chromium are two elements of particular concern within the DOE complex that, owing to their abundance and toxicity, appear well suited for biologically mediated reductive stabilization. Subsurface microbial activity can alter the redox state of toxic metals and radionuclides, rending them immobile. Imparting an important criterion on the probability that contaminants will undergo reductive stabilization, however, is the chemical and physical heterogeneity of the media. Our research first examined microbially induced transformation of iron (hydr)oxide minerals and their impact on contaminant attenuation. We revealed that in intricate cascade of geochemical reactions is induced by microbially produced Fe(II), and that during transformation contaminants such as U(VI) can be incorporated into the structure, and a set of Fe(II) bearing solids capable of reducing Cr(VI) and stabilizing resulting Cr(III). We also note, however, that common subsurface constituents such as phosphate can modify iron oxide transformation pathways and thus impact contaminant sequestration - affecting both Cr and U

  10. Uranium problem in production of wet phosphoric acid

    Energy Technology Data Exchange (ETDEWEB)

    Gorecka, H; Gorecki, H [Politechnika Wroclawska (Poland)

    1980-01-01

    The balance of the uranium in the wet dihydrate method was presented. This balance shows that a large quantity of the uranium compounds shift from mineral phosphate rock to liquid phase of decomposition pulp (about 70-85% U) and the rest moves to phosphogypsum (about 15-25% U). The contents of uranium in phosphate rock imported for our country and in products and by-products of the fertilizer industry, were determined. Concentration of uranium in the phosphogypsum is dependent on the type of mineral rock and the process of phosphogypsum crystallization. Analysis of the uranium contents in phosphogypsum samples and results of the sedimentation analysis indicated influence of the specific surface of phosphogypsum crystals on the uranium concentration. Investigation of the sets of samples obtained in the industrial plant proved that phosphogypsum cake washed counter-currently on the filter contained from 10 to 20 ..mu..g U/g. The radioactivity of these samples fluctuated from 35 to 60 pCi/g. Using solution sulphuric acid of concentration in range 2-4% by weight H/sub 2/SO/sub 4/ to washing and repulpation of the phosphogypsum enables to reduce its radioactivity to level below 25 pCi/g. This processing makes possible to utilize this waste material in the building industry. Extraction of uranium from the wet phosphoric acid using kerosen solution of the reaction product between octanol -1 and phosphorus pentaoxide showed possibility to recover over 80% of uranium contained in phosphate rock.

  11. Chemical vapor deposition (CVD) of uranium for alpha spectrometry

    International Nuclear Information System (INIS)

    Ramirez V, M. L.; Rios M, C.; Ramirez O, J.; Davila R, J. I.; Mireles G, F.

    2015-09-01

    The uranium determination through radiometric techniques as alpha spectrometry requires for its proper analysis, preparation methods of the source to analyze and procedures for the deposit of this on a surface or substrate. Given the characteristics of alpha particles (small penetration distance and great loss of energy during their journey or its interaction with the matter), is important to ensure that the prepared sources are thin, to avoid problems of self-absorption. The routine methods used for this are the cathodic electro deposition and the direct evaporation, among others. In this paper the use of technique of chemical vapor deposition (CVD) for the preparation of uranium sources is investigated; because by this, is possible to obtain thin films (much thinner than those resulting from electro deposition or evaporation) on a substrate and comprises reacting a precursor with a gas, which in turn serves as a carrier of the reaction products to achieve deposition. Preliminary results of the chemical vapor deposition of uranium are presented, synthesizing and using as precursor molecule the uranyl acetylacetonate, using oxygen as carrier gas for the deposition reaction on a glass substrate. The uranium films obtained were found suitable for alpha spectrometry. The variables taken into account were the precursor sublimation temperatures and deposition temperature, the reaction time and the type and flow of carrier gas. Of the investigated conditions, two depositions with encouraging results that can serve as reference for further work to improve the technique presented here were selected. Alpha spectra obtained for these depositions and the characterization of the representative samples by scanning electron microscopy and X-ray diffraction are also presented. (Author)

  12. Chlorination of uranium oxides with CCl4 using a mechanochemical method

    International Nuclear Information System (INIS)

    Kitawaki, Shinichi; Nagai, Takayuki; Sato, Nobuaki

    2013-01-01

    Highlights: • UCl 4 or UOCl 2 could be synthesized from U 3 O 8 with CCl 4 by using a planetary ball mill. • The chlorination could not be observed when using UO 2 powder as the starting material. • Extension of milling time was effective for chlorinating U 3 O 8 with the appropriate amount of CCl 4 . -- Abstract: A chlorination method for uranium oxides at low temperature was investigated by using a mechanochemical method. In particular, the possibility of the chlorination of uranium oxides, such as UO 2 and U 3 O 8 , via mechanochemical reaction with CCl 4 was studied using a planetary ball mill. Mechanochemical experiments were conducted to evaluate the effect of milling time, CCl 4 /uranium oxide molar ratio, and revolution speed on the reaction. The synthesized products were then subjected to X-ray diffraction analysis, and it was found that the chlorination of U 3 O 8 with CCl 4 to UOCl 2 , UCl 4 , and U 2 O 2 Cl 5 proceeded. However, the chlorination reaction could not be observed when using UO 2 powder as the raw material

  13. Uranium conversion

    International Nuclear Information System (INIS)

    Oliver, Lena; Peterson, Jenny; Wilhelmsen, Katarina

    2006-03-01

    FOI, has performed a study on uranium conversion processes that are of importance in the production of different uranium compounds in the nuclear industry. The same conversion processes are of interest both when production of nuclear fuel and production of fissile material for nuclear weapons are considered. Countries that have nuclear weapons ambitions, with the intention to produce highly enriched uranium for weapons purposes, need some degree of uranium conversion capability depending on the uranium feed material available. This report describes the processes that are needed from uranium mining and milling to the different conversion processes for converting uranium ore concentrate to uranium hexafluoride. Uranium hexafluoride is the uranium compound used in most enrichment facilities. The processes needed to produce uranium dioxide for use in nuclear fuel and the processes needed to convert different uranium compounds to uranium metal - the form of uranium that is used in a nuclear weapon - are also presented. The production of uranium ore concentrate from uranium ore is included since uranium ore concentrate is the feed material required for a uranium conversion facility. Both the chemistry and principles or the different uranium conversion processes and the equipment needed in the processes are described. Since most of the equipment that is used in a uranium conversion facility is similar to that used in conventional chemical industry, it is difficult to determine if certain equipment is considered for uranium conversion or not. However, the chemical conversion processes where UF 6 and UF 4 are present require equipment that is made of corrosion resistant material

  14. The mechanism of uranium adsorption on Resin 508 and isoelectric point of the resin

    International Nuclear Information System (INIS)

    Han Qingping; Lu Weichang; Su Huijuan; Hu Jinbo; Zhang Liqin; Chen Banglin

    1990-01-01

    The adsorption process of uranium by Resin 508 at the solid-liquid interface was investigated and the mechanism of uranium adsorption including adsorption dynamics, adsorption thermodynamics and isoelectric point of resin was studied. The results are as follows: The maximum of uranium adsorption is attained at pH5-7; Uranium adsorption isotherm by Resin 508 in experimental conditions agrees with Langmuir's adsorption isotherm, the maximum of uranium adsorbed (Vm) is 716 mg U/g-dried resin; The adsorption of uranium by Resin 508 is an endothermic reaction and ΔH = 16.87 kJ/mol; The exchange-adsorption rate is mainly controlled by liquid film diffusion; The isoelectric points of Resin 508 before and after uranium adsorption are found to be pH7.5 and pH5.7 respectively. It is a specific adsorption for uranium

  15. Study on removal effect and mechanism of uranium by hydroxyapatite and natural apatite

    International Nuclear Information System (INIS)

    Zhang Xiaofeng; Chen Diyun; Tu Guoqing; Huang Xiaozhui

    2014-01-01

    By the static experiments, the effects of reaction time, pH value, initial concentration of uranium, dosage of apatite on adsorption of hydroxyapatite and natural apatite for uranium were studied respectively. The adsorption process was analyzed by thermodynamics and kinetics, and the adsorption mechanism was analyzed by infrared spectroscopy, X-ray diffraction and scanning electron microscope. The results of hydroxyapatite show that the removal capacity of uranium increases with the initial concentration of uranium, and the adsorption rate of hydroxyapatite on UO_2"2"+ reaches 85%, when the pH value is 4 to 5 and dosage of hydroxyapatite is 0.75 g. The results of natural apatite show that the removal capacity of uranium increases with the initial concentration of uranium, and the adsorption rate of natural apatite on UO_2"2"+ is up to 80%, when the pH value is 3 and dosage of hydroxyapatite is l.0 g. Similarly, at 120 minutes both of the removal reactions by hydroxyapatite and natural apatite substantially reach equilibrium. Moreover, both of the reactions by hydroxyapatite and natural apatite are in line with quasi secondary dynamics equation, and follow the Langmuir adsorption isotherm. Infrared spectra indicate that the removal of hydroxyapatite for uranium depends on the complexation of phosphate, which is almost the same as that of natural apatite. X-ray diffraction analysis shows that hydroxyapatite has the composition and structure of pure material, whereas the natural apatite is mainly composed of Ca_5H_2(PO_4)_3F and Ca_8H_2(PO_4)_6H_2O. In addition, scanning electron microscope demonstrates that hydroxyapatite has the appearance of spherical with a hole and the hole has a cavity containing a large amount of floc, while the surface becomes smooth and pores are closed after removal of uranium, which is due to the adsorption of UO_2"2"+ leading a link between molecules on hydroxyapatite surface. But for natural apatite, it depicts the angular mineral shape

  16. Precipitation of uranium oxide by reduction in alkaline solution; Precipitation d'oxyde d'uranium par reduction en milieu alcalin

    Energy Technology Data Exchange (ETDEWEB)

    Pottier, P; Claus, J [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1964-07-01

    In the first part of the report the authors study the reaction mechanism for this reduction which makes it possible to precipitate a hydrated uranium oxide from alkaline uranyl carbonate solutions. The research into the effects of different variables on numerous cycles are then summarized. Optical, X-ray and thermogravimetric examinations then make it possible to predict the properties of this oxide. In the second part the authors carry out calculations for the continuous operation of single cells and cells in series. These calculations give the data required for the construction of 2 cells having capacities of 0.3 and 10 litres. Results obtained from the continuous operation of this latter cell lead to certain conclusions concerning the applicability of this method to the hydrometallurgy of uranium. (authors) [French] Dans une premiere partie, les auteurs etudient le mecanisme de reaction de cette reduction qui permet la precipitation d'un oxyde d'uranium hydrate dans les solutions d'uranyle-carbonates alcalins. Les etudes de diverses variables sur de nombreux cycles sont ensuite resumees. Puis des examens optiques, aux rayons X et par thermogravimetrie, permettent de proposer une hypothese sur les proprietes de l'oxyde obtenu. Dans la deuxieme partie, les auteurs developpent un calcul prevoyant la marche continue de cellules uniques et en cascades. De ces calculs on tire les elements permettant la realisation de deux cellules de 0,3 et 10 litres. Des resultats de marche continue sur cette derniere cellule, on peut conclure a l'applicabilite de cette methode a l'hydrometallurgie de l'uranium. (auteurs)

  17. Study the oxidation kinetics of uranium using XRD and Rietveld method

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Yanzhi; Guan Weijun; Wang Qinguo; Wang Xiaolin; Lai Xinchun; Shuai Maobing, E-mail: yanzhizh@163.com [China Academy of Engineering Physics, PO Box 919-71, Mianyang, Sichuan, 621900 (China)

    2010-03-15

    The surface oxidation of uranium metal has been studied by X-ray diffraction (XRD) and Rietveld method in the range of 50{approx}300deg. C in air. The oxidation processes are analyzed by XRD to determine the extent of surface oxidation and the oxide structure. The dynamics expression for the formation of UO{sub 2} was derived. At the beginning, the dynamic expression was nonlinear, but switched to linear subsequently for uranium in air and humid oxygen. That is, the growth kinetics of UO{sub 2} can be divided into two stages: nonlinear portion and linear portion. Using the kinetic data of linear portion, the activation energy of reaction between uranium and air was calculated about 46.0 kJ/mol. However the content of oxide as a function of time was linear in humid helium ambience. Contrast the dynamics results, it prove that the absence of oxygen would accelerate the corrosion rate of uranium in the humid gas. We can find that the XRD and Rietveld method are a useful convenient method to estimate the kinetics and thermodynamics of solid-gas reaction.

  18. Machining of uranium and uranium alloys

    International Nuclear Information System (INIS)

    Morris, T.O.

    1981-01-01

    Uranium and uranium alloys can be readily machined by conventional methods in the standard machine shop when proper safety and operating techniques are used. Material properties that affect machining processes and recommended machining parameters are discussed. Safety procedures and precautions necessary in machining uranium and uranium alloys are also covered. 30 figures

  19. Uranium, depleted uranium, biological effects; Uranium, uranium appauvri, effets biologiques

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2001-07-01

    Physicists, chemists and biologists at the CEA are developing scientific programs on the properties and uses of ionizing radiation. Since the CEA was created in 1945, a great deal of research has been carried out on the properties of natural, enriched and depleted uranium in cooperation with university laboratories and CNRS. There is a great deal of available data about uranium; thousands of analyses have been published in international reviews over more than 40 years. This presentation on uranium is a very brief summary of all these studies. (author)

  20. Optimization of dissolution process parameters for uranium ore concentrate powders

    Energy Technology Data Exchange (ETDEWEB)

    Misra, M.; Reddy, D.M.; Reddy, A.L.V.; Tiwari, S.K.; Venkataswamy, J.; Setty, D.S.; Sheela, S.; Saibaba, N. [Nuclear Fuel Complex, Hyderabad (India)

    2013-07-01

    Nuclear fuel complex processes Uranium Ore Concentrate (UOC) for producing uranium dioxide powder required for the fabrication of fuel assemblies for Pressurized Heavy Water Reactor (PHWR)s in India. UOC is dissolved in nitric acid and further purified by solvent extraction process for producing nuclear grade UO{sub 2} powder. Dissolution of UOC in nitric acid involves complex nitric oxide based reactions, since it is in the form of Uranium octa oxide (U{sub 3}O{sub 8}) or Uranium Dioxide (UO{sub 2}). The process kinetics of UOC dissolution is largely influenced by parameters like concentration and flow rate of nitric acid, temperature and air flow rate and found to have effect on recovery of nitric oxide as nitric acid. The plant scale dissolution of 2 MT batch in a single reactor is studied and observed excellent recovery of oxides of nitrogen (NO{sub x}) as nitric acid. The dissolution process is automated by PLC based Supervisory Control and Data Acquisition (SCADA) system for accurate control of process parameters and successfully dissolved around 200 Metric Tons of UOC. The paper covers complex chemistry involved in UOC dissolution process and also SCADA system. The solid and liquid reactions were studied along with multiple stoichiometry of nitrous oxide generated. (author)

  1. Simultaneous determination of a binary mixture: kinetic method for determination of uranium and vanadium

    International Nuclear Information System (INIS)

    Jianhua, W.; Ronghuan, H.

    1993-01-01

    A kinetic method for simultaneous determination of a binary mixture is proposed, and a procedure for simultaneous determination of uranium (IV) and vanadium (IV) is established based on their inductive effect on chromium (VI)-iodide redox reaction in a weak acidic medium. The reaction was monitored by FIA-spectrophotometry using the I 3 - -starch complex as indicator. The calibration graphs are linear for uranium (IV) and vanadium (IV) within the range of 0 ∼ 3.6 μg/ml and 0 ∼ 2.5 μg/ml respectively. Most foreign ions, except for iron (II) and antimony (III), do not interfere with the determination. The uranium and vanadium content in different samples was determined, and the results were satisfactory. (author). 2 tabs., 2 figs., 9 refs

  2. Obtaining of uranium tetrafluoride UF4 by electrodialysis reactive from uranium concentrates

    International Nuclear Information System (INIS)

    Munoz Lay, Danny Mauricio

    2014-01-01

    The generation of uranium fuels has always been a topic worldwide. The uranium fuel manufacturing base is made under very strict parameters of radiological and industrial safety, being a stage called 'nuclear fuel cycle'. In Chile, it is done constant research for fuels. This report focuses primarily on participating in such research; mainly in the production of uranium tetrafluoride (UF 4 ) .The tetrafluoride production is very crucial for the nuclear fuel industry. Its production varies from precipitation in stirred conditions to electrolysis in mercury. However, both processes has shortcomings either in performance and environmental pollution, which is why it is proposed a new method of production based on a friendly process to the environment and easier to operate, the reactive electrodialysis (RED). Electrodialysis is a hybrid reactive process of separation by membranes, cationic and / or anionic, namely, ionic species. In the process, ions are induced to move by an electric potential applied and separated by these membranes, a highly selective physical barrier which allows passage of ions with certain charge, and prevents the passage of oppositely charged ions. And in turn, it is reactive because it forces a chemical reaction, redox, to obtain uranium tetrafluoride (UF 4 ). The results of these experiments show that by reactive electrodialysis, NH 4 UF 5 deposits were obtained. However, calcinating the NH 4 UF 5 to 450 o C, it decomposes to obtain uranium tetrafluoride, UF 4 . The best working conditions were obtained with an electric current of 0.5 (A), 41 o C and a flow of 16 (ml / s) of the electrolyte. It was possible to obtain 5,995 (g) to 3 (h), giving a current efficiency of 71.42%. In turn, working at high temperatures and flow recirculation is possible to operate with a potential difference of 1.7 (V)

  3. Semi-automated uranium analysis by a modified Davies--Gray procedure

    International Nuclear Information System (INIS)

    Swanson, G.C.

    1977-01-01

    To rapidly and reliably determine uranium in fuel materials a semi-automated implementation of the Davies-Gray uranium titration was developed. The Davies-Gray method is essentially a three step procedure. First uranium is reduced quantitatively from +6 valence to +4 valence by excess of iron (II) in strong phosphoric acid in the absence of nitrite. Prior to the uranium reduction nitrite is destroyed by addition of sulfamic acid. In the second step iron (II) is selectively oxidized to iron (III) by nitric acid in the presence of Mo (VI) catalyst. Finally after dilution to reduce phosphate concentration, the uranium is titrated to U (VI) by standard dichromate. The original sluggish colorimetric endpoint determination used by Davies and Gray is seldom used since New Brunswick Laboratory discovered that addition of vanadium (IV) just prior to titration sufficiently improves reaction rate to allow a potentiometric endpoint determination. One of the advantages of the Davies-Gray uranium titration is that it is quite specific for uranium, most common impurity elements do not interfere with the analysis, and specifically high levels of Pu, Th, and Fe are tolerated

  4. Criticality safety considerations for MSRE fuel drain tank uranium aggregation

    International Nuclear Information System (INIS)

    Hollenbach, D.F.; Hopper, C.M.

    1997-01-01

    This paper presents the results of a preliminary criticality safety study of some potential effects of uranium reduction and aggregation in the Molten Salt Reactor Experiment (MSRE) fuel drain tanks (FDTs) during salt removal operations. Since the salt was transferred to the FDTs in 1969, radiological and chemical reactions have been converting the uranium and fluorine in the salt to UF 6 and free fluorine. Significant amounts of uranium (at least 3 kg) and fluorine have migrated out of the FDTs and into the off-gas system (OGS) and the auxiliary charcoal bed (ACB). The loss of uranium and fluorine from the salt changes the chemical properties of the salt sufficiently to possibly allow the reduction of the UF 4 in the salt to uranium metal as the salt is remelted prior to removal. It has been postulated that up to 9 kg of the maximum 19.4 kg of uranium in one FDT could be reduced to metal and concentrated. This study shows that criticality becomes a concern when more than 5 kg of uranium concentrates to over 8 wt% of the salt in a favorable geometry

  5. Nonaqueous chlorination of uranium metal in tributyl phosphate

    International Nuclear Information System (INIS)

    Buchikhin, E.P.; Kuznetsov, A.Yu.; Shatalov, V.V.; Vidanov, V.L.; Chekmarev, A.M.

    2005-01-01

    Low-temperature (30-50 deg C) chlorination of uranium metal in the TBP-TCE-Cl 2 system (TCE = tetrachloroethylene) was studied. Dissolution of uranium in the dipolar aprotic solvent proceeds with formation of U(IV) compounds. The activation energy of this process is 31.24 kJ mol -1 , and relative reaction order with respect to Cl 2 is 2. The effect of TBP concentration on chlorination was examined. The chlorination rate sharply increases at a water content in the TBP-TCE system of 0.2- 0.6 vol % [ru

  6. Uranium removal during low discharge in the Ganges-Brahmaputra mixing zone

    International Nuclear Information System (INIS)

    Carroll, J.; Moore, W.S.

    1993-01-01

    The Ganges-Brahmaputra river system supplies more dissolved uranium to the ocean than any other system in the world (Sarin et al., 1990; Sackett et al., 1973). However, there have been no investigations to determine whether riverine supplies of uranium are altered by geochemical reactions in the river-ocean mixing zone. In this study, uranium and salinity data were collected in the Ganges-Brahmaputra mixing zone during a period of low river discharge. The uranium distribution with salinity shows that in waters <12 ppt salinity, uranium activities are significantly lower than predicted from conservative mixing of river and seawater. This suggests that uranium is being removed within the mixing zone. The behavior of uranium in the Ganges-Brahmaputra is in sharp contrast to its behavior in the Amazon mixing zone where McKee et al. (1978) found uranium activities significantly higher than predicted from conservative mixing. The contrasting behaviors for uranium in these systems are due to the different locations where mixing between river and seawater occurs. For the Amazon, mixing takes place on the continental shelf whereas for the Ganges-Brahmaputra, mixing occurs within shoreline sedimentary environments. The physiochemical processes controlling uranium removal to sediment deposits in the Amazon are partly known. The authors discuss mechanisms which may be removing uranium to suspended and mangrove sediments in the Ganges-Brahmaputra

  7. Aquifer restoration at in-situ leach uranium mines: evidence for natural restoration processes

    International Nuclear Information System (INIS)

    Deutsch, W.J.; Serne, R.J.; Bell, N.E.; Martin, W.J.

    1983-04-01

    Pacific Northwest Laboratory conducted experiments with aquifer sediments and leaching solution (lixiviant) from an in-situ leach uranium mine. The data from these laboratory experiments and information on the normal distribution of elements associated with roll-front uranium deposits provide evidence that natural processes can enhance restoration of aquifers affected by leach mining. Our experiments show that the concentration of uranium (U) in solution can decrease at least an order of magnitude (from 50 to less than 5 ppM U) due to reactions between the lixiviant and sediment, and that a uranium solid, possibly amorphous uranium dioxide, (UO 2 ), can limit the concentration of uranium in a solution in contact with reduced sediment. The concentrations of As, Se, and Mo in an oxidizing lixiviant should also decrease as a result of redox and precipitation reactions between the solution and sediment. The lixiviant concentrations of major anions (chloride and sulfate) other than carbonate were not affected by short-term (less than one week) contact with the aquifer sediments. This is also true of the total dissolved solids level of the solution. Consequently, we recommend that these solution parameters be used as indicators of an excursion of leaching solution from the leach field. Our experiments have shown that natural aquifer processes can affect the solution concentration of certain constituents. This effect should be considered when guidelines for aquifer restoration are established

  8. Nuclear waste viewed in a new light; a synchrotron study of uranium encapsulated in grout.

    Science.gov (United States)

    Stitt, C A; Hart, M; Harker, N J; Hallam, K R; MacFarlane, J; Banos, A; Paraskevoulakos, C; Butcher, E; Padovani, C; Scott, T B

    2015-03-21

    How do you characterise the contents of a sealed nuclear waste package without breaking it open? This question is important when the contained corrosion products are potentially reactive with air and radioactive. Synchrotron X-rays have been used to perform micro-scale in-situ observation and characterisation of uranium encapsulated in grout; a simulation for a typical intermediate level waste storage packet. X-ray tomography and X-ray powder diffraction generated both qualitative and quantitative data from a grout-encapsulated uranium sample before, and after, deliberately constrained H2 corrosion. Tomographic reconstructions provided a means of assessing the extent, rates and character of the corrosion reactions by comparing the relative densities between the materials and the volume of reaction products. The oxidation of uranium in grout was found to follow the anoxic U+H2O oxidation regime, and the pore network within the grout was observed to influence the growth of uranium hydride sites across the metal surface. Powder diffraction analysis identified the corrosion products as UO2 and UH3, and permitted measurement of corrosion-induced strain. Together, X-ray tomography and diffraction provide means of accurately determining the types and extent of uranium corrosion occurring, thereby offering a future tool for isolating and studying the reactions occurring in real full-scale waste package systems. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. NGSI FY15 Final Report. Innovative Sample Preparation for in-Field Uranium Isotopic Determinations

    Energy Technology Data Exchange (ETDEWEB)

    Yoshida, Thomas M. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Meyers, Lisa [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2015-11-10

    Our FY14 Final Report included an introduction to the project, background, literature search of uranium dissolution methods, assessment of commercial off the shelf (COTS) automated sample preparation systems, as well as data and results for dissolution of bulk quantities of uranium oxides, and dissolution of uranium oxides from swipe filter materials using ammonium bifluoride (ABF). Also, discussed were reaction studies of solid ABF with uranium oxide that provided a basis for determining the ABF/uranium oxide dissolution mechanism. This report details the final experiments for optimizing dissolution of U3O8 and UO2 using ABF and steps leading to development of a Standard Operating Procedure (SOP) for dissolution of uranium oxides on swipe filters.

  10. Combustion modeling and kinetic rate calculations for a stoichiometric cyclohexane flame. 1. Major reaction pathways.

    Science.gov (United States)

    Zhang, Hongzhi R; Huynh, Lam K; Kungwan, Nawee; Yang, Zhiwei; Zhang, Shaowen

    2007-05-17

    The Utah Surrogate Mechanism was extended in order to model a stoichiometric premixed cyclohexane flame (P = 30 Torr). Generic rates were assigned to reaction classes of hydrogen abstraction, beta scission, and isomerization, and the resulting mechanism was found to be adequate in describing the combustion chemistry of cyclohexane. Satisfactory results were obtained in comparison with the experimental data of oxygen, major products and important intermediates, which include major soot precursors of C2-C5 unsaturated species. Measured concentrations of immediate products of fuel decomposition were also successfully reproduced. For example, the maximum concentrations of benzene and 1,3-butadiene, two major fuel decomposition products via competing pathways, were predicted within 10% of the measured values. Ring-opening reactions compete with those of cascading dehydrogenation for the decomposition of the conjugate cyclohexyl radical. The major ring-opening pathways produce 1-buten-4-yl radical, molecular ethylene, and 1,3-butadiene. The butadiene species is formed via beta scission after a 1-4 internal hydrogen migration of 1-hexen-6-yl radical. Cascading dehydrogenation also makes an important contribution to the fuel decomposition and provides the exclusive formation pathway of benzene. Benzene formation routes via combination of C2-C4 hydrocarbon fragments were found to be insignificant under current flame conditions, inferred by the later concentration peak of fulvene, in comparison with benzene, because the analogous species series for benzene formation via dehydrogenation was found to be precursors with regard to parent species of fulvene.

  11. Applications of Qualitative Microanalysis to the Determination of Secondary Species Associated with Uranium; Application de la microanalyse qualitative a la determination des especes secondaires d'uranium

    Energy Technology Data Exchange (ETDEWEB)

    Agrinier, H

    1959-02-01

    Microanalytical techniques are described which allow rapid determinations of secondary species associated with uranium. They consist in exposing the constituent elements of the ores by means of characteristic microchemical reactions. Because of their rapidity and the small amount of apparatus needed, these techniques can be used either in the field or in the laboratory. (author) [French] Les techniques de microanalyse decrites dans cet ouvrage permettent la determination rapide des especes secondaires d'uranium. Elles consistent a mettre en evidence les elements constitutifs des mineraux par des reactions microchimiques caracteristiques. En raison de leur rapidite et du peu de materiel qu'elles necessitent, ces techniques peuvent etre utilisees aussi bien sur le terrain qu'au laboratoire. (auteur)

  12. Computational simulation studies of the reduction process of UF4 to metallic uranium

    International Nuclear Information System (INIS)

    Borges, Wesden de Almeida

    2011-01-01

    The production of metallic uranium is essential for production of fuel elements for using in nuclear reactors manufacturing of radioisotopes and radiopharmaceuticals. In IPEN, metallic uranium is produced by magnesiothermical reduction of UF 4 . This reaction is performed in a closed graphite crucible inserted in a sealed metal reactor and no contact with the outside environment. The set is gradually heated in an oven pit, until it reaches the ignition temperature of the reaction (between 600-650 degree C). The modeling of the heating profile of the system can be made using simulation programs by finite element method. Through the thermal profiles in the load, we can have a notion of heating period required for the reaction to occur, allowing the identification of the same group in a greater or smaller yield in metallic uranium production. Thermal properties of UF 4 are estimated, obtaining thermal conductivity and heat capacity using the Flash Laser Method, and for the load UF 4 + Mg, either. The results are compared to laboratory tests to simulate the primary production process. (author)

  13. A study on the electrolytic reduction of uranium oxide in a LiCl-Li2O molten salt

    International Nuclear Information System (INIS)

    Su, J. S.; Hu, J. M.; Hong, S. S.; Jang, D. S.; Park, S. W.

    2003-01-01

    New electrolytic reduction technology was proposed that is based on the integration of metallization of uranium oxide and Li 2 O electrowinning. In this electrolytic reduction reaction, electrolytically reduced Li deposits on cathode and simultaneously reacts with uranium oxides to produce uranium metal showing more than 99% conversion. For the verification of process feasibility, the experiments to obtain basic data on the metallization of uranium oxide, investigation of reaction mechanism, the characteristics of closed recycle of Li 2 O and mass transfer were carried out. This evolutionary electrolytic reduction technology would give benefits over the conventional Li-reduction process improving economic viability such as: avoidance of handling of chemically active Li-LiCl molten salt, increase of metallization yield, and simplification of process

  14. An Alternative Reaction Pathway for Iridium Catalyzed Water Oxidation Driven by CAN

    KAUST Repository

    Bucci, Alberto; Menendez Rodriguez, Gabriel; Bellachioma, Gianfranco; Zuccaccia, Cristiano; Poater, Albert; Cavallo, Luigi; Macchioni, Alceo

    2016-01-01

    The generation of solar fuels by means of a photosynthetic apparatus strongly relies on the development of an efficient water oxidation catalyst (WOC). Cerium ammonium nitrate (CAN) is the most commonly used sacrificial oxidant to explore the potentiality of WOCs. It is usually assumed that CAN has the unique role to oxidatively energize WOCs, making them capable to offer a low energy reaction pathway to transform H2O to O2. Herein we show that CAN might have a much more relevant and direct role in WO, mainly related to the capture and liberation of O–O containing molecular moieties.

  15. An Alternative Reaction Pathway for Iridium Catalyzed Water Oxidation Driven by CAN

    KAUST Repository

    Bucci, Alberto

    2016-06-10

    The generation of solar fuels by means of a photosynthetic apparatus strongly relies on the development of an efficient water oxidation catalyst (WOC). Cerium ammonium nitrate (CAN) is the most commonly used sacrificial oxidant to explore the potentiality of WOCs. It is usually assumed that CAN has the unique role to oxidatively energize WOCs, making them capable to offer a low energy reaction pathway to transform H2O to O2. Herein we show that CAN might have a much more relevant and direct role in WO, mainly related to the capture and liberation of O–O containing molecular moieties.

  16. Possible uranium sources of Streltsovsky uranium ore field

    International Nuclear Information System (INIS)

    Zhang Lisheng

    2005-01-01

    The uranium deposit of the Late Jurassic Streltsovaky caldera in Transbaikalia of Russia is the largest uranium field associated with volcanics in the world, its uranium reserves are 280 000 t U, and it is the largest uranium resources in Russia. About one third of the caldera stratigraphic pile consists of strongly-altered rhyolites. Uranium resources of the Streltsovsky caldera are much larger than any other volcanic-related uranium districts in the world. Besides, the efficiency of hydrothermal alteration, uranium resources appear to result from the juxtaposition of two major uranium sources; highly fractionated peralkaline rhyolites of Jurassic age in the caldera, and U-rich subalkaline granites of Variscan age in the basement in which the major uranium-bearing accessory minerals were metamict at the time of the hydrothermal ore formation. (authors)

  17. Characterization of Uranium Contamination, Transport, and Remediation at Rocky Flats - Across Remediation into Post-Closure

    Science.gov (United States)

    Janecky, D. R.; Boylan, J.; Murrell, M. T.

    2009-12-01

    The Rocky Flats Site is a former nuclear weapons production facility approximately 16 miles northwest of Denver, Colorado. Built in 1952 and operated by the Atomic Energy Commission and then Department of Energy, the Site was remediated and closed in 2005, and is currently undergoing long-term surveillance and monitoring by the DOE Office of Legacy Management. Areas of contamination resulted from roughly fifty years of operation. Of greatest interest, surface soils were contaminated with plutonium, americium, and uranium; groundwater was contaminated with chlorinated solvents, uranium, and nitrates; and surface waters, as recipients of runoff and shallow groundwater discharge, have been contaminated by transport from both regimes. A region of economic mineralization that has been referred to as the Colorado Mineral Belt is nearby, and the Schwartzwalder uranium mine is approximately five miles upgradient of the Site. Background uranium concentrations are therefore elevated in many areas. Weapons-related activities included work with enriched and depleted uranium, contributing anthropogenic content to the environment. Using high-resolution isotopic analyses, Site-related contamination can be distinguished from natural uranium in water samples. This has been instrumental in defining remedy components, and long-term monitoring and surveillance strategies. Rocky Flats hydrology interlinks surface waters and shallow groundwater (which is very limited in volume and vertical and horizontal extent). Surface water transport pathways include several streams, constructed ponds, and facility surfaces. Shallow groundwater has no demonstrated connection to deep aquifers, and includes natural preferential pathways resulting primarily from porosity in the Rocky Flats alluvium, weathered bedrock, and discontinuous sandstones. In addition, building footings, drains, trenches, and remedial systems provide pathways for transport at the site. Removal of impermeable surfaces (buildings

  18. Process for continuous production of metallic uranium and uranium alloys

    Science.gov (United States)

    Hayden, Jr., Howard W.; Horton, James A.; Elliott, Guy R. B.

    1995-01-01

    A method is described for forming metallic uranium, or a uranium alloy, from uranium oxide in a manner which substantially eliminates the formation of uranium-containing wastes. A source of uranium dioxide is first provided, for example, by reducing uranium trioxide (UO.sub.3), or any other substantially stable uranium oxide, to form the uranium dioxide (UO.sub.2). This uranium dioxide is then chlorinated to form uranium tetrachloride (UCl.sub.4), and the uranium tetrachloride is then reduced to metallic uranium by reacting the uranium chloride with a metal which will form the chloride of the metal. This last step may be carried out in the presence of another metal capable of forming one or more alloys with metallic uranium to thereby lower the melting point of the reduced uranium product. The metal chloride formed during the uranium tetrachloride reduction step may then be reduced in an electrolysis cell to recover and recycle the metal back to the uranium tetrachloride reduction operation and the chlorine gas back to the uranium dioxide chlorination operation.

  19. Process for continuous production of metallic uranium and uranium alloys

    Science.gov (United States)

    Hayden, H.W. Jr.; Horton, J.A.; Elliott, G.R.B.

    1995-06-06

    A method is described for forming metallic uranium, or a uranium alloy, from uranium oxide in a manner which substantially eliminates the formation of uranium-containing wastes. A source of uranium dioxide is first provided, for example, by reducing uranium trioxide (UO{sub 3}), or any other substantially stable uranium oxide, to form the uranium dioxide (UO{sub 2}). This uranium dioxide is then chlorinated to form uranium tetrachloride (UCl{sub 4}), and the uranium tetrachloride is then reduced to metallic uranium by reacting the uranium chloride with a metal which will form the chloride of the metal. This last step may be carried out in the presence of another metal capable of forming one or more alloys with metallic uranium to thereby lower the melting point of the reduced uranium product. The metal chloride formed during the uranium tetrachloride reduction step may then be reduced in an electrolysis cell to recover and recycle the metal back to the uranium tetrachloride reduction operation and the chlorine gas back to the uranium dioxide chlorination operation. 4 figs.

  20. Combined quantum mechanical and molecular mechanical reaction pathway calculation for aromatic hydroxylation by p-hydroxybenzoate-3-hydroxylase

    NARCIS (Netherlands)

    Ridder, L.; Mulholland, A.; Rietjens, I.M.C.M.; Vervoort, J.

    1999-01-01

    The reaction pathway for the aromatic 3-hydroxylation of p-hydroxybenzoate by the reactive C4a-hydroperoxyflavin cofactor intermediate in p-hydroxybenzoate hydroxylase (PHBH) has been investigated by a combined quantum mechanical and molecular mechanical (QM/MM) method. A structural model for the

  1. Recoil properties of antimony isotopes produced by the reaction of 570 MeV and 18.2 GeV protons with uranium

    CERN Document Server

    Hagebø, E

    1969-01-01

    Using the method of thick target and thick catchers, the ranges and other recoil properties of 13 (12) antimony isotopes between A = 115 and A = 131 (130) have been measured for the reaction of 570 MeV (18·2 GeV) protons with uranium. The kinetic energies T are almost independent of product mass number at 570 MeV but show a strong dependence at 18·2 GeV, the lightest isotopes having only about half the kinetic energy of the heavy ones. \\\\ \\\\The cascade deposition energies for production of antimony isotopes are almost equal at 570 MeV and 18·2 GeV and fit well to straight lines of the form E$^{∗}$ (A, Z) = E$^{∗}$ (A$_{0}$, Z) + b(A − A$_{0}$). Exceptions are the cascade deposition energies for $^{115}$Sb and $^{116}$Sb which seem to be somewhat too high at 18·2 GeV. By comparison with other work it seems that the slope $b$ of these lines is independent of product element, target and of proton irradiation energy above 450 MeV. \\\\ \\\\If we assume at 570 MeV, that the fissioning nucleus is a uranium ...

  2. Development of uranium milling and conversion

    International Nuclear Information System (INIS)

    Takada, Shingo; Hirono, Shuichiro.

    1983-11-01

    The development and improvement of uranium milling and refining producing uranium tetrafluoride from ores by the wet process, without producing yellowcake as an intermediate product, have been carried out for over ten years with a small pilot plant (50 t-ore/day). In the past several years, a process for converting uranium tetrafluoride into hexafluoride has been developed successfully. To develop the process further, the construction of an integrated milling and conversion pilot plant (200 t-U/year) started in 1979 and was completed in 1981. This new plant has two systems of solvent extraction using tri-noctylamine: one of the systems treats the pregnant solution (uranyl sulphate) by heap-leaching followed by ion exchange, and the other treats the uranyl sulphate solution by dissolving imported yellowcake. The uranium loading solvents from the two systems are stripped with hydrochloric acid solution to obtain the concentrated uranium solution containing 100 g-U/1. Uranyl sulphate solution from the stripping circuit is reduced to a uranous sulphate solution by the electrolytic method. In a reduction cell, uranyl sulphate solution and dilute sulphuric acid are used respectively as catholyte and anolyte, and a cation exchange membrane is used to prevent re-oxidation of the uranous sulphate. In the following hydrofluorination step, uranium tetrafluoride, UF 4 .1-1.2H 2 O (particle size: 50-100μ), is produced continuously as the precipitate in an improved reaction vessel, and this makes it possible to simplify the procedures of liquid-solid separation, drying and granulation. The uranium tetrafluoride is dehydrated by heating to 350 0 C in an inert gas flow. The complete conversion from UF 4 into UF 6 is achieved by a fluidized-bed reactor and a high value of utilization efficiency of fluorine, over 99.9 percent, is attained at about 400 0 C. (author)

  3. Gas Generation from K East Basin Sludges and Irradiated Metallic Uranium Fuel Particles Series III Testing

    International Nuclear Information System (INIS)

    Schmidt, Andrew J.; Delegard, Calvin H.; Bryan, Samuel A.; Elmore, Monte R.; Sell, Rachel L.; Silvers, Kurt L.; Gano, Susan R.; Thornton, Brenda M.

    2003-01-01

    The path forward for managing of Hanford K Basin sludge calls for it to be packaged, shipped, and stored at T Plant until final processing at a future date. An important consideration for the design and cost of retrieval, transportation, and storage systems is the potential for heat and gas generation through oxidation reactions between uranium metal and water. This report, the third in a series (Series III), describes work performed at the Pacific Northwest National Laboratory (PNNL) to assess corrosion and gas generation from irradiated metallic uranium particles (fuel particles) with and without K Basin sludge addition. The testing described in this report consisted of 12 tests. In 10 of the tests, 4.3 to 26.4 g of fuel particles of selected size distribution were placed into 60- or 800-ml reaction vessels with 0 to 100 g settled sludge. In another test, a single 3.72-g fuel fragment (i.e., 7150-mm particle) was placed in a 60 ml reaction vessel with no added sludge. The twelfth test contained only sludge. The fuel particles were prepared by crushing archived coupons (samples) from an irradiated metallic uranium fuel element. After loading the sludge materials (whether fuel particles, mixtures of fuel particles and sludge, or sludge-only) into reaction vessels, the solids were covered with an excess of K Basin water, the vessels closed and connected to a gas measurement manifold, and the vessels back-flushed with inert neon cover gas. The vessels were then heated to a constant temperature. The gas pressures and temperatures were monitored continuously from the times the vessels were purged. Gas samples were collected at various times during the tests, and the samples analyzed by mass spectrometry. Data on the reaction rates of uranium metal fuel particles with water as a function of temperature and particle size were generated. The data were compared with published studies on metallic uranium corrosion kinetics. The effects of an intimate overlying sludge layer

  4. Observation of even-parity autoionization states of uranium by three-colour photoionization optogalvanic spectroscopy in U–Ne hollow cathode discharges

    International Nuclear Information System (INIS)

    Mandal, P.K.; Seema, A.U.; Das, R.C.; Shah, M.L.; Dev, Vas; Suri, B.M.

    2013-01-01

    Three-colour three-step photoionization spectroscopy of uranium has been performed in a U–Ne hollow cathode discharge tube by temporally resolving three-colour photoionization optogalvanic (PIOG) signal from the normal optogalvanic (OG) signal using three tunable pulsed dye lasers. U–Ne hollow cathode discharge tube has been used as a source of uranium atomic vapours and photoionization detector. Using this technique, photoionization spectra of uranium have been investigated systematically in the energy region 52,150–52,590 cm −1 , through three different excitation pathways, originating from its ground state, 0 cm −1 ( 5 L o 6 ). By analysing the three-colour photoionization spectra sixty new even-parity autoionization resonances of uranium have been identified and their probable total angular momentum (J) values have been assigned according to the J-momentum selection rule. The J-value of five autoionization resonances, which have been observed either through all three excitation pathways or through two different excitation pathways where J-value of the second excited levels differs by two, has been assigned uniquely. -- Highlights: ► Three-colour photoionization optogalvanic spectroscopy of uranium was performed in a U–Ne hollow cathode discharge tube. ► Hollow cathode discharge tube was used as a source of atomic vapour and laser ionisation detector. ► Uranium photoionization spectra were investigated through three different three-colour photoionization schemes. ► Sixty new even-parity autoionization levels of uranium were identified. ► J-value of five autoionization levels was assigned uniquely

  5. Environmental impact of uranium mining and milling: an American view

    International Nuclear Information System (INIS)

    Momeni, M.H.

    1981-01-01

    The radiation dose rates to man from uranium milling activities are discussed. The sources of radiation, the radioisotopes involved, and the environmental exposure pathways are described. Risks of cancer to exposed individuals are presented and recommendations made for mitigation of contamination

  6. Theoretical study of adsorption of water vapor on surface of metallic uranium

    CERN Document Server

    Xiong Bi Tao; Xue Wei Dong; Zhu Zheng He; Jiang Gang; Wang Hong Yan; Gao Tao

    2002-01-01

    According to the experimental data, there is an intermediate substance that formed in the initial stage of oxidation reaction when water vapor is absorbed onto the metallic uranium. The minimum energy of UOH sub 2 witch C sub 2 subupsilon configuration is obtained in the state of sup 5 A sub 1 by B3LYP method of the density function theory (DFT), which is consistent with that by statics of atoms and molecules reaction (AMRS) and group theory. The results from calculations indicate that the adsorption of water vapor on the metallic uranium is an exothermic reaction and that the adsorbed amount decreases with the elevated temperatures. The adsorptive heat at 1 atm is -205.4747 kJ centre dot mol sup - sup 1 , which indicates a typical chemical adsorption

  7. Preparation and Characterization of Uranium Oxides in Support of the K Basin Sludge Treatment Project

    International Nuclear Information System (INIS)

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2008-01-01

    Uraninite (UO2) and metaschoepite (UO3-2H2O) are the uranium phases most frequently observed in K Basin sludge. Uraninite arises from the oxidation of uranium metal by anoxic water and metaschoepite arises from oxidation of uraninite by atmospheric or radiolytic oxygen. Studies of the oxidation of uraninite by oxygen to form metaschoepite were performed at 21 C and 50 C. A uranium oxide oxidation state characterization method based on spectrophotometry of the solution formed by dissolving aqueous slurries in phosphoric acid was developed to follow the extent of reaction. This method may be applied to determine uranium oxide oxidation state distribution in K Basin sludge. The uraninite produced by anoxic corrosion of uranium metal has exceedingly fine particle size (6 nm diameter), forms agglomerates, and has the formula UO2.004 ± 0.007; i.e., is practically stoichiometric UO2. The metaschoepite particles are flatter and wider when prepared at 21 C than the particles prepared at 50 C. These particles are much smaller than the metaschoepite observed in prolonged exposure of actual K Basin sludge to warm moist oxidizing conditions. The uraninite produced by anoxic uranium metal corrosion and the metaschoepite produced by reaction of uraninite aqueous slurries with oxygen may be used in engineering and process development testing. A rapid alternative method to determine uranium metal concentrations in sludge also was identified.

  8. Uranium Sequestration by Aluminum Phosphate Minerals in Unsaturated Soils

    International Nuclear Information System (INIS)

    Jerden, James L. Jr.

    2007-01-01

    A mineralogical and geochemical study of soils developed from the unmined Coles Hill uranium deposit (Virginia) was undertaken to determine how phosphorous influences the speciation of uranium in an oxidizing soil/saprolite system typical of the eastern United States. This paper presents mineralogical and geochemical results that identify and quantify the processes by which uranium has been sequestered in these soils. It was found that uranium is not leached from the saturated soil zone (saprolites) overlying the deposit due to the formation of a sparingly soluble uranyl phosphate mineral of the meta-autunite group. The concentration of uranium in the saprolites is approximately 1000 mg uranium per kg of saprolite. It was also found that a significant amount of uranium was retained in the unsaturated soil zone overlying uranium-rich saprolites. The uranium concentration in the unsaturated soils is approximately 200 mg uranium per kg of soil (20 times higher than uranium concentrations in similar soils adjacent to the deposit). Mineralogical evidence indicates that uranium in this zone is sequestered by a barium-strontium-calcium aluminum phosphate mineral of the crandallite group (gorceixite). This mineral is intimately inter-grown with iron and manganese oxides that also contain uranium. The amount of uranium associated with both the aluminum phosphates (as much as 1.4 weight percent) has been measured by electron microprobe micro-analyses and the geochemical conditions under which these minerals formed has been studied using thermodynamic reaction path modeling. The geochemical data and modeling results suggest the meta-autunite group minerals present in the saprolites overlying the deposit are unstable in the unsaturated zone soils overlying the deposit due to a decrease in soil pH (down to a pH of 4.5) at depths less than 5 meters below the surface. Mineralogical observations suggest that, once exposed to the unsaturated environment, the meta-autunite group

  9. Experimental leaching of uranium from tuffaceous rocks

    International Nuclear Information System (INIS)

    Goodell, P.C.; Trentham, R.C.

    1980-07-01

    The premise to be tested in this work is that felsic volcanic rocks particularly ash-flow tuffs, can serve as source rocks for certain uranium deposits. The applicability of this idea to several geologic environments is investigated. A genetic model is developed dealing with the behavior of uranium during and subsequent to ash-flow tuff deposition. It is based upon previously described investigations, geologic logic, data presented here, and speculation. Ash-flow tuff sequences described in the literature show significant alkali element variation, particularly in thick tuff units. Some variation is attributed to initial magma variations, whereas additional change may be produced during cooling and degassing of the tuff. Uranium variations have been documented in tuff sequences which are assumed to represent magmatic compositions. Uranium may be released during the initial degassing, during hydrothermal alteration, and/or during later diagenesis. Experimental studies have been designed and carried out to simulate natural leaching conditions such as might occur during diagenesis. Synthetic ground waters have been pumped through pulverized uraniferous vitrophyres. Major and minor element contents have been determined. The most significant chemical changes take place quickly, within a matter of days. Several starting and product leachant solutions were analyzed fluorimetrically for uranium. They show significant increases in uranium contents, from less than 1 ppB at the start to greater than 10 ppB maximu. Such leachant solutions might be significant transport agents of uranium given geologic time. Leaching at low temperatures appears to involve a thin surface reaction and diffusion layer. Both dissolution and ion exchange influence the leachant composition. It is also concluded that glassy ash-flow tuffs may serve as uranium source rocks during low temperature diagenetic changes

  10. Device for the chlorinating volatization of thorium and/or uranium

    International Nuclear Information System (INIS)

    Laser, M.; Bohnenstingl, J.; Fischer, E.

    1976-01-01

    The invention relates to a device for the chlorinating volatization of nuclear fuel or breeding elements, preferably of thorium or uranium carbide and/or thorium or uranium oxide. A cupola furnace serves as reaction vessel, being connected to the condenser via a reactiongas pipe. In the interior of the cupola furnace, a tube is arranged consisting of porous graphite and heatable by direct current transfer, the tube being surrounded by a casing of ceramic material (sillimanite or rotosile). The chlorine gas is introduced into the cupola furnace via an additional socket. The gaseous reaction products penetrate the porous wall of the inner tube and enter the condenser first via the space between casing and inner tube and then via the reaction-gas pipe. The condenser consists of a gas-permeable tube and a surrounding tube, the space between being passed by the coolant gas. The maximum grain size of the ground pellets should be smaller than 300 μm. (HPH) [de

  11. Uranium isotope separation using styrene cation exchangers

    International Nuclear Information System (INIS)

    Kahovec, J.

    1980-01-01

    The separation of 235 U and 238 U isotopes is carried out either by simple isotope exchange in the system uranium-cation exchanger (sulphonated styrene divinylbenzene resin), or by combination of isotope exchange in a uranium-cation exchanger (Dowex 50, Amberlite IR-120) system and a chemical reaction. A review is presented of elution agents used, the degree of cation exchanger cross-linking, columns length, and 235 U enrichment. The results are described of the isotope effect study in a U(IV)-U(VI)-cation exchanger system conducted by Japanese and Romanian authors (isotope exchange kinetics, frontal analysis, reverse (indirect) frontal analysis). (H.S.)

  12. Pathway analysis concepts for radiological impact assessment

    International Nuclear Information System (INIS)

    Moroney, J.R.

    1992-06-01

    The concepts underlying exposure pathways analysis are outlined with reference to the features of the two broad types of radionuclide transport models now in use - dynamic and steady-state - and the methods for constructing and developing them. By way of illustration, representative radiation doses are estimated for the four main exposure pathways likely to be involved in the land application of effluent water from Retention Pond 2 of Ranger Uranium Mines. These include: external irradiation by 226 Ra and natural uranium (Un at) in soil, ingestion of 226 Ra and Un at in food, inhalation of 222 Rn daughter products from 226 Rn in soil, and inhalation of 226 Ra and Un at in airborne dust resuspended from soil. Consideration has been given to local residents pursuing a traditional lifestyle on conclusion of the land application program. Because of the possible importance of the contribution from resuspended dust, currently available data are explored in refining the methodology for the pathway and developing a more appropriate model for it. 37 refs., 9 tabs., 6 figs

  13. Absorption spectra and cyclic voltammograms of uranium species in molten lithium molybdate-sodium molybdate eutectic at 550 C

    International Nuclear Information System (INIS)

    Nagai, T.; Fukushima, M.; Myochin, M.; Uehara, A.; Fujii, T.; Yamana, H.; Sato, N.

    2011-01-01

    Absorption spectra of uranium species dissolved in molten lithium molybdate.sodium molybdate eutectic of 0.51Li 2 MoO 4 -0.49Na 2 MoO 4 mixture at 550 C were measured by UV/Vis/NIR spectrophotometry, and their redox reactions were investigated by cyclic voltammetry. We found that the major ions of uranium species dissolved in the melt were uranyl penta-valent. After purging dry oxygen gas into the melt, pentavalent species were oxidized to the uranyl hexa-valent. In the cyclic voltammetry of the melt without uranium species, it was confirmed that the lithium-sodium molybdenum oxide compounds were deposited on the working electrode at the negative potential and the lithium molybdenum oxide compounds were deposited on the counter electrode at positive potential. When UO 2 was dissolved into the melt, the reductive reaction of the uranium species was observed at the reductive potential of the pure melt. This suggests that the uranium species dissolved in the melts could be recovered as mixed uranium-molybdenum oxides by electrolysis. (orig.)

  14. Final Report - Elucidating Bioreductive Transformations within Physically Complex Media: Impact on the Fate and Transport of Uranium and Chromium

    International Nuclear Information System (INIS)

    Benner, Shawn G.; Fendorf, Scott

    2009-01-01

    In situ stabilization (inclusive of natural attenuation) of toxic metals and radionuclides is an attractive approach for remediating many contaminated DOE sites. By immobilizing toxic metals and radionuclides in place, the removal of contaminated water to the surface for treatment as well as the associated disposal costs are avoided. To enhance in situ remediaton, microbiological reductive stabilization of contaminant metals has been, and continues to be, actively explored. It is likely that surface and subsurface microbial activity can alter the redox state of toxic metals and radionuclides, either directly or indirectly, so they are rendered immobile. Furthermore, anaerobic bacterial metabolic products will help to buffer pulses of oxidation, typically from fluxes of nitrate or molecular oxygen, and thus may stabilize reduced contaminants from oxidative mobilization. Uranium and chromium are two elements of particular concern within the DOE complex that, owing to their abundance and toxicity, appear well suited for biologically mediated reductive stabilization. Subsurface microbial activity can alter the redox state of toxic metals and radionuclides, rending them immobile. Imparting an important criterion on the probability that contaminants will undergo reductive stabilization, however, is the chemical and physical heterogeneity of the media. Our research first examined microbially induced transformation of iron (hydr)oxide minerals and their impact on contaminant attenuation. We revealed that in intricate cascade of geochemical reactions is induced by microbially produced Fe(II), and that during transformation contaminants such as U(VI) can be incorporated into the structure, and a set of Fe(II) bearing solids capable of reducing Cr(VI) and stabilizing resulting Cr(III). We also note, however, that common subsurface constituents such as phosphate can modify iron oxide transformation pathways and thus impact contaminant sequestration - 'affecting both Cr and U

  15. The precipitation of double fluoride salts of uranium

    Energy Technology Data Exchange (ETDEWEB)

    Muir, C. W.A.

    1963-02-15

    Bench-scale kinetic tests were conducted to study the reduction and precipitation reactions involved in the preparation of ammonium uranous fluoride from high-purity uranyl nitrate solutions. Sulphur dioxide and formic acid were used to form the active reducing agent, nascent hyposulphite ion. The reduction was affected in the presence of ammonium fluoride, resulting in the precipitation of the highly insoluble double salt. It was found that uranium was precipituted at a constant rate throughout the progress of the reaction. It is postulated that the reducing agent was continuously regenerated, and that this reaction was rate controlling. As a result of this study, a reaction mechanism is proposed. (auth)

  16. A Study on the Electrolytic Reduction Mechanism of Uranium Oxide in a LiCl-Li2O Molten Salt

    International Nuclear Information System (INIS)

    Oh, Seung Chul; Hur, Jin Mok; Seo, Chung Seok; Park, Seong Won

    2003-01-01

    This study proposed a new electrolytic reduction technology that is based on the integration of simultaneous uranium oxide metallization and Li 2 O electrowinning. In this electrolytic reduction reaction, electrolytically reduced Li deposits on cathode and simultaneously reacts with uranium oxides to produce uranium metal showing more than 99% conversion. For the verification of process feasibility, the experiments to obtain basic data on the metallization of uranium oxide, investigation of reaction mechanism, the characteristics of closed recycle of Li 2 O and mass transfer were carried out. This evolutionary electrolytic reduction technology would give benefits over the conventional Li-reduction process improving economic viability such as: avoidance of handling of chemically active Li-LiCl molten salt increase of metallization yield, and simplification of process.

  17. Technology of uranium recovery from wet-process phosphoric acid

    Energy Technology Data Exchange (ETDEWEB)

    Inoue, Katsutoshi [Saga Univ. (Japan). Faculty of Science and Engineering; Nakashio, Fumiyuki

    1982-12-01

    Rock phosphate contains from 0.005 to 0.02 wt.% of uranium. Though the content is a mere 5 to 10 % of that in uranium ore, the total recovery of uranium is significant since it is used for fertilizer manufacture in a large quantity. Wet-process phosphoric acid is produced by the reaction of rock phosphate with sulfuric acid. The recovery of uranium from this phosphoric acid is mostly by solvent extraction at present. According to U/sup 4 +/ or UO/sub 2//sup 2 +/ as the form of its existence, the technique of solvent extraction differs. The following matters are described: processing of rock phosphate; recovery techniques including the extraction by OPPA-octyl pyrophosphoric acid for U/sup 4 +/, and by mixed DEHPA-Di-(2)-ethylhexyl phosphoric acid and TOPO-tryoctyl phosphine oxide for UO/sub 2//sup 2 +/, and by OPAP-octylphenyl acid phosphate for U/sup 4 +/; the recent progress of the technology as seen in patents.

  18. Reaction pathways of biomass-derived oxygenates on noble metal surfaces

    Science.gov (United States)

    McManus, Jesse R.

    As the global demand for energy continues to rise, the environmental concerns associated with increased fossil fuel consumption have motivated the use of biomass as an alternative, carbon-renewable energy feedstock. Controlling reactive chemistry of the sugars that comprise biomass through the use of catalysis becomes essential in effectively producing green fuels and value-added chemicals. Recent work on biomass conversion catalysts have demonstrated the efficacy of noble metal catalyst systems for the reforming of biomass to hydrogen fuel, and the hydrodeoxygenation of biomass-derived compounds to value-added chemicals. In particular, Pt and Pd surfaces have shown considerable promise as reforming catalysts in preliminary aqueous phase reforming studies. It becomes important to understand the mechanisms by which these molecules react on the catalyst surfaces in order to determine structure-activity relationships and bond scission energetics as to provide a framework for engineering more active and selective catalysts. Fundamental surface science techniques provide the tools to do this; however, work in this field has been so far limited to simple model molecules like ethanol and ethylene glycol. Herein, temperature programmed desorption and high resolution electron energy loss spectroscopy are utilized in an ultra-high vacuum surface science study of the biomass-derived sugar glucose on Pt and Pd single crystal catalysts. Overall, it was determined that the aldehyde function of a ring-open glucose molecule plays an integral part in the initial bonding and reforming reaction pathway, pointing to the use of aldoses glycolaldehyde and glyceraldehyde as the most appropriate model compounds for future studies. Furthermore, the addition of adatom Zn to a Pt(111) surface was found to significantly decrease the C-H and C-C bond scission activity in aldehyde containing compounds, resulting in a preferred deoxygenation pathway in opposition to the decarbonylation pathway

  19. Electrode Reaction Pathway in Oxide Anode for Solid Oxide Fuel Cells

    Science.gov (United States)

    Li, Wenyuan

    the electrolyte to change 3PB kinetics. Compared to Ni, Co doping activates the bulk oxygen more significantly, promoting the reaction at 2PB. The active surface reaction zone is found to be enlarged by the electrolyte with high oxygen activity (SSZ vs. YSZ) when charge transfer is one of the RDS. Due to the larger exchange current for charge transfer in 3PB with SSZ electrolyte, the adsorption gradient zone is broadened, leading to enhanced surface reaction kinetics. The potential application of such finding is demonstrated on SSZ/YSZ/SSZ sandwich, showing largely improved electrode performance, opening a wide door for the utilization of electrolytes that are too expensive, fragile or instable to be used before. The bulk path way in 2PB reaction can be affected by overpotential in terms of local vacancy concentration, built-in electrical field and stability. It is proven that an uneven distribution of lattice oxygen is established under operation conditions with overpotential by both qualitative analysis and analytic solution. An electrostatic field force is present besides the concentration gradient in the anode lattice to control the motion of oxygen ions. Compared to the usual estimation based on chemical diffusion mechanism, the real deviation of ionic defects concentration under polarization from the equilibrium state near electrode/electrolyte interface is smaller with the built-in electrical field. The overpotential is demonstrated to be able to open up or shut down the bulk pathway depending on the ionic defects of electrodes. The analysis on the bulk pathway in terms of local charged species and various potentials provides new insight in anion diffusion and electrode stability.

  20. Recovery of uranium from crude uranium tetrafluoride

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, S K; Bellary, M P; Keni, V S [Chemical Engineering Division, Bhabha Atomic Research Centre, Mumbai (India)

    1994-06-01

    An innovative process has been developed for recovery of uranium from crude uranium tetrafluoride cake. The process is based on direct dissolution of uranium tetrafluoride in nitric acid in presence of aluminium hydroxide and use of solvent extraction for removal of fluorides and other bulk impurities to make uranium amenable for refining. It is a simple process requiring minimum process step and has advantage of lesser plant corrosion. This process can be applied for processing of uranium tetrafluoride generated from various sources like uranium by-product during thorium recovery from thorium concentrate, first stage product of uranium recovery from phosphoric acid by OPPA process and off grade uranium tetrafluoride material. The paper describes the details of the process developed and demonstrated on bench and pilot scale and its subsequent modification arising out of bulky solid waste generation. The modified process uses a lower quantity of aluminium hydroxide by allowing a lower dissolution of uranium per cycle and recycles the undissolved material to the next cycle, maintaining the overall recovery at high level. This innovation has reduced the solid waste generated by a factor of four at the cost of a slightly larger dissolution vessel and its increased corrosion rate. (author). 4 refs., 1 fig., 3 tabs.

  1. Recovery of uranium from crude uranium tetrafluoride

    International Nuclear Information System (INIS)

    Ghosh, S.K.; Bellary, M.P.; Keni, V.S.

    1994-01-01

    An innovative process has been developed for recovery of uranium from crude uranium tetrafluoride cake. The process is based on direct dissolution of uranium tetrafluoride in nitric acid in presence of aluminium hydroxide and use of solvent extraction for removal of fluorides and other bulk impurities to make uranium amenable for refining. It is a simple process requiring minimum process step and has advantage of lesser plant corrosion. This process can be applied for processing of uranium tetrafluoride generated from various sources like uranium by-product during thorium recovery from thorium concentrate, first stage product of uranium recovery from phosphoric acid by OPPA process and off grade uranium tetrafluoride material. The paper describes the details of the process developed and demonstrated on bench and pilot scale and its subsequent modification arising out of bulky solid waste generation. The modified process uses a lower quantity of aluminium hydroxide by allowing a lower dissolution of uranium per cycle and recycles the undissolved material to the next cycle, maintaining the overall recovery at high level. This innovation has reduced the solid waste generated by a factor of four at the cost of a slightly larger dissolution vessel and its increased corrosion rate. (author)

  2. 1. Mono([8]annulene)Uranium(4) half-sandwich complexes, 2. Novel syntheses of symmetrically substituted cyclooctatetetraenes

    International Nuclear Information System (INIS)

    Boussie, T.R.

    1991-10-01

    A reproducible, high-yield synthesis of mono([8]annulene)uranium(4)dichloride (1) is reported, along with the X-ray crystal structural of the bis(pyridine) adduct. Metathesis reactions of the half-sandwich complex 1 with a variety of simple alkyl and alkoxy reagents failed to generate any isolable mono-ring complexes. Reactions of 1 with polydentate, delocalized anions did produce stable derivatives, including mono([8]annulene)uranium(4)bis(acetylacetonate) (4). An X-ray crystal structure of 4 is reported

  3. 1. Mono([8]annulene)Uranium(4) half-sandwich complexes, 2. Novel syntheses of symmetrically substituted cyclooctatetetraenes

    Energy Technology Data Exchange (ETDEWEB)

    Boussie, Thomas Richard [Univ. of California, Berkeley, CA (United States)

    1991-10-01

    A reproducible, high-yield synthesis of mono([8]annulene)uranium(4)dichloride (1) is reported, along with the X-ray crystal structural of the bis(pyridine) adduct. Metathesis reactions of the half-sandwich complex 1 with a variety of simple alkyl and alkoxy reagents failed to generate any isolable mono-ring complexes. Reactions of 1 with polydentate, delocalized anions did produce stable derivatives, including mono([8]annulene)uranium(4)bis(acetylacetonate) (4). An X-ray crystal structure of 4 is reported.

  4. 1. Mono((8)annulene)Uranium(4) half-sandwich complexes, 2. Novel syntheses of symmetrically substituted cyclooctatetetraenes

    Energy Technology Data Exchange (ETDEWEB)

    Boussie, T.R.

    1991-10-01

    A reproducible, high-yield synthesis of mono((8)annulene)uranium(4)dichloride (1) is reported, along with the X-ray crystal structural of the bis(pyridine) adduct. Metathesis reactions of the half-sandwich complex 1 with a variety of simple alkyl and alkoxy reagents failed to generate any isolable mono-ring complexes. Reactions of 1 with polydentate, delocalized anions did produce stable derivatives, including mono((8)annulene)uranium(4)bis(acetylacetonate) (4). An X-ray crystal structure of 4 is reported.

  5. Sulphatising roasting of a Greenlandic uranium ore, reactivity of minerals and recovery

    International Nuclear Information System (INIS)

    Gamborg Hansen, J.K.

    1977-03-01

    Uranium in the lujavrite ore from Kvanefjeld, South Greenland, can be solubilised by sulphatising roasting at 700degC. The reactivity of various lujavrite minerals in the roasting process and the mechanism of the reaction were investigated by X-ray diffraction, optical microscopy, electron microprobe, thermal analysis, Moessbauer and infrared spectroscopy. Soluble sulphates are formed on the surface of the grains; an outer zone of the grains is transformed; usually a core remains unchanged. Variations in uranium recovery can be explained by variations in the contents of the uranium-bearing minerals, steenstrupine and uranium-containing pigmentary material (altered Zr containing silicate minerals), and in the degree of alteration os steenstrupine. Characterization of these minerals required many qualitative and a few quantitative electron microprobe analyses. (author)

  6. The influence of surface morphology and oxide microstructure on the nucleation and growth of uranium hydride on alpha uranium

    International Nuclear Information System (INIS)

    Hanrahan, R.J. Jr.; Hawley, M.E.; Brown, G.W.

    1998-01-01

    While the bulk kinetics of the uranium-hydrogen reaction are well understood, the mechanisms underlying the initial nucleation of uranium hydride on uranium remain controversial. In this study, the authors have employed environmental cell optical microscopy, Scanning Electron Microscopy (SEM) and Atomic Force Microscopy, (AFM) in an attempt to relate the structure of the surface and the microstructure of the substrate with the susceptibility and site of hydride nucleation. Samples have been investigated with varying grain size, inclusion (carbide) concentration, and thermal history. There is a clear correlation to heat treatment immediately prior to hydrogen exposure. Susceptibility to hydride formation also appears to be related to impurities in the uranium. The oxidized surface is very complex, exhibiting wide variations in thickness and topography between samples, between grains in the same sample, and within individual grains. It is, however, very difficult to relate this fine scale variability to the relatively sparse hydride initiation sites. Therefore, the surface oxide layer itself does not appear to control the sites where hydride attack is initiated, although it must play a role in the induction period prior to hydride initiation

  7. The influence of surface morphology and oxide microstructure on the nucleation and growth of uranium hydride on alpha uranium

    Energy Technology Data Exchange (ETDEWEB)

    Hanrahan, R.J. Jr.; Hawley, M.E.; Brown, G.W. [Los Alamos National Lab., NM (United States). Materials Science and Technology Div.

    1998-12-31

    While the bulk kinetics of the uranium-hydrogen reaction are well understood, the mechanisms underlying the initial nucleation of uranium hydride on uranium remain controversial. In this study the authors have employed environmental cell optical microscopy, Scanning Electron Microscopy (SEM) and Atomic Force Microscopy, (AFM) in an attempt to relate the structure of the surface and the microstructure of the substrate with the susceptibility and site of hydride nucleation. Samples have been investigated with varying grain size, inclusion (carbide) concentration, and thermal history. There is a clear correlation to heat treatment immediately prior to hydrogen exposure. Susceptibility to hydride formation also appears to be related to impurities in the uranium. The oxidized surface is very complex, exhibiting wide variations in thickness and topography between samples, between grains in the same sample, and within individual grains. It is, however, very difficult to relate this fine scale variability to the relatively sparse hydride initiation sites. Therefore, the surface oxide layer itself does not appear to control the sites where hydride attack is initiated, although it must play a role in the induction period prior to hydride initiation.

  8. The influence of surface morphology and oxide microstructure on the nucleation and growth of uranium hydride on alpha uranium

    Energy Technology Data Exchange (ETDEWEB)

    Hanrahan, R.J. Jr.; Hawley, M.E.; Brown, G.W.

    1998-12-31

    While the bulk kinetics of the uranium-hydrogen reaction are well understood, the mechanisms underlying the initial nucleation of uranium hydride on uranium remain controversial. In this study, the authors have employed environmental cell optical microscopy, Scanning Electron Microscopy (SEM) and Atomic Force Microscopy, (AFM) in an attempt to relate the structure of the surface and the microstructure of the substrate with the susceptibility and site of hydride nucleation. Samples have been investigated with varying grain size, inclusion (carbide) concentration, and thermal history. There is a clear correlation to heat treatment immediately prior to hydrogen exposure. Susceptibility to hydride formation also appears to be related to impurities in the uranium. The oxidized surface is very complex, exhibiting wide variations in thickness and topography between samples, between grains in the same sample, and within individual grains. It is, however, very difficult to relate this fine scale variability to the relatively sparse hydride initiation sites. Therefore, the surface oxide layer itself does not appear to control the sites where hydride attack is initiated, although it must play a role in the induction period prior to hydride initiation.

  9. Probabilistic pathway construction.

    Science.gov (United States)

    Yousofshahi, Mona; Lee, Kyongbum; Hassoun, Soha

    2011-07-01

    Expression of novel synthesis pathways in host organisms amenable to genetic manipulations has emerged as an attractive metabolic engineering strategy to overproduce natural products, biofuels, biopolymers and other commercially useful metabolites. We present a pathway construction algorithm for identifying viable synthesis pathways compatible with balanced cell growth. Rather than exhaustive exploration, we investigate probabilistic selection of reactions to construct the pathways. Three different selection schemes are investigated for the selection of reactions: high metabolite connectivity, low connectivity and uniformly random. For all case studies, which involved a diverse set of target metabolites, the uniformly random selection scheme resulted in the highest average maximum yield. When compared to an exhaustive search enumerating all possible reaction routes, our probabilistic algorithm returned nearly identical distributions of yields, while requiring far less computing time (minutes vs. years). The pathways identified by our algorithm have previously been confirmed in the literature as viable, high-yield synthesis routes. Prospectively, our algorithm could facilitate the design of novel, non-native synthesis routes by efficiently exploring the diversity of biochemical transformations in nature. Copyright © 2011 Elsevier Inc. All rights reserved.

  10. Analytical method of uranium (IV) and uranium (VI) in uranium ores and uranium-bearing rocks

    International Nuclear Information System (INIS)

    Shen Zhuqin; Zheng Yongfeng; Li Qingzhen; Zhong Miaolan; Gu Dingxiang

    1995-11-01

    The best conditions for keeping the original valences of uranium during the dissolution and separation procedure of geological samples (especially those micro uranium-bearing rock) were studied. With the exist of high concentration protectants, the sample was decomposed with concentration HF at 40 +- 5 degree C. The U(VI) was dissolved completely and formed stable complex UO 2 F 2 , the U(IV) was precipitated rapidly and carried by carrier. Quantitative separation was carried out immediately with suction. The decomposition of sample and separation of solid/liquid phases was completed within two minutes. After separation, the U(IV) and U(VI) were determined quantitatively with laser fluorescence or voltametry respectively according to the uranium content. The limit of detection for this method is 0.7 μg/g, RSD is 10.5%, the determinate range of uranium is 2 x 10 -6 ∼10 -1 g/g. The uranium contents and their valence state ratio were measured for more than one hundred samples of sand stone and granite, the accuracy and precision of these results are satisfactory for uranium geological research. (12 tabs.; 11 refs.)

  11. Obtention of powdered UO{sub 2} oxide by water vapor action on calcium-reduced uranium; Obtention d'oxyde UO{sub 2} pulverulent par action de la vapeur d'eau sur l'uranium calciothermique

    Energy Technology Data Exchange (ETDEWEB)

    Moreau, Claude; Barnoud, Louis [Commissariat a l' energie atomique et aux energies alternatives - CEA, Centre d' etudes nucleaires de Grenoble (France)

    1960-07-01

    The oxidation method used allows to control and to easily vary the reaction kinetics in order to obtain oxidized uranium samples with predetermined UO{sub 2} contents. The solid reagent, made of spherical uranium grains of constant size, is an interesting material for the application of heterogeneous kinetic principles. An experimental continuation of this study is expected. Reprint of a paper published in Comptes rendus des seances de l'Academie des Sciences, t. 250, p. 1495-1497, sitting of 22 February 1960 [French] La methode d'oxydation utilisee permet de controler, et de faire varier facilement la vitesse de reaction de facon a obtenir des echantillons d'uranium oxydes en UO{sub 2} a des teneurs predeterminees. En outre le reactif solide, compose de grains d'uranium spheriques de meme taille constitue un materiau interessant pour l'application des principes de la cinetique heterogene. Un prolongement experimental de cette etude est envisage. Reproduction d'un article publie dans les Comptes rendus des seances de l'Academie des Sciences, t. 250, p. 1495-1497, seance du 22 fevrier 1960.

  12. Precise coulometric titration of uranium in a high-purity uranium metal and in uranium compounds

    International Nuclear Information System (INIS)

    Tanaka, Tatsuhiko; Yoshimori, Takayoshi

    1975-01-01

    Uranium in uranyl nitrate, uranium trioxide and a high-purity uranium metal was assayed by the coulometric titration with biamperometric end-point detection. Uranium (VI) was reduced to uranium (IV) by solid bismuth amalgam in 5M sulfuric acid solution. The reduced uranium was reoxidized to uranium (VI) with a large excess of ferric ion at a room temperature, and the ferrous ion produced was titrated with the electrogenerated manganese(III) fluoride. In the analyses of uranium nitrate and uranium trioxide, the results were precise enough when the error from uncertainty in water content in the samples was considered. The standard sample of pure uranium metal (JAERI-U4) was assayed by the proposed method. The sample was cut into small chips of about 0.2g. Oxides on the metal surface were removed by the procedure shown by National Bureau of Standards just before weighing. The mean assay value of eleven determinations corrected for 3ppm of iron was (99.998+-0.012) % (the 95% confidence interval for the mean), with a standard deviation of 0.018%. The proposed coulometric method is simple and permits accurate and precise determination of uranium which is matrix constituent in a sample. (auth.)

  13. 31 CFR 540.317 - Uranium feed; natural uranium feed.

    Science.gov (United States)

    2010-07-01

    ... 31 Money and Finance: Treasury 3 2010-07-01 2010-07-01 false Uranium feed; natural uranium feed... (Continued) OFFICE OF FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.317 Uranium feed; natural uranium feed. The...

  14. Uranium exploration

    International Nuclear Information System (INIS)

    De Voto, R.H.

    1984-01-01

    This paper is a review of the methodology and technology that are currently being used in varying degrees in uranium exploration activities worldwide. Since uranium is ubiquitous and occurs in trace amounts (0.2 to 5 ppm) in virtually all rocks of the crust of the earth, exploration for uranium is essentially the search of geologic environments in which geologic processes have produced unusual concentrations of uranium. Since the level of concentration of uranium of economic interest is dependent on the present and future price of uranium, it is appropriate here to review briefly the economic realities of uranium-fueled power generation. (author)

  15. Uranium

    International Nuclear Information System (INIS)

    1982-01-01

    The development, prospecting, research, processing and marketing of South Africa's uranium industry and the national policies surrounding this industry form the headlines of this work. The geology of South Africa's uranium occurences and their positions, the processes used in the extraction of South Africa's uranium and the utilisation of uranium for power production as represented by the Koeberg nuclear power station near Cape Town are included in this publication

  16. Uranium fixation by mineralization at the redox front

    International Nuclear Information System (INIS)

    Isobe, Hiroshi

    1998-01-01

    The behavior of actinide elements including uranium in geomedia is controlled by redox conditions. Under the oxidized conditions, uranium forms uranyl ion (UO 2 2+ ) and its complexes, and dissolves in ground water. Under the reduced conditions, U(IV) has much lower solubility than uranyl ion. In the Koongarra uranium deposit, Australia, lead-bearing uraninite, uranyl lead oxide and uranyl silicate minerals occur in the unweathered, primary ore zone, and uranyl phosphate minerals occur in the weathered, secondary ore zone. Between unweathered and weathered zones, the transition zone exists as a redox front. In the transition zone, graphite and sulfide minerals react as reducing agents for species dissolved in ground water. By SEM, spherical grains of uraninite were observed in veins with graphite. Pyrite had coffinite rim with crystals of uraninite. Calculation based on the ground water chemistry and hydrology at Koongarra shows that the uranium in the transition zone may be fixed from the ground water. In the Koongarra transition zone, recent mineralization of uranium by reduction takes place. Mineralization is much stronger fixation mechanism than adsorption on clay minerals. Pyrite in the buffer materials of possible radioactive waste repositories can fix radionuclides in oxidized ground water by mineralization with reducing reactions. (author)

  17. Preparation and melting of uranium from U3O8

    International Nuclear Information System (INIS)

    Hur, Jin-Mok; Choi, In-Kyu; Cho, Soo-Haeng; Jeong, Sang-Mun; Seo, Chung-Seok

    2008-01-01

    In this paper, we report on the preparation and melting of uranium in association with a spent nuclear fuel conditioning process. U 3 O 8 powder was electrochemically reduced in a mixture of molten LiCl-Li 2 O (∼3 wt.% of Li 2 O in LiCl) at 650 deg. C resulting in the formation of uranium and Li 2 O with a yield of >99%. When the powder of uranium with a residual LiCl-Li 2 O salt was heated in order to melt the metal, the uranium oxidation to UO 2 due to the reaction with Li 2 O was observed. We were able to synthesize FeU 6 by using a Fe based cathode during the U 3 O 8 reduction procedure. FeU 6 could be melted to below the temperatures where the oxidation of uranium by Li 2 O occurred. The idea of compound formation and melting is applicable to the melting and casting of a spent nuclear fuel which contains oxidative residual salts due to its conditioning in a molten salt

  18. Preparation and Characterization of Uranium Oxides in Support of the K Basin Sludge Treatment Project

    Energy Technology Data Exchange (ETDEWEB)

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2008-07-08

    Uraninite (UO2) and metaschoepite (UO3·2H2O) are the uranium phases most frequently observed in K Basin sludge. Uraninite arises from the oxidation of uranium metal by anoxic water and metaschoepite arises from oxidation of uraninite by atmospheric or radiolytic oxygen. Studies of the oxidation of uraninite by oxygen to form metaschoepite were performed at 21°C and 50°C. A uranium oxide oxidation state characterization method based on spectrophotometry of the solution formed by dissolving aqueous slurries in phosphoric acid was developed to follow the extent of reaction. This method may be applied to determine uranium oxide oxidation state distribution in K Basin sludge. The uraninite produced by anoxic corrosion of uranium metal has exceedingly fine particle size (6 nm diameter), forms agglomerates, and has the formula UO2.004±0.007; i.e., is practically stoichiometric UO2. The metaschoepite particles are flatter and wider when prepared at 21°C than the particles prepared at 50°C. These particles are much smaller than the metaschoepite observed in prolonged exposure of actual K Basin sludge to warm moist oxidizing conditions. The uraninite produced by anoxic uranium metal corrosion and the metaschoepite produced by reaction of uraninite aqueous slurries with oxygen may be used in engineering and process development testing. A rapid alternative method to determine uranium metal concentrations in sludge also was identified.

  19. Uranium association with halophilic and non-halophilic bacteria and archaea

    International Nuclear Information System (INIS)

    Francis, A.J.; Gillow, J.B.; Dodge, C.J.; Harris, R.; Beveridge, T.J.; Papenguth, H.W.

    2004-01-01

    We determined the association of uranium with bacteria isolated from the Waste Isolation Pilot Plant (WIPP), Carlsbad, New Mexico, and compared this with known strains of halophilic and non-halophilic bacteria and archaea. Examination of the cultures by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) showed uranium accumulation extracellularly and/or intracellularly to a varying degree. In Pseudomonas fluorescens and Bacillus subtilis uranium was associated with the cell surface and in the latter it was present as irregularly shaped grains. In Halobacterium halobium, the only archeon studied here, uranium was present as dense deposits and with Haloanaerobium praevalens as spikey deposits. Halomonas sp. isolated from the WIPP site accumulated uranium both extracellularly on the cell surface and intracellularly as electron-dense discrete granules. Extended X-ray absorption fine structure (EXAFS) analysis of uranium with the halophilic and non-halophilic bacteria and archaea showed that the uranium present in whole cells was bonded to an average of 2.4 ± 0.7 phosphoryl groups at a distance of 3.65 ± 0.03 Aa. Comparison of whole cells of Halomonas sp. with the cell wall fragments of lysed cells showed the presence of a uranium bidentate complex at 2.91 ± 0.03 Aa with the carboxylate group on the cell wall, and uranyl hydroxide with U-U interaction at 3.71 ± 0.03 Aa due to adsorption or precipitation reactions; no U-P interaction was observed. Addition of uranium to the cell lysate of Halomonas sp. resulted in the precipitation of uranium due to the inorganic phosphate produced by the cells. These results show that the phosphates released from bacteria bind a significant amount of uranium. However, the bacterially immobilized uranium was readily solubilized by bicarbonate with concurrent release of phosphate into solution. (orig.)

  20. Study of the pyrophoric characteristics of uranium-iron alloys; Etude du caractere pyrophorique des alliages uranium fer

    Energy Technology Data Exchange (ETDEWEB)

    Duplessis, X

    2000-02-23

    The objective of the study is to understand the pyrophoric characteristics of uranium-iron alloys. In order to carry out this research we have elected to use uranium-iron alloy powder with granules of 200 {mu}m and 1000 {mu}m diameter with 4%, 10.8% and 14% iron content. The experiments were performed on small samples of few milligrams and on larger quantities of few hundred grams. The main conclusions obtained are the followings: -The reaction start at 453 K (180 deg. C) and the ignition at 543 K (270 deg. C) - The influence of the specific area seems more important than the iron concentration in the alloys - When the alloy ignites, the fire spreads quickly and the alloy rapidly consumes. (author)

  1. The relationship between tectonic-thermal evolution and sandstone-type uranium ore-formation in Ordos basin

    International Nuclear Information System (INIS)

    Zhao Honggang

    2005-01-01

    The comprehensive study of the volcanic activities, the geothermal field, the thermal flow field, the paleogeo-thermal activity and the tectonic evolution of the Ordos basin indicates that the tectonic-thermal evolution of the Ordos basin has offered the basis for the fluid-fluid and fluid-rock mutual reactions, and has created favourable conditions for the formation of organic mineral resources and sandstone-type uranium deposits. Especially, the tectonic-thermal event during middle-Late Jurassic to Cretaceous played an important role in providing uranium source material, and assisting the migration, the concentration and precipitation of uranium and uranium ore-formation. (authors)

  2. Gas-phase chemistry of actinides ions: new insights into the reaction of UO+ and UO+2 with H2O

    International Nuclear Information System (INIS)

    Michelini, M.D.C.; Russo, N.; Sicilia, E.

    2007-01-01

    Complete text of publication follows: Reaction pathways for the interaction of uranium monoxide cations with water were studied by using different approaches of Density Functional Theory. Firstly, relativistic small-core pseudopotentials were used together with B3LYP hybrid functional. In addition, frozen-core PW91-PW91 calculations were performed within the ZORA approximation. A close description of the reaction mechanisms leading to different dissociation channels is presented, including all the involved minima and transition states [1]. Different possible spin states were considered as well as the effect of spin-orbit interactions (SO-ZORA) on the transition state barrier heights. The obtained results are compared with recent experimental data [2] as well as with previous theoretical studies of the reaction of bare uranium cations with water [3], in order to analyse the influence of the oxo-ligand in reactivity. References: [1] Michelini, M.C.; Russo, N.; Sicilia, E.J. Am. Chem. Soc., to be published; [2] (a) Jackson, G. P.; King, F. L.; Goeringer, D. E.; Duckworth, D. C. J. Phys. Chem. A 2002, 106, 7788; (b) Cornehl, H.H.; Wesendrup, R.; Diefenbach, M.; Schwarz, H. Chem. Eur. J. 1997, 3, 1083; (c) Gibson, J. K.; Haire, R. G.; Santos, M.; Marcalo, J.; Pires de Matos, A. J. Phys. Chem. A 2005, 109, 2768; [3] Michelini, M.C.; Russo, N.; Sicilia, E. Angew. Chem. Int. Ed., 2006, 45, 1095

  3. Natural uranium-series radionuclide inventories in coastal and oceanic waters of the south-western Pacific - insights into trace metal flux and removal pathway analysis

    International Nuclear Information System (INIS)

    Szymczak, R.; Jeffree, R.A.; Peck, G.A.

    2003-01-01

    Participate scavenging of trace metals plays a major role in determining their ecosystem flux and incident dissolved concentrations. Differences in the half-lives and biogeochemical behaviour of natural uranium series radioisotope pairs (eg. 238 U/ 234 Th, 210 Pb/ 210 Po) allow their application as oceanic process tracers. Coincidental measurements of dissolved and particulate trace element concentrations and inventories of radionuclides in the Noumea coral lagoon and adjacent offshore waters were used to quantify water column flux rates and provide insights on removal pathway analysis. Understanding prevailing pathways and respective flux rates of pollutants in specific coastal and oceanic systems will assist to establish the fate and consequence of pollutants and allow sustainable management strategies to be developed. Both natural and pollutant chemical species introduced to the marine environment may either remain benign in solution or undergo physiological uptake by biota, but most often associate with colloids and fine particles, which subsequent undergo aggregation, sedimentation and removal to the sea floor

  4. Synthesis and reactivity of uranium (III) cyclopentadienyl complexes

    International Nuclear Information System (INIS)

    Foyentin, M.

    1987-01-01

    New uranium organometallic complexes are synthetized from the addition compound Cp U (THF). Reactions with lithium compounds, chlorides, alkynes and borohydrides. Oxidizing addition reactions are evidenced with alkyl halogenides. With a strong reducing agent, the complex Cp-UCH-Li allows the fixation and the reduction of nitrogen into ammonia. Lability of ligands bound to U (III) is evidenced, giving very reactive species and hence catalytic properties for these compounds. Catalytic hydrogenation of olefins is studied. Substitution reactions of alkyl groups of these complexes with olefins in presence or not of hydrogen or with alkyllithium are original [fr

  5. Uranium conversion; Urankonvertering

    Energy Technology Data Exchange (ETDEWEB)

    Oliver, Lena; Peterson, Jenny; Wilhelmsen, Katarina [Swedish Defence Research Agency (FOI), Stockholm (Sweden)

    2006-03-15

    FOI, has performed a study on uranium conversion processes that are of importance in the production of different uranium compounds in the nuclear industry. The same conversion processes are of interest both when production of nuclear fuel and production of fissile material for nuclear weapons are considered. Countries that have nuclear weapons ambitions, with the intention to produce highly enriched uranium for weapons purposes, need some degree of uranium conversion capability depending on the uranium feed material available. This report describes the processes that are needed from uranium mining and milling to the different conversion processes for converting uranium ore concentrate to uranium hexafluoride. Uranium hexafluoride is the uranium compound used in most enrichment facilities. The processes needed to produce uranium dioxide for use in nuclear fuel and the processes needed to convert different uranium compounds to uranium metal - the form of uranium that is used in a nuclear weapon - are also presented. The production of uranium ore concentrate from uranium ore is included since uranium ore concentrate is the feed material required for a uranium conversion facility. Both the chemistry and principles or the different uranium conversion processes and the equipment needed in the processes are described. Since most of the equipment that is used in a uranium conversion facility is similar to that used in conventional chemical industry, it is difficult to determine if certain equipment is considered for uranium conversion or not. However, the chemical conversion processes where UF{sub 6} and UF{sub 4} are present require equipment that is made of corrosion resistant material.

  6. Uranium mineralization environment and prospecting potential of Dawan ore field in Nanling metallogenic belt

    International Nuclear Information System (INIS)

    Yang Shanghai

    2011-01-01

    Located in the middle part of Jiuyishan complex pluton, Nanling metallogenic belt, Dawan uranium ore field in Hunan Province is an important uranium-producing and rare metal, nonferrous metal cluster area due to the favourable mineralization environment. The Cambrian is the main uranium source bed and their contact zone to the pluton is the favorable part for mineralization. The uranium deposits which have been explored are all located in the exocontact zone of Jinjiling pluton in the middle part of Jiuyishan complex pluton which is composed of the independent eastern and western magma evolution centers. In the west center, Jinjiling pluton is closely related to uranium mineralization where the trinity geologic setting was formed with magma evolution, hydrothermal fluid action and mineralization. The deep slitted and large faults provide the pathway and thermodynamic source for circulating migration of mineralizing fluid. The uranium mineralization mainly occurred in crustal stress conversion period of Late Cretaceous and related to the tensive NW extending fault and deep originated fluid. The gravity, aero magnetic, airborne gamma-ray spectrometry anomalies and radioactivity hydrochemical anomaly are important criteria for uranium prospecting. Based on the analysis of regional uranium mineralization environment, the prospecting potential is forecasted. (authors)

  7. Incidents of chemical reactions in cell equipment

    Energy Technology Data Exchange (ETDEWEB)

    Baldwin, N.M.; Barlow, C.R. [Uranium Enrichment Organization, Oak Ridge, TN (United States)

    1991-12-31

    Strongly exothermic reactions can occur between equipment structural components and process gases under certain accident conditions in the diffusion enrichment cascades. This paper describes the conditions required for initiation of these reactions, and describes the range of such reactions experienced over nearly 50 years of equipment operation in the US uranium enrichment program. Factors are cited which can promote or limit the destructive extent of these reactions, and process operations are described which are designed to control the reactions to minimize equipment damage, downtime, and the possibility of material releases.

  8. The oxidative corrosion of carbide inclusions at the surface of uranium metal during exposure to water vapour.

    Science.gov (United States)

    Scott, T B; Petherbridge, J R; Harker, N J; Ball, R J; Heard, P J; Glascott, J; Allen, G C

    2011-11-15

    The reaction between uranium and water vapour has been well investigated, however discrepancies exist between the described kinetic laws, pressure dependence of the reaction rate constant and activation energies. Here this problem is looked at by examining the influence of impurities in the form of carbide inclusions on the reaction. Samples of uranium containing 600 ppm carbon were analysed during and after exposure to water vapour at 19 mbar pressure, in an environmental scanning electron microscope (ESEM) system. After water exposure, samples were analysed using secondary ion mass spectrometry (SIMS), focused ion beam (FIB) imaging and sectioning and transmission electron microscopy (TEM) with X-ray diffraction (micro-XRD). The results of the current study indicate that carbide particles on the surface of uranium readily react with water vapour to form voluminous UO(3) · xH(2)O growths at rates significantly faster than that of the metal. The observation may also have implications for previous experimental studies of uranium-water interactions, where the presence of differing levels of undetected carbide may partly account for the discrepancies observed between datasets. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

  9. Chronic Exposure to Uranium from Gestation: Effects on Behavior and Neurogenesis in Adulthood.

    Science.gov (United States)

    Dinocourt, Céline; Culeux, Cécile; Legrand, Marie; Elie, Christelle; Lestaevel, Philippe

    2017-05-17

    Uranium exposure leads to cerebral dysfunction involving for instance biochemical, neurochemical and neurobehavioral effects. Most studies have focused on mechanisms in uranium-exposed adult animals. However, recent data on developing animals have shown that the developing brain is also sensitive to uranium. Models of uranium exposure during brain development highlight the need to improve our understanding of the effects of uranium. In a model in which uranium exposure began from the first day of gestation, we studied the neurobehavioral consequences as well as the progression of hippocampal neurogenesis in animals from dams exposed to uranium. Our results show that 2-month-old rats exposed to uranium from gestational day 1 displayed deficits in special memory and a prominent depressive-like phenotype. Cell proliferation was not disturbed in these animals, as shown by 5-bromo-2'deoxyuridine (BrdU)/neuronal specific nuclear protein (NeuN) immunostaining in the dentate gyrus. However, in some animals, the pyramidal cell layer was dispersed in the CA3 region. From our previous results with the same model, the hypothesis of alterations of neurogenesis at prior stages of development is worth considering, but is probably not the only one. Therefore, further investigations are needed to correlate cerebral dysfunction and its underlying mechanistic pathways.

  10. Overview of selective photo-reaction

    International Nuclear Information System (INIS)

    Arisawa, Takashi

    1995-01-01

    Selective reaction process especially isotope separation is a key technology for the development of the technologies related to the nuclear energy. However only a few species are separated on a production scale using the conventional processes such as thermal diffusion, chemical exchange reaction and distillation for lighter isotopes, and gas centrifuge and gaseous diffusion for uranium. As these methods are based on statistical thermodynamics and have low enrichment factors, they need repetitive operations of separation with many separating units combined together. Electro-magnetic separation method known as the one with high separation factor can be applied to most of the elements, but extremely low production rate is realized, which is uneconomical. From the above point of view, much attention has been pain to the laser process. This method can be applied to either gas, liquid or solid phase, and high separation factors are basically realized only in gaseous phase. Since the beginning of the studies on isotope separation in early 1970s, many ideas have been proposed for the selective photo-reaction process such as photoionization, multiphoton dissociation and state selective chemical reaction. As a result of experimental and theoretical efforts, large scale production of some isotopes have been intended. Production of deuterium by infrared multi-photodissociation method was studied aiming at the replacement of the conventional dual temperature exchange process, and lots of experiments have been achieved intensively for the uranium enrichment. A stepwise selective photoionization method has also been studied for the isotopic separation of many elements, especially uranium enrichment. To implement the laser processes on a large scale production system, advanced performances are required not only for the tunable laser systems but also for many related technologies such as atomic/molecular source, photo-reactor and extractor of products. (author)

  11. Radiological impact of surface water and sediment near uranium mining sites.

    Science.gov (United States)

    Ivanova, K; Stojanovska, Z; Badulin, V; Kunovska, B; Yovcheva, M

    2015-12-01

    The aim of this study is to assess the radiological impact of surface water and sediment around uranium mining sites 20 years after their closing. The areas under observations are 31 former classical underground uranium mining and exploratory sites in Bulgaria, named as objects. The extraction and processing of uranium ores in the Republic of Bulgaria were ended in 1992. To assess the radiological impact of radionuclides field expeditions were performed to sample water and bottom sediment. The migration of uranium through surface water was examined as one of the major pathways for contamination spread. The range of uranium concentration in water flowing from the mining sites was from 0.012 to 6.8 mgU l(-1) with a geometric mean of 0.192 mgU l(-1). The uranium concentrations in water downstream the mining sites were approximately 3 times higher than the background value (upstream). The concentrations of Unat, (226)Ra, (210)Pb, and (232)Th in the sediment of downstream river were higher than those upstream by 3.4, 2.6, 2, and 1.7 times, respectively. The distribution coefficient of uranium reflects its high mobility in most of the sites. In order to evaluate the impact on people as well as site prioritization for more detailed assessment and water management, screening dose assessments were done.

  12. Chlorination of uranium oxides with CCl{sub 4} using a mechanochemical method

    Energy Technology Data Exchange (ETDEWEB)

    Kitawaki, Shinichi, E-mail: kitawaki.shinichi@jaea.go.jp [Nuclear Fuel Cycle Engineering Laboratories, Japan Atomic Energy Agency, 4-33 Muramatsu, Tokai, Naka, Ibaraki 319-1194 (Japan); Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba, Sendai, Miyagi 980-8577 (Japan); Nagai, Takayuki [Nuclear Fuel Cycle Engineering Laboratories, Japan Atomic Energy Agency, 4-33 Muramatsu, Tokai, Naka, Ibaraki 319-1194 (Japan); Sato, Nobuaki [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba, Sendai, Miyagi 980-8577 (Japan)

    2013-08-15

    Highlights: • UCl{sub 4} or UOCl{sub 2} could be synthesized from U{sub 3}O{sub 8} with CCl{sub 4} by using a planetary ball mill. • The chlorination could not be observed when using UO{sub 2} powder as the starting material. • Extension of milling time was effective for chlorinating U{sub 3}O{sub 8} with the appropriate amount of CCl{sub 4}. -- Abstract: A chlorination method for uranium oxides at low temperature was investigated by using a mechanochemical method. In particular, the possibility of the chlorination of uranium oxides, such as UO{sub 2} and U{sub 3}O{sub 8}, via mechanochemical reaction with CCl{sub 4} was studied using a planetary ball mill. Mechanochemical experiments were conducted to evaluate the effect of milling time, CCl{sub 4}/uranium oxide molar ratio, and revolution speed on the reaction. The synthesized products were then subjected to X-ray diffraction analysis, and it was found that the chlorination of U{sub 3}O{sub 8} with CCl{sub 4} to UOCl{sub 2}, UCl{sub 4}, and U{sub 2}O{sub 2}Cl{sub 5} proceeded. However, the chlorination reaction could not be observed when using UO{sub 2} powder as the raw material.

  13. Uranium

    International Nuclear Information System (INIS)

    Mackay, G.A.

    1978-01-01

    The author discusses the contribution made by various energy sources in the production of electricity. Estimates are made of the future nuclear contribution, the future demand for uranium and future sales of Australian uranium. Nuclear power growth in the United States, Japan and Western Europe is discussed. The present status of the six major Australian uranium deposits (Ranger, Jabiluka, Nabarlek, Koongarra, Yeelerrie and Beverley) is given. Australian legislation relevant to the uranium mining industry is also outlined

  14. A Networks Approach to Modeling Enzymatic Reactions.

    Science.gov (United States)

    Imhof, P

    2016-01-01

    Modeling enzymatic reactions is a demanding task due to the complexity of the system, the many degrees of freedom involved and the complex, chemical, and conformational transitions associated with the reaction. Consequently, enzymatic reactions are not determined by precisely one reaction pathway. Hence, it is beneficial to obtain a comprehensive picture of possible reaction paths and competing mechanisms. By combining individually generated intermediate states and chemical transition steps a network of such pathways can be constructed. Transition networks are a discretized representation of a potential energy landscape consisting of a multitude of reaction pathways connecting the end states of the reaction. The graph structure of the network allows an easy identification of the energetically most favorable pathways as well as a number of alternative routes. © 2016 Elsevier Inc. All rights reserved.

  15. Czechoslovak uranium

    International Nuclear Information System (INIS)

    Pluskal, O.

    1992-01-01

    Data and knowledge related to the prospecting, mining, processing and export of uranium ores in Czechoslovakia are presented. In the years between 1945 and January 1, 1991, 98,461.1 t of uranium were extracted. In the period 1965-1990 the uranium industry was subsidized from the state budget to a total of 38.5 billion CSK. The subsidies were put into extraction, investments and geologic prospecting; the latter was at first, ie. till 1960 financed by the former USSR, later on the two parties shared costs on a 1:1 basis. Since 1981 the prospecting has been entirely financed from the Czechoslovak state budget. On Czechoslovak territory uranium has been extracted from deposits which may be classified as vein-type deposits, deposits in uranium-bearing sandstones and deposits connected with weathering processes. The future of mining, however, is almost exclusively being connected with deposits in uranium-bearing sandstones. A brief description and characteristic is given of all uranium deposits on Czechoslovak territory, and the organization of uranium mining in Czechoslovakia is described as is the approach used in the world to evaluate uranium deposits; uranium prices and actual resources are also given. (Z.S.) 3 figs

  16. Development of very-high-density low-enriched-uranium fuels

    International Nuclear Information System (INIS)

    Snelgrove, J.L.; Hofman, G.L.; Meyer, M.K.; Trybus, C.L.; Wiencek, T.C.

    1997-01-01

    Following a hiatus of several years and following its successful development and qualification of 4.8 g U cm -3 U 3 Si 2 -Al dispersion fuel for application with low-enriched uranium in research and test reactors, the US Reduced Enrichment for Research and Test Reactors program has embarked on the development of even-higher-density fuels. Our goal is to achieve uranium densities of 8-9 g cm -3 in aluminum-based dispersion fuels. Achieving this goal will require the use of high-density, γ-stabilized uranium alloy powders in conjunction with the most-advanced fuel fabrication techniques. Key issues being addressed are the reaction of the fuel alloys with aluminum and the irradiation behavior of the fuel alloys and any reaction products. Test irradiations of candidate fuels in very-small (micro) plates are scheduled to begin in the Advanced Test Reactor during June, 1997. Initial results are expected to be available in early 1998. We are performing out-of-reactor studies on the phase structure of the candidate alloys on diffusion of the matrix material into the aluminum. In addition, we are modifying our current dispersion fuel irradiation behavior model to accommodate the new fuels. Several international partners are participating in various phases of this work. (orig.)

  17. Uranium in Niger; L'uranium au Niger

    Energy Technology Data Exchange (ETDEWEB)

    Gabelmann, E

    1978-03-15

    This document presents government policy in the enhancement of uranium resources, existing mining companies and their productions, exploitation projects and economical outcome related to the uranium mining and auxiliary activities. [French] Le document presente la politique de l'Etat dans le cadre de la mise en valeur des ressources d'uranium, les societes minieres existantes et leurs productions, les projets d'exploitation d'uranium et les retombees economiques liees aux activites uraniferes et connexes.

  18. Reaction pathway and oxidation mechanisms of dibutyl phthalate by persulfate activated with zero-valent iron

    Energy Technology Data Exchange (ETDEWEB)

    Li, Huanxuan [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); Wan, Jinquan, E-mail: ppjqwan@scut.edu.cn [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); State Key Lab Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640 (China); Ma, Yongwen [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); State Key Lab Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640 (China); Wang, Yan [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China)

    2016-08-15

    This study investigated reaction pathway and oxidation mechanisms of dibutyl phthalate (DBP) by persulfate (PS) activated with zero-valent iron (ZVI). The DBP degradation was studied at three pH values (acidic, neutral and basic) in the presence of different organic scavengers. Using a chemical probe method, both sulfate radical (SO{sub 4}·{sup −}) and hydroxyl radical (·OH) were found to be primary oxidants at pH 3.0 and pH 7.0, respectively while ·OH was the major specie to oxidize DBP at pH 11.0. A similar result was found in an experiment of Electron Spin Resonance spin-trapping where in addition to ·OH, superoxide radical (O{sub 2}·{sup −}) was detected at pH 11.0. The transformation of degradation products including dimethyl phthalate (DMP), diethyl phthalate (DEP), phthalic anhydride, and acetophenone exhibited diverse variation during the reaction processes. The phthalic anhydride concentration appeared to be maximum at all pHs. Another eleven intermediate products were also found at pH 3.0 by GC–MS and HPLC analysis, and their degradation mechanisms and pathways were proposed. It was suggested that dealkylation, hydroxylation, decarboxylation and hydrogen extraction were the dominant degradation mechanisms of DBP at pH 3.0. - Highlights: • Both SO{sub 4}{sup −}· and ·OH were found to be the major active species at pH 3.0 and pH 7.0. • ·OH and ·O2– were the primary oxidants pH 11.0. • The intermediate products were investigated as well as the degradation pathway. • Dealkylation, hydroxylation, decarboxylation, H-extraction were the major mechanisms.

  19. Reaction pathways for reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes

    International Nuclear Information System (INIS)

    Cunha, M.C.P.M. da; De Souza, J.P.I.; Nart, F.C.

    2000-01-01

    The reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes has been investigated using differential electrochemical mass spectrometry and in situ FTIR measurements. For 3 M HNO 3 concentration it has been found that nitrate starts the reduction with partial N-O bond dissociation and N-N bond formation generating NO and N 2 O. At potentials lower than 0.2 V the reaction proceeds forming dissolved NH 4 + . For potentials lower than 0 V the reduction continues via a multiple pathway reaction leading to the nonselective production of N 2 , NH 2 OH, and N 2 H 2 . On the alloyed electrodes, the production of NO and N 2 O has been observed in both cathodic and anodic scans, while on pure platinum and rhodium electrodes the reaction has been observed only during the cathodic scan. Contrasting with the pure platinum and rhodium alloys, where the N-O bond break starts forming NO and N 2 O, on the alloys HNO 2 has been observed as the first reaction step. For alloys with higher rhodium composition, like Pt 75 Rh 25 , no N 2 has been detected for potentials lower than 0 V

  20. Difficulties in preparing a standard sample of uranium metal having traces of nitrogen

    International Nuclear Information System (INIS)

    Toteja, R.S.D.; Jangida, B.L.; Sundaresan, M.

    1991-01-01

    Normally in the analysis of uranium for nitrogen, the nitrides are hydrolysed to give NH 3 and that for standardisation purposes to approximate the closest conditions of analysis of ammonia, NH 4 Cl is added to the sample and the recovery is tested. An appropriate method will be to have a standard sample of uranium with known amounts of nitrogen to be used as reference sample. The present work describes the efforts made in the preparation of such a reference sample and a general assessment of such methods available. In present work, known microamounts of nitrogen in an enclosed volume were allowed to react at a temperature of 773 K with a fixed amount of uranium metal of nitrogen content determined chemically. As the reaction of nitrogen with uranium is essentially a surface reaction, a sample had to be homogenised by allowing the nitrided sample to melt at about 1500 K and allow the nitrogen to diffuse through so that the concentration gradient along the profile will disappear. Attempts were made to prepare such samples in the range to 40 to 100 ppm of nitrogen. The density differences of uranium nitride and uranium metal made this diffusion and homogenisation process difficult. The prepared samples were analysed by the micro-kjeldahl's method and the recoveries tested. The equipment used for the preparation of the nitrided samples, for homogenisation and analysis of the results obtained are detailed in the paper together with the assessment of the general methods. (author). 2 refs., 1 fig., 1 tab

  1. Uranium tetracyclopentadienyl interaction with carbon oxide and dioxide

    International Nuclear Information System (INIS)

    Leonov, M.R.; Solov'eva, G.V.; Kozina, I.Z.; Bolotova, G.T.

    1983-01-01

    Using the methods of gas-liquid chromatography, IR and UV spectroscopy and element analysis, the reactions of tetracyclogentadienyluranium with carbon oxide and dioxide have been studied. It is shown that complete uranium cyclopentadienyl π-complex-tetracyclopentadienyluranium - in pentane under normal conditions for 100 hr reacts with carbon oxide and dioxide with the formation of polymeric complex ([(etasup(5)-Csub(5)Hsub(5))x(-CO-)U(etasup(5)-Csub(5)Hsub(4))(-CO-)]sub(2)]sub(n), in which two uranium atoms are bonded with two bridge fragments (eta 5 -C 5 H 4 -CO-), and dimeric complex [(eta 5 -C 5 H 5 ) 2 UH 2 xCO 2 ] 2 respectively

  2. Sorbent selection and design considerations for uranium trapping

    International Nuclear Information System (INIS)

    Schultz, R.M.; Hobbs, W.E.; Norton, J.L.; Stephenson, M.J.

    1981-07-01

    The efficient removal of UF 6 from effluent streams can be accomplished through the selection of the best solid sorbent and the implementation of good design principles. Pressure losses, sorbent capacity, reaction kinetics, sorbent regeneration/uranium recovery requirements and the effects of other system components are the performance factors which are summarized. The commonly used uranium trapping materials highlighted are sodium fluoride, H-151 alumina, XF-100 alumina, and F-1 alumina. Sorbent selection and trap design have to be made on a case-by-case basis but the theoretical modeling studies and the evaluation of the performance factors presented can be used as a guide for other chemical trap applications

  3. Elevated Arsenic and Uranium Concentrations in Unregulated Water Sources on the Navajo Nation, USA

    OpenAIRE

    Hoover, Joseph; Gonzales, Melissa; Shuey, Chris; Barney, Yolanda; Lewis, Johnnye

    2016-01-01

    Regional water pollution and use of unregulated water sources can be an important mixed metals exposure pathway for rural populations located in areas with limited water infrastructure and an extensive mining history.?Using censored data analysis and mapping techniques we analyzed the joint geospatial distribution of arsenic and uranium in unregulated water sources throughout the Navajo Nation, where over 500 abandoned uranium mine sites are located in the rural southwestern United States. Re...

  4. Uranium ores

    International Nuclear Information System (INIS)

    Poty, B.; Roux, J.

    1998-01-01

    The processing of uranium ores for uranium extraction and concentration is not much different than the processing of other metallic ores. However, thanks to its radioactive property, the prospecting of uranium ores can be performed using geophysical methods. Surface and sub-surface detection methods are a combination of radioactive measurement methods (radium, radon etc..) and classical mining and petroleum prospecting methods. Worldwide uranium prospecting has been more or less active during the last 50 years, but the rise of raw material and energy prices between 1970 and 1980 has incited several countries to develop their nuclear industry in order to diversify their resources and improve their energy independence. The result is a considerable increase of nuclear fuels demand between 1980 and 1990. This paper describes successively: the uranium prospecting methods (direct, indirect and methodology), the uranium deposits (economical definition, uranium ores, and deposits), the exploitation of uranium ores (use of radioactivity, radioprotection, effluents), the worldwide uranium resources (definition of the different categories and present day state of worldwide resources). (J.S.)

  5. The first nuclear chain reaction

    International Nuclear Information System (INIS)

    Zinn, W.H.

    1989-01-01

    The author offers his recollections of the experimental efforts beginning in 1939 which culminated in the Chain Reaction in the squash court on December 2, 1942. Recalled are Columbia University experiments which did much to establish the feasibility of the chain in natural uranium and which stimulated the creation of the Manhattan District. The Columbia group moved to the University of Chicago, where, in early summer of 1942, construction and analysis of a number of subcritical reactors (piles) gave assurance with a high probability that only a reasonable amount of uranium and moderator would be required

  6. Measurement of nuclear properties of steel and uranium in thermal neutron flux

    International Nuclear Information System (INIS)

    Markovic, V.; Kocic, A.

    1965-01-01

    This paper describes measurements of effective cross sections of steel and uranium reaction with thermal neutrons. Results obtained for domestic steel were compared to the values for Russian steel, and showed that the absorption cross sections are lower, meaning that the domestic steel has less Ni and Cr additions. Comparison of domestic UO 2 with Russian metal uranium showed similar properties. In estimating the precision of measurements the selfshielding factors were predominant

  7. A contribution to the study of mass transfer: uranium extraction from phosphoric acid

    International Nuclear Information System (INIS)

    Maher, A.

    1985-12-01

    Liquid-liquid extraction of uranium (VI) contained in phosphoric acid is examined. Synergism and thermodynamical equilibria are studied. Influence of drop size, extractant concentration and temperature on reaction kinetics are determined. The experimental study concerns extraction by HDEHP, TOPO and the mixture of both. Reaction mechanisms are interpreted [fr

  8. Uranium potentiometer determination in inactive atmosphere with ferric sulfate

    International Nuclear Information System (INIS)

    Fernandez Cellini, R.; Alonso Lopez, J.

    1956-01-01

    Potenciometric titration of Uranium with (SO 4 ) 3 Fe 2 , using Cd as reducing agent has been studied; acidity and sensibility of this reaction are fixed. This method yields good results for uranite group, removing previously phosphate by ion exchange with Amberlite IR-120. (Author)

  9. In situ spectroscopy and spectroelectrochemistry of uranium in high-temperature alkali chloride molten salts.

    Science.gov (United States)

    Polovov, Ilya B; Volkovich, Vladimir A; Charnock, John M; Kralj, Brett; Lewin, Robert G; Kinoshita, Hajime; May, Iain; Sharrad, Clint A

    2008-09-01

    Soluble uranium chloride species, in the oxidation states of III+, IV+, V+, and VI+, have been chemically generated in high-temperature alkali chloride melts. These reactions were monitored by in situ electronic absorption spectroscopy. In situ X-ray absorption spectroscopy of uranium(VI) in a molten LiCl-KCl eutectic was used to determine the immediate coordination environment about the uranium. The dominant species in the melt was [UO 2Cl 4] (2-). Further analysis of the extended X-ray absorption fine structure data and Raman spectroscopy of the melts quenched back to room temperature indicated the possibility of ordering beyond the first coordination sphere of [UO 2Cl 4] (2-). The electrolytic generation of uranium(III) in a molten LiCl-KCl eutectic was also investigated. Anodic dissolution of uranium metal was found to be more efficient at producing uranium(III) in high-temperature melts than the cathodic reduction of uranium(IV). These high-temperature electrolytic processes were studied by in situ electronic absorption spectroelectrochemistry, and we have also developed in situ X-ray absorption spectroelectrochemistry techniques to probe both the uranium oxidation state and the uranium