Controlling plasma properties under differing degrees of electronegativity using odd harmonic dual frequency excitation

NASA Astrophysics Data System (ADS)

Gibson, Andrew R.; Gans, Timo

2017-11-01

The charged particle dynamics in low-pressure oxygen plasmas excited by odd harmonic dual frequency waveforms (low frequency of 13.56 MHz and high frequency of 40.68 MHz) are investigated using a one-dimensional numerical simulation in regimes of both low and high electronegativity. In the low electronegativity regime, the time and space averaged electron and negative ion densities are approximately equal and plasma sustainment is dominated by ionisation at the sheath expansion for all combinations of low and high frequency and the phase shift between them. In the high electronegativity regime, the negative ion density is a factor of 15-20 greater than the low electronegativity cases. In these cases, plasma sustainment is dominated by ionisation inside the bulk plasma and at the collapsing sheath edge when the contribution of the high frequency to the overall voltage waveform is low. As the high frequency component contribution to the waveform increases, sheath expansion ionisation begins to dominate. It is found that the control of the average voltage drop across the plasma sheath and the average ion flux to the powered electrode are similar in both regimes of electronegativity, despite the differing electron dynamics using the considered dual frequency approach. This offers potential for similar control of ion dynamics under a range of process conditions, independent of the electronegativity. This is in contrast to ion control offered by electrically asymmetric waveforms where the relationship between the ion flux and ion bombardment energy is dependent upon the electronegativity.

Principles of Electronegativity Part 1. General Nature.

ERIC Educational Resources Information Center

Sanderson, R. T.

1988-01-01

Summarizes the general principles governing the significance and applications of electronegativity. Presents and discusses seven principles in a general way. Describes electronegativity in general as a consequence of incompletely screened nuclear charge effective within stable outer orbital vacancies, which in turn is a function of the atomic…

Atomic orbitals in molecules: general electronegativity and improvement of Mulliken population analysis.

PubMed

Lu, Haigang; Dai, Dadi; Yang, Pin; Li, Lemin

2006-01-21

An approach of atomic orbitals in molecules (AOIM) has been developed to study the atomic properties in molecules, in which the molecular orbitals are expressed in terms of the optimized minimal atomic orbitals. The atomic electronegativities are calculated using Pauling's electronegativity of free atom and are employed to find the electronegativity equilibrium in molecules and to describe the amphoteric properties of the transition metals from the groups 4 to 10. AOIM can also improve the numerical stability and accuracy of the original Mulliken population analysis.

Toward an alternative hardness kernel matrix structure in the Electronegativity Equalization Method (EEM).

PubMed

Chaves, J; Barroso, J M; Bultinck, P; Carbó-Dorca, R

2006-01-01

This study presents an alternative of the Electronegativity Equalization Method (EEM), where the usual Coulomb kernel has been transformed into a smooth function. The new framework, as the classical EEM, permits fast calculations of atomic charges in a given molecule for a small computational cost. The original EEM procedure needs to previously calibrate the different implied atomic hardness and electronegativity, using a chosen set of molecules. In the new EEM algorithm half the number of parameters needs to be calibrated, since a relationship between electronegativities and hardnesses has been found.

Electronegativity determination of individual surface atoms by atomic force microscopy.

PubMed

Onoda, Jo; Ondráček, Martin; Jelínek, Pavel; Sugimoto, Yoshiaki

2017-04-26

Electronegativity is a fundamental concept in chemistry. Despite its importance, the experimental determination has been limited only to ensemble-averaged techniques. Here, we report a methodology to evaluate the electronegativity of individual surface atoms by atomic force microscopy. By measuring bond energies on the surface atoms using different tips, we find characteristic linear relations between the bond energies of different chemical species. We show that the linear relation can be rationalized by Pauling's equation for polar covalent bonds. This opens the possibility to characterize the electronegativity of individual surface atoms. Moreover, we demonstrate that the method is sensitive to variation of the electronegativity of given atomic species on a surface due to different chemical environments. Our findings open up ways of analysing surface chemical reactivity at the atomic scale.

Electronegativity determination of individual surface atoms by atomic force microscopy

PubMed Central

Onoda, Jo; Ondráček, Martin; Jelínek, Pavel; Sugimoto, Yoshiaki

2017-01-01

Electronegativity is a fundamental concept in chemistry. Despite its importance, the experimental determination has been limited only to ensemble-averaged techniques. Here, we report a methodology to evaluate the electronegativity of individual surface atoms by atomic force microscopy. By measuring bond energies on the surface atoms using different tips, we find characteristic linear relations between the bond energies of different chemical species. We show that the linear relation can be rationalized by Pauling's equation for polar covalent bonds. This opens the possibility to characterize the electronegativity of individual surface atoms. Moreover, we demonstrate that the method is sensitive to variation of the electronegativity of given atomic species on a surface due to different chemical environments. Our findings open up ways of analysing surface chemical reactivity at the atomic scale. PMID:28443645

Particle-in-cell simulation of an electronegative plasma under direct current bias studied in a large range of electronegativity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oudini, N.; Laboratoire des plasmas de Decharges, Centre de Developement des Technologies Avancees, Cite du 20 Aout BP 17 Baba Hassen, 16081 Algiers; Raimbault, J.-L.

2013-04-15

A one-dimensional electronegative plasma situated between two symmetrical parallel electrodes under DC bias is studied by Particle-In-Cell simulation with Monte Carlo Collisions. By varying the electronegativity {alpha}{identical_to}n{sub -}/n{sub e} from the limit of electron-ion plasmas (negative ion free) to ion-ion plasmas (electron free), the sheaths formation, the negative ion flux flowing towards the electrodes, and the particle velocities at the sheath edges are investigated. Depending on {alpha}, it is shown that the electronegative plasma behavior can be described by four regimes. In the lowest regime of {alpha}, i.e., {alpha} < 50, negative ions are confined by two positive sheaths withinmore » the plasma, while in the higher regimes of {alpha}, a negative sheath is formed and the negative ion flux can be extracted from the bulk plasma. In the two intermediate regimes of {alpha}, i.e., 50 < {alpha} < 10{sup 5}, both the electron and the negative ion fluxes are involved in the neutralization of the positive ions flux that leaves the plasma. In particular, we show that the velocity of the negative ions entering the negative sheath is affected by the presence of the electrons, and is not given by the modified Bohm velocity generally accepted for electronegative plasmas. For extremely high electronegativity, i.e., {alpha} > 10{sup 5}, the presence of electrons in the plasma is marginal and the electronegative plasma can be considered as an ion-ion plasma (electron free).« less

Demystifying Introductory Chemistry. Part 3: Ionization Energies, Electronegativity, Polar Bonds, and Partial Charges.

ERIC Educational Resources Information Center

Spencer, James; And Others

1996-01-01

Shows how ionization energies provide a convenient method for obtaining electronegativity values that is simpler than the conventional methods. Demonstrates how approximate atomic charges can be calculated for polar molecules and how this method of determining electronegativities may lead to deeper insights than are typically possible for the…

A group electronegativity equalization scheme including external potential effects.

PubMed

Leyssens, Tom; Geerlings, Paul; Peeters, Daniel

2006-07-20

By calculating the electron affinity and ionization energy of different functional groups, CCSD electronegativity values are obtained, which implicitly account for the effect of the molecular environment. This latter is approximated using a chemically justified point charge model. On the basis of Sanderson's electronegativity equalization principle, this approach is shown to lead to reliable "group in molecule" electronegativities. Using a slight adjustment of the modeled environment and first-order principles, an electronegativity equalization scheme is obtained, which implicitly accounts for the major part of the external potential effect. This scheme can be applied in a predictive manner to estimate the charge transfer between two functional groups, without having to rely on cumbersome calibrations. A very satisfactory correlation is obtained between these charge transfers and those obtained from an ab initio calculation of the entire molecule.

Hyperhalogens and highly electronegative compositions

DOEpatents

Jena, Puru; Gantefoer, Gerd

2016-08-16

Hyperhalogens, a new class of highly electronegative species, are now invented. A hyperhalogen is a superhalogen-containing composition in which the electron affinity (EA) of the hyperhalogen is even larger than that of the superhalogens they are composed of. Novel production methods are provided in which highly electronegative species are produced by surrounding a central metal atom by superhalogen moieties.

Is Electronegativity a Useful Descriptor for the "Pseudo-Alkali-Metal" NH4?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Whiteside, Alexander; Xantheas, Sotiris S.; Gutowski, Maciej S.

2011-11-18

Molecular ions in the form of "pseudo-atoms" are common structural motifs in chemistry, with properties that are transferrable between different compounds. We have determined the electronegativity of the "pseudo-alkali metal" ammonium (NH4) and evaluated its reliability as a descriptor in comparison to the electronegativities of the alkali metals. The computed properties of its binary complexes with astatine and of selected borohydrides confirm the similarity of NH4 to the alkali metal atoms, although the electronegativity of NH4 is relatively large in comparison to its cationic radius. We paid particular attention to the molecular properties of ammonium (angular anisotropy, geometric relaxation, andmore » reactivity), which can cause deviations from the behaviour expected of a conceptual "true alkali metal" with this electronegativity. These deviations allow for the discrimination of effects associated with the polyatomic nature of NH4.« less

A new method to derive electronegativity from resonant inelastic x-ray scattering.

PubMed

Carniato, S; Journel, L; Guillemin, R; Piancastelli, M N; Stolte, W C; Lindle, D W; Simon, M

2012-10-14

Electronegativity is a well-known property of atoms and substituent groups. Because there is no direct way to measure it, establishing a useful scale for electronegativity often entails correlating it to another chemical parameter; a wide variety of methods have been proposed over the past 80 years to do just that. This work reports a new approach that connects electronegativity to a spectroscopic parameter derived from resonant inelastic x-ray scattering. The new method is demonstrated using a series of chlorine-containing compounds, focusing on the Cl 2p(-1)LUMO(1) electronic states reached after Cl 1s → LUMO core excitation and subsequent KL radiative decay. Based on an electron-density analysis of the LUMOs, the relative weights of the Cl 2p(z) atomic orbital contributing to the Cl 2p(3/2) molecular spin-orbit components are shown to yield a linear electronegativity scale consistent with previous approaches.

Estimation of electronegativity values of elements in different valence states.

PubMed

Li, Keyan; Xue, Dongfeng

2006-10-05

The electronegativities of 82 elements in different valence states and with the most common coordination numbers have been quantitatively calculated on the basis of an effective ionic potential defined by the ionization energy and ionic radius. It is found that for a given cation, the electronegativity increases with increasing oxidation state and decreases with increasing coordination number. For the transition-metal cations, the electronegativity of the low-spin state is higher than that of the high-spin state. The ligand field stabilization, the first filling of p orbitals, the transition-metal contraction, and especially the lanthanide contraction are well-reflected by the relative values of our proposed electronegativity. This new scale is useful for us to estimate some quantities (e.g., the Lewis acid strength for the main group elements and the hydration free energy for the first transition series) and predict the structure and property of materials.

Is electronegativity a useful descriptor for the pseudo-alkali metal NH4?

PubMed

Whiteside, Alexander; Xantheas, Sotiris S; Gutowski, Maciej

2011-11-18

Molecular ions in the form of "pseudo-atoms" are common structural motifs in chemistry, with properties that are transferrable between different compounds. We have determined one such property--the electronegativity--for the "pseudo-alkali metal" ammonium (NH(4)), and evaluated its reliability as a descriptor versus the electronegativities of the alkali metals. The computed properties of ammonium's binary complexes with astatine and of selected borohydrides confirm the similarity of NH(4) to the alkali metal atoms, although the electronegativity of NH(4) is relatively large in comparison to its cationic radius. We have paid particular attention to the molecular properties of ammonium (angular anisotropy, geometric relaxation and reactivity), which can cause deviations from the behaviour expected of a conceptual "true alkali metal" with this electronegativity. These deviations allow for the discrimination of effects associated with the molecular nature of NH(4). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduced electronegativity difference as a factor leading to the formation of Al-based glassy alloys with a large supercooled liquid region of 50 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Louzguine-Luzgin, Dmitri V.; Inoue, Akihisa; Botta, Walter Jose

2006-01-02

The influence of the electronegativity difference among the constituent elements on the stability of the supercooled liquid in two Al-based glassy alloys is studied. A record-large value of the supercooled liquid region of about 50 K is obtained based on the electronegativity difference concept within a certain composition range.

Initial Thrust Measurements of Marshall's Ion-ioN Thruster

NASA Technical Reports Server (NTRS)

Schloeder, Natalie R.; Scogin, Tyler; Liu, Thomas M.; Walker, Mitchell L. R.; Polzin, Kurt A.; Dankanich, John W.; Aanesland, Ane

2015-01-01

Electronegative ion thrusters are a variation of tradition gridded ion thruster technology differentiated by the production and acceleration of both positive and negative ions. Benefits of electronegative ion thrusters include the elimination of lifetime-limiting cathodes from the thruster architecture and the ability to generate appreciable thrust from both charge species. Following the continued development of electronegative ion thruster technology as exhibited by the PEGASES (Plasma Propulsion with Electronegative GASES) thruster, direct thrust measurements are required to push interest in electronegative ion thruster technology forward. For this work, direct thrust measurements of the MINT (Marshall's Ion-ioN Thruster) will be taken on a hanging pendulum thrust stand for propellant mixtures of Sulfur Hexafluoride and Argon at volumetric flow rates of 5-25 sccm at radio frequency power levels of 100-600 watts at a radio frequency of 13.56 MHz. Acceleration grid operation is operated using a square waveform bias of +/-300 volts at a frequency of 25 kHz.

A new method to derive electronegativity from resonant inelastic x-ray scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carniato, S.; Journel, L.; Guillemin, R.

2012-10-14

Electronegativity is a well-known property of atoms and substituent groups. Because there is no direct way to measure it, establishing a useful scale for electronegativity often entails correlating it to another chemical parameter; a wide variety of methods have been proposed over the past 80 years to do just that. This work reports a new approach that connects electronegativity to a spectroscopic parameter derived from resonant inelastic x-ray scattering. The new method is demonstrated using a series of chlorine-containing compounds, focusing on the Cl 2p{sup -1}LUMO{sup 1} electronic states reached after Cl 1s{yields} LUMO core excitation and subsequent KL radiativemore » decay. Based on an electron-density analysis of the LUMOs, the relative weights of the Cl 2p{sub z} atomic orbital contributing to the Cl 2p{sub 3/2} molecular spin-orbit components are shown to yield a linear electronegativity scale consistent with previous approaches.« less

Optoelectronic tuning of organoborylazadipyrromethenes via effective electronegativity at the metalloid center.

PubMed

Berhe, Seare A; Rodriguez, Marco T; Park, Eunsol; Nesterov, Vladimir N; Pan, Hongjun; Youngblood, W Justin

2014-03-03

Organoborylazadipyrromethenes were synthesized from free base and fluoroborylazadipyrromethenes and characterized with regard to their structural and electronic properties. B-N bond lengths, along with photophysical and redox behavior, appear dependent on the effective electronegativity at the boron atom as tuned by its substituents, with stronger electronegativity correlating to a shorter B-N bond length, red-shifted absorbance, enhanced fluorescence lifetime and yield, and positively shifted redox potentials.

Floating potential in electronegative plasmas for non-zero ion temperatures

NASA Astrophysics Data System (ADS)

Regodón, Guillermo Fernando; Fernández Palop, José Ignacio; Tejero-del-Caz, Antonio; Díaz-Cabrera, Juan Manuel; Carmona-Cabezas, Rafael; Ballesteros, Jerónimo

2018-02-01

The floating potential of a Langmuir probe immersed in an electronegative plasma is studied theoretically under the assumption of radial positive ion fluid movement for non-zero positive ion temperature: both cylindrical and spherical geometries are studied. The model is solvable exactly. The special characteristics of the electronegative pre-sheath are found and the influence of the stratified electronegative pre-sheath is shown to be very small in practical applications. It is suggested that the use of the floating potential in the measurement of negative ions population density is convenient, in view of the numerical results obtained. The differences between the two radial geometries, which become very important for small probe radii of the order of magnitude of the Debye length, are studied.

Effect of group electronegativity on electron transfer in bis(hydrazine) radical cations.

PubMed

Qin, Haimei; Zhong, Xinxin; Si, Yubing; Zhang, Weiwei; Zhao, Yi

2011-04-14

The radical cation of 4,10-ditert-butyl-5,9-diisopropyl-4,5,9,10-tetraazatetracyclo[6.2.2.2]-tetradecane (sBI4T(+)), as well as its substituted bis(hydrazine) radical cations, is chosen for the investigation of the electronegativity dependence of its intramolecular electron transfer. To do so, two parameters, reorganization energy and electronic coupling, are calculated with several ab initio approaches. It is found that the electronic couplings decrease with the increase of the group electronegativity while the reorganization energies do not show an explicit dependency. Furthermore, Marcus formula is employed to reveal those effect on the electron transfer rates. The predicted rates of electron transfer generally decrease with increasing group electronegativity, although not monotonically.

Electronegativity and hardness as coordinates in structure stability diagrams.

PubMed Central

Shankar, S; Parr, R G

1985-01-01

With electronegativity and hardness of an atom defined as 1/2(I + A) and 1/2(I - A), respectively, where I and A are the ionization potential and electron affinity, electronegativity difference and hardness sum are proposed as coordinates in structure stability diagrams. With these coordinates a successful topological classification of the crystal structures of octet and suboctet binary compounds is obtained, and a clear delineation of the structural classes portraying chemical periodicity is found. PMID:3855552

Electronegativity effects and single covalent bond lengths of molecules in the gas phase.

PubMed

Lang, Peter F; Smith, Barry C

2014-06-07

This paper discusses in detail the calculation of internuclear distances of heteronuclear single bond covalent molecules in the gaseous state. It reviews briefly the effect of electronegativity in covalent bond length. A set of single bond covalent radii and electronegativity values are proposed. Covalent bond lengths calculated by an adapted form of a simple expression (which calculated internuclear separation of different Group 1 and Group 2 crystalline salts to a remarkable degree of accuracy) show very good agreement with observed values. A small number of bond lengths with double bonds as well as bond lengths in the crystalline state are calculated using the same expression and when compared with observed values also give good agreement. This work shows that covalent radii are not additive and that radii in the crystalline state are different from those in the gaseous state. The results also show that electronegativity is a major influence on covalent bond lengths and the set of electronegativity scale and covalent radii proposed in this work can be used to calculate covalent bond lengths in different environments that have not yet been experimentally measured.

Solution-phase electronegativity scale: insight into the chemical behaviors of metal ions in solution.

PubMed

Li, Keyan; Li, Min; Xue, Dongfeng

2012-04-26

By incorporating the solvent effect into the Born effective radius, we have proposed an electronegativity scale of metal ions in aqueous solution with the most common oxidation states and hydration coordination numbers in terms of the effective ionic electrostatic potential. It is found that the metal ions in aqueous solution are poorer electron acceptors compared to those in the gas phase. This solution-phase electronegativity scale shows its efficiency in predicting some important properties of metal ions in aqueous solution such as the aqueous acidities of the metal ions, the stability constants of metal complexes, and the solubility product constants of the metal hydroxides. We have elaborated that the standard reduction potential and the solution-phase electronegativity are two different quantities for describing the processes of metal ions in aqueous solution to soak up electrons with different final states. This work provides a new insight into the chemical behaviors of the metal ions in aqueous solution, indicating a potential application of this electronegativity scale to the design of solution reactions.

Charged particle mobility refrigerant analyzer

DOEpatents

Allman, S.L.; Chunghsuan Chen; Chen, F.C.

1993-02-02

A method for analyzing a gaseous electronegative species comprises the steps of providing an analysis chamber; providing an electric field of known potential within the analysis chamber; admitting into the analysis chamber a gaseous sample containing the gaseous electronegative species; providing a pulse of free electrons within the electric field so that the pulse of free electrons interacts with the gaseous electronegative species so that a swarm of electrically charged particles is produced within the electric field; and, measuring the mobility of the electrically charged particles within the electric field.

Charged particle mobility refrigerant analyzer

DOEpatents

Allman, Steve L.; Chen, Chung-Hsuan; Chen, Fang C.

1993-01-01

A method for analyzing a gaseous electronegative species comprises the steps of providing an analysis chamber; providing an electric field of known potential within the analysis chamber; admitting into the analysis chamber a gaseous sample containing the gaseous electronegative species; providing a pulse of free electrons within the electric field so that the pulse of free electrons interacts with the gaseous electronegative species so that a swarm of electrically charged particles is produced within the electric field; and, measuring the mobility of the electrically charged particles within the electric field.

Design and Preliminary Testing Plan of Electronegative Ion Thruster

NASA Technical Reports Server (NTRS)

Schloeder, Natalie R.; Liu, Thomas M.; Walker, Mitchell L. R.; Polzin, Kurt A.; Dankanich, John W.; Aanesland, Ane

2014-01-01

Electronegative ion thrusters are a new iteration of existing gridded ion thruster technology differentiated by their ability to produce and accelerate both positive and negative ions. The primary motivations for electronegative ion thruster development include the elimination of lifetime-limiting cathodes from a thruster system and the ability to generate appreciable thrust through the acceleration of both positive or negative-charged ions. Proof-of-concept testing of the PEGASES (Plasma Propulsion with Electronegative GASES) thruster demonstrated the production of positively and negatively-charged ions (argon and sulfur hexafluoride, respectively) in an RF discharge and the subsequent acceleration of each charge species through the application of a time-varying electric field to a pair of metallic grids similar to those found in gridded ion thrusters. Leveraging the knowledge gained through experiments with the PEGASES I and II prototypes, the MINT (Marshall's Ion-ioN Thruster) is being developed to provide a platform for additional electronegative thruster proof-of-concept validation testing including direct thrust measurements. The design criteria used in designing the MINT are outlined and the planned tests that will be used to characterize the performance of the prototype are described.

Nucleoside conformation is determined by the electronegativity of the sugar substituent.

PubMed Central

Guschlbauer, W; Jankowski, K

1980-01-01

The proton and 13C NMR spectra of uridine, deoxyuridine and four 2' substituted uridines (dUn, dUz, dUcl and dUfl) are reported. A linear relationship between the electronegativity of the 2'-substituent and the carbon-13 chemical shift of C2' is observed. Taking into account the effect of electronegativity by using the correction proposed by Karplus or by Jankowski, the proton-proton coupling constants have been used to compute the conformational equilibria of the six uridines. It is shown that the contribution of the N form (3'-endo -2'-exo) increases with the electronegativity of the 2' substituent. Thus dUfl contains some 85% N form in solution. - Applying similar corrections to published data in the adenosine series, a similar correlation is observed. This observation, that the most polar substituent pulls the pucker to its side, holds also for 3'-substituted compounds, like cordycepin (3'dAdo) and 3'-deoxy-3'-amino-adenosine. It is suggested that the influence of the electronegativity could be the dominating effect of nucleoside conformations and would also hold for arabinosides and xylosides. This effect should therefore also be the principal force which determines the differences between DNA and RNA. PMID:7433125

Self-similar expansion of adiabatic electronegative dusty plasma

NASA Astrophysics Data System (ADS)

Shahmansouri, M.; Bemooni, A.; Mamun, A. A.

2017-12-01

The self-similar expansion of an adiabatic electronegative dusty plasma (consisting of inertialess adiabatic electrons, inertialess adiabatic ions and inertial adiabatic negatively charged dust fluids) is theoretically investigated by employing the self-similar approach. It is found that the effects of the plasma adiabaticity (represented by the adiabatic index ) and dusty plasma parameters (determined by dust temperature and initial dust population) significantly modify the nature of the plasma expansion. The implications of our results are expected to play an important role in understanding the physics of the expansion of space and laboratory electronegative dusty plasmas.

The Catalytic Effect of Electronegative Additives on Removal of Perchloroethylene Vapor from Air by Pulsed Corona Discharge

NASA Astrophysics Data System (ADS)

Filatov, I. E.; Uvarin, V. V.; Kuznetsov, D. L.

2017-12-01

It is established that electronegative additives (CCl4, freon-113) produce a catalytic effect on the conversion of volatile organic compounds (VOCs) under the action of atmospheric-pressure nonequilibrium plasma generated in pulsed corona discharge. At concentrations below 0.1%, these additives significantly decrease the discharge current, but the energy efficiency of the process of VOC removal from air increases. The catalytic effect of electronegative additives on the VOC conversion in air and nitrogen is quantitatively demonstrated in the case of perchloroethylene C2Cl4 (PCE) vapor removal. The addition of 0.085% CCl4 to air reduces the energy consumption for PCE removal at initial concentration of 0.09% by half (from 12 to 6 eV per molecule) at a 63% degree of cleaning. Mechanisms explaining the active inf luence of electronegative additives on the discharge current and the process of impurity removal are suggested.

An electronegativity-induced spin repulsion effect.

PubMed

Stirling, Andras; Pasquarello, Alfredo

2005-09-22

We present a spin delocalization effect in radical Si-containing systems, featuring a heteroatom of high electronegativity (such as N, O, or Cl) bonded to the unsaturated Si atom. We find that the higher the electronegativity of the heteroatom, the more the localized spin shifts away from the unsaturated Si atom and the heteroatom toward saturated Si neighbors. We demonstrate that this spin repulsion toward saturated Si atoms is induced by the electronegativity difference between the Si atom and the heteroatoms. We present a simple molecular-orbital-based mechanism which fully explains the structural and electronic effects. We contrast the present spin delocalization mechanism with the classical hyperconjugation in organic chemistry. The most important consequences of this spin redistribution are the electron-spin-resonance activity of the saturated Si neighbors and the enhanced stability of the radical centers. We predict a similar effect for Ge radicals and discuss why organic systems based on carbon do not feature such spin repulsion.

Redox and Lewis acid-base activities through an electronegativity-hardness landscape diagram.

PubMed

Das, Ranjita; Vigneresse, Jean-Louis; Chattaraj, Pratim Kumar

2013-11-01

Chemistry is the science of bond making and bond breaking which requires redistribution of electron density among the reactant partners. Accordingly acid-base and redox reactions form cardinal components in all branches of chemistry, e.g., inorganic, organic, physical or biochemistry. That is the reason it forms an integral part of the undergraduate curriculum all throughout the globe. In an electronegativity (χ)- hardness (η) landscape diagram the diagonal χ = η line separates reducing agents from oxidizing agents as well as Lewis acids from Lewis bases. While electronegativity is related to the degree of electron transfer between two reactants, hardness is related to the resistance to that process. Accordingly the electronegativities of oxidizing agents/Lewis acids are generally greater than the corresponding hardness values and the reverse is true for reducing agents/Lewis bases. Electrophiles and nucleophiles are also expected to follow similar trends.

Electronegative Guests in CoSb 3

DOE PAGES

Duan, Bo; Yang, Jiong; Salvador, James R.; ...

2016-04-19

Introducing guests into a host framework to form a so called inclusion compound can be used to design materials with new and fascinating functionalities. The vast majority of inclusion compounds have electropositive guests with neutral or negatively charged frameworks. Here, we show a series of electronegative guest filled skutterudites with inverse polarity. The strong covalent guest-host interactions observed for the electronegative group VIA guests, i.e., S and Se, feature a unique localized cluster vibration which significantly influences the lattice dynamics, together with the point-defect scattering caused by element substitutions, resulting in very low lattice thermal conductivity values. The findings ofmore » electronegative guests provide a new perspective for guest-filling in skutterudites, and the covalent filler/lattice interactions lead to an unusual lattice dynamics phenomenon which can be used for designing high-efficiency thermoelectric materials and novel functional inclusion compounds with open structures.« less

Enhancing the low frequency THz resonances (< 1 THz) of organic molecules via electronegative atom substitution

NASA Astrophysics Data System (ADS)

Dash, Jyotirmayee; Ray, Shaumik; Pesala, Bala

2015-03-01

Terahertz (THz) technology is an active area of research with various applications in non-intrusive imaging and spectroscopy. Very few organic molecules have significant resonances below 1 THz. Understanding the origin of low frequency THz modes in these molecules and their absence in other molecules could be extremely important in design and engineering molecules with low frequency THz resonances. These engineered molecules can be used as THz tags for anti-counterfeiting applications. Studies show that low frequency THz resonances are commonly observed in molecules having higher molecular mass and weak intermolecular hydrogen bonds. In this paper, we have explored the possibility of enhancing the strength of THz resonances below 1 THz through electronegative atom substitution. Adding an electronegative atom helps in achieving higher hydrogen bond strength to enhance the resonances below 1 THz. Here acetanilide has been used as a model system. THz-Time Domain Spectroscopy (THz-TDS) results show that acetanilide has a small peak observed below 1 THz. Acetanilide can be converted to 2-fluoroacetanilide by adding an electronegative atom, fluorine, which doesn't have any prominent peak below 1 THz. However, by optimally choosing the position of the electronegative atom as in 4-fluoroacetanilide, a significant THz resonance at 0.86 THz is observed. The origin of low frequency resonances can be understood by carrying out Density Functional Theory (DFT) simulations of full crystal structure. These studies show that adding an electronegative atom to the organic molecules at an optimized position can result in significantly enhanced resonances below 1 THz.

The Quantification of Electronegativity: Some Precursors

ERIC Educational Resources Information Center

Jensen, William B.

2012-01-01

This paper calls attention to the early work of the American chemists Worth Rodebush and Groves Cartledge, and their anticipations of a quantitative electronegativity scale, which predate the classic 1932 paper of Linus Pauling by several years. (Contains 2 figures.)

Oxidation Numbers and Their Limitations.

ERIC Educational Resources Information Center

Woolf, A. A.

1988-01-01

Reviews a method for determining oxidation numbers in covalent compounds and balancing mixed organic-inorganic or purely organic systems. Points out ambiguities presented when adjacent atoms have small or zero electronegativity differences. Presents other limitations that arise when using electronegativity values. (CW)

An Improved Experiment to Illustrate the Effect of Electronegativity on Chemical Shift.

ERIC Educational Resources Information Center

Boggess, Robert K.

1988-01-01

Describes a method for using nuclear magnetic resonance to observe the effect of electronegativity on the chemical shift of protons in similar compounds. Suggests the use of 1,3-dihalopropanes as samples. Includes sample questions. (MVL)

Electronegativity estimation of electronic polarizabilities of semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Keyan; Xue, Dongfeng, E-mail: dfxue@chem.dlut.edu.cn

2010-03-15

On the basis of the viewpoint of structure-property relationship in solid state matters, we proposed some useful relations to quantitatively calculate the electronic polarizabilities of binary and ternary chalcopyrite semiconductors, by using electronegativity and principal quantum number. The calculated electronic polarizabilities are in good agreement with reported values in the literature. Both electronegativity and principal quantum number can effectively reflect the detailed chemical bonding behaviors of constituent atoms in these semiconductors, which determines the magnitude of their electronic polarizabilities. The present work provides a useful guide to compositionally design novel semiconductor materials, and further explore advanced electro-optic devices.

Tracking the Effect of Adatom Electronegativity on Systematically Modified AlGaN/GaN Schottky Interfaces.

PubMed

Reiner, Maria; Pietschnig, Rudolf; Ostermaier, Clemens

2015-10-21

The influence of surface modifications on the Schottky barrier height for gallium nitride semiconductor devices is frequently underestimated or neglected in investigations thereof. We show that a strong dependency of Schottky barrier heights for nickel/aluminum-gallium nitride (0001) contacts on the surface terminations exists: a linear correlation of increasing barrier height with increasing electronegativity of superficial adatoms is observed. The negatively charged adatoms compete with the present nitrogen over the available gallium (or aluminum) orbital to form an electrically improved surface termination. The resulting modification of the surface dipoles and hence polarization of the surface termination causes observed band bending. Our findings suggest that the greatest Schottky barrier heights are achieved by increasing the concentration of the most polarized fluorine-gallium (-aluminum) bonds at the surface. An increase in barrier height from 0.7 to 1.1 eV after a 15% fluorine termination is obtained with ideality factors of 1.10 ± 0.05. The presence of surface dipoles that are changing the surface energy is proven by the sessile drop method as the electronegativity difference and polarization influences the contact angle. The extracted decrease in the Lifshitz-van-der-Waals component from 48.8 to 40.4 mJ/m(2) with increasing electronegativity and concentration of surface adatoms confirms the presence of increasing surface dipoles: as the polarizability of equally charged anions decreases with increasing electronegativity, the diiodomethane contact angles increase significantly from 14° up to 39° after the 15% fluorine termination. Therefore, a linear correlation between increasing anion electronegativity of the (Al)GaN termination and total surface energy within a 95% confidence interval is obtained. Furthermore, our results reveal a generally strong Lewis basicity of (Al)GaN surfaces explaining the high chemical inertness of the surfaces.

Novel model of negative secondary ion formation and its use to refine the electronegativity of almost fifty elements.

PubMed

Wittmaack, Klaus

2014-06-17

This study aimed to examine the recently proposed idea that the ionic contribution to atomic bonds is essential in determining the charge state of sputtered atoms. Use was made of negative secondary ion yields reported by Wilson for a large number of elements implanted in silicon and then sputter profiled by Cs bombardment. The derived normalized ion yields (or fractions) P vary by 6 orders of magnitude, but the expected exponential dependence on the electron affinity EA is evident only vaguely. Remarkably, a correlation of similar quality is observed if the data are presented as a function of the ionization potential IP. With IP being the dominant (if not sole) contributor to the electronegativity χ, one is led to assume that P depends on the sum χ + EA. About 72% of the "nonsaturated" ion yields are in accordance with a dependence of the form P ∝ exp[(χ + EA)/ε], with ε ≅ 0.2 eV, provided the appropriate value of χ is selected from the electronegativity tables of Pauling (read in eV), Mulliken or Allen. However, each of the three sources contributes only about one-third to the favorable electronegativity data. This unsatisfactory situation initiated the idea to derive the "true" electronegativity χSIMS from the measured ion yields P(χ + EA), verified for 48 elements. Significant negative deviations of χSIMS from a smooth increase with increasing atomic number are evident for elements with special outer-shell electron configurations such as (n-1)d(g-1)ns(1) or (n-1)d(10)ns(2)np(1). The results strongly support the new model of secondary ion formation and provide means for refining electronegativity data.

Effect of Electronegativity on Bipolar Resistive Switching in a WO3-Based Asymmetric Capacitor Structure.

PubMed

Kim, Jongmin; Inamdar, Akbar I; Jo, Yongcheol; Woo, Hyeonseok; Cho, Sangeun; Pawar, Sambhaji M; Kim, Hyungsang; Im, Hyunsik

2016-04-13

This study investigates the transport and switching time of nonvolatile tungsten oxide based resistive-switching (RS) memory devices. These devices consist of a highly resistive tungsten oxide film sandwiched between metal electrodes, and their RS characteristics are bipolar in the counterclockwise direction. The switching voltage, retention, endurance, and switching time are strongly dependent on the type of electrodes used, and we also find quantitative and qualitative evidence that the electronegativity (χ) of the electrodes plays a key role in determining the RS properties and switching time. We also propose an RS model based on the role of the electronegativity at the interface.

Effect of Compositional Variation in TiO2-Based Flux-Cored Arc Welding Fluxes on the Thermo-physical Properties and Mechanical Behavior of a Weld Zone

NASA Astrophysics Data System (ADS)

Kim, J. B.; Lee, T. H.; Sohn, I.

2018-04-01

The effect of compositional variation in TiO2-based flux-cored arc welding fluxes on viscosity, wettability, and electronegativity was studied. The thermo-physical properties of the retrieved fluxes and their relationship with the mechanical properties of the weld zone, including tensile strength and micro-Vickers hardness, after welding were identified. Microstructural observation under similar welding conditions revealed significant grain coarsening at a corrected optical basicity (Λcorr) of 0.62, resulting in reduced strength and hardness due to greater heat transfer. Welding fluxes containing TiO2-based simple structural units should result in greater heat transfer due to the deficiency in complex [AlO4]5-- and [SiO4]4--based structural units, as identified through spectroscopic analyses using fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. The electronegativity of the retrieved fluxes was also evaluated since higher electronegativity results in greater absorption of electrons in the arc, resulting in arc condensation towards the center direction. Consequently, deeper penetration could be obtained, where the highest electronegativity was identified to be approximately 0.62 of the corrected optical basicity. Thus, both the thermal conductivity and electronegativity of the welding fluxes were identified to determine the heat transfer phenomenon during flux-cored arc welding.

Effect of Compositional Variation in TiO2-Based Flux-Cored Arc Welding Fluxes on the Thermo-physical Properties and Mechanical Behavior of a Weld Zone

NASA Astrophysics Data System (ADS)

Kim, J. B.; Lee, T. H.; Sohn, I.

2018-07-01

The effect of compositional variation in TiO2-based flux-cored arc welding fluxes on viscosity, wettability, and electronegativity was studied. The thermo-physical properties of the retrieved fluxes and their relationship with the mechanical properties of the weld zone, including tensile strength and micro-Vickers hardness, after welding were identified. Microstructural observation under similar welding conditions revealed significant grain coarsening at a corrected optical basicity (Λcorr) of 0.62, resulting in reduced strength and hardness due to greater heat transfer. Welding fluxes containing TiO2-based simple structural units should result in greater heat transfer due to the deficiency in complex [AlO4]5-- and [SiO4]4--based structural units, as identified through spectroscopic analyses using fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. The electronegativity of the retrieved fluxes was also evaluated since higher electronegativity results in greater absorption of electrons in the arc, resulting in arc condensation towards the center direction. Consequently, deeper penetration could be obtained, where the highest electronegativity was identified to be approximately 0.62 of the corrected optical basicity. Thus, both the thermal conductivity and electronegativity of the welding fluxes were identified to determine the heat transfer phenomenon during flux-cored arc welding.

Inductive electronegativity scale. Iterative calculation of inductive partial charges.

PubMed

Cherkasov, Artem

2003-01-01

A number of novel QSAR descriptors have been introduced on the basis of the previously elaborated models for steric and inductive effects. The developed "inductive" parameters include absolute and effective electronegativity, atomic partial charges, and local and global chemical hardness and softness. Being based on traditional inductive and steric substituent constants these 3D descriptors provide a valuable insight into intramolecular steric and electronic interactions and can find broad application in structure-activity studies. Possible interpretation of physical meaning of the inductive descriptors has been suggested by considering a neutral molecule as an electrical capacitor formed by charged atomic spheres. This approximation relates inductive chemical softness and hardness of bound atom(s) with the total area of the facings of electrical capacitor formed by the atom(s) and the rest of the molecule. The derived full electronegativity equalization scheme allows iterative calculation of inductive partial charges on the basis of atomic electronegativities, covalent radii, and intramolecular distances. A range of inductive descriptors has been computed for a variety of organic compounds. The calculated inductive charges in the studied molecules have been validated by experimental C-1s Electron Core Binding Energies and molecular dipole moments. Several semiempirical chemical rules, such as equalized electronegativity's arithmetic mean, principle of maximum hardness, and principle of hardness borrowing could be explicitly illustrated in the framework of the developed approach.

Electronegativity and the Bond Triangle

ERIC Educational Resources Information Center

Meek, Terry L.; Garner, Leah D.

2005-01-01

The usefulness of the bond triangle for categorizing compounds of the main-group elements may be extended by the use of weighted average electronegativities to allow distinction between compounds of the same elements with different stoichiometries. In such cases a higher valency for the central atom leads to greater covalent character and the…

Solitary waves and double layers in a dusty electronegative plasma.

PubMed

Mamun, A A; Shukla, P K; Eliasson, B

2009-10-01

A dusty electronegative plasma containing Boltzmann electrons, Boltzmann negative ions, cold mobile positive ions, and negatively charged stationary dust has been considered. The basic features of arbitrary amplitude solitary waves (SWs) and double layers (DLs), which have been found to exist in such a dusty electronegative plasma, have been investigated by the pseudopotential method. The small amplitude limit has also been considered in order to study the small amplitude SWs and DLs analytically. It has been shown that under certain conditions, DLs do not exist, which is in good agreement with the experimental observations of Ghim and Hershkowitz [Y. Ghim (Kim) and N. Hershkowitz, Appl. Phys. Lett. 94, 151503 (2009)].

Electronegativity identification of novel superhard materials.

PubMed

Li, Keyan; Wang, Xingtao; Zhang, Fangfang; Xue, Dongfeng

2008-06-13

We show that electronegativity can be used to effectively identify the hardness of crystal materials on the basis of a new microscopic model for hardness. Bond electronegativity is proposed to characterize the electron-holding energy of a bond, which is the intrinsic origin of hardness. Applying this model to c-BC(2)N materials, we confirm the proper bond composition of the experimentally observed phase of c-BC(2)N, in which the bond ratio N(C-C):N(B-N):N(B-C):N(C-N) is 3:3:1:1. A number of bonds that can or cannot form a superhard material are qualitatively distinguished, which enables us to explore novel superhard materials by screening possible elemental combinations.

Convenient Relations for the Estimation of Bond Ionicity in A-B Type Compounds.

ERIC Educational Resources Information Center

Barbe, Jacques

1983-01-01

Bond character is directly conditioned by the peculiar capacity of bonded atoms to exchange electrons; such a capacity is clearly illustrated by electronegativity. The determination of bond character using the electronegativity difference between the bonded atoms is discussed and an equation focusing on relationships between bonds is provided. (JN)

Temperature Dependence of Dissociative Electron Attachment to Halogenated Hydrocarbons

NASA Astrophysics Data System (ADS)

Wang, Yicheng; Christophorou, Loucas G.

1996-10-01

Most of the gas mixtures currently in use for plasma processing of semiconductors involve halogenated hydrocarbons such as the strongly electronegative gases CCl4 and CFCl_3, the weakly electronegative gas CF_2Cl2 and the very weakly electronegative gases CHF3 and CF_4. Many dissociation processes are known to occur for these molecules. One of these dissociation reactions which is particularly effective for the strongly electronegative hydrocarbons is dissociative electron attachment. Even for weakly electron attaching gases, molecular dissociation via dissociative electron attachment at low energies can be an efficient dissociation process if the gas temperature is higher than ambient. Dissociative electron attachment is known to increase with increasing temperature above room temperature for many such compounds. In this paper, we report our measurements on the increases of the total electron attachment rate constant for CF_2Cl2 with increasing gas temperature from room temperature to about 600 K. -Research sponsored in part by the U.S. Air Force Wright Laboratory under contract F33615-96-C-2600 with the University of Tennessee. Also, Department of Physics, The University of Tennessee, Knoxville, TN.

Low-density lipoprotein electronegativity is a novel cardiometabolic risk factor.

PubMed

Hsu, Jing-Fang; Chou, Tzu-Chieh; Lu, Jonathan; Chen, Shu-Hua; Chen, Fang-Yu; Chen, Ching-Chu; Chen, Jeffrey L; Elayda, MacArthur; Ballantyne, Christie M; Shayani, Steven; Chen, Chu-Huang

2014-01-01

Low-density lipoprotein (LDL) plays a central role in cardiovascular disease (CVD) development. In LDL chromatographically resolved according to charge, the most electronegative subfraction-L5-is the only subfraction that induces atherogenic responses in cultured vascular cells. Furthermore, increasing evidence has shown that plasma L5 levels are elevated in individuals with high cardiovascular risk. We hypothesized that LDL electronegativity is a novel index for predicting CVD. In 30 asymptomatic individuals with metabolic syndrome (MetS) and 27 healthy control subjects, we examined correlations between plasma L5 levels and the number of MetS criteria fulfilled, CVD risk factors, and CVD risk according to the Framingham risk score. L5 levels were significantly higher in MetS subjects than in control subjects (21.9±18.7 mg/dL vs. 11.2±10.7 mg/dL, P:0.01). The Jonckheere trend test revealed that the percent L5 of total LDL (L5%) and L5 concentration increased with the number of MetS criteria (P<0.001). L5% correlated with classic CVD risk factors, including waist circumference, body mass index, waist-to-height ratio, smoking status, blood pressure, and levels of fasting plasma glucose, triglyceride, and high-density lipoprotein. Stepwise regression analysis revealed that fasting plasma glucose level and body mass index contributed to 28% of L5% variance. The L5 concentration was associated with CVD risk and contributed to 11% of 30-year general CVD risk variance when controlling the variance of waist circumference. Our findings show that LDL electronegativity was associated with multiple CVD risk factors and CVD risk, suggesting that the LDL electronegativity index may have the potential to be a novel index for predicting CVD. Large-scale clinical trials are warranted to test the reliability of this hypothesis and the clinical importance of the LDL electronegativity index.

Low-Density Lipoprotein Electronegativity Is a Novel Cardiometabolic Risk Factor

PubMed Central

Lu, Jonathan; Chen, Shu-Hua; Chen, Fang-Yu; Chen, Ching-Chu; Chen, Jeffrey L.; Elayda, MacArthur; Ballantyne, Christie M.; Shayani, Steven; Chen, Chu-Huang

2014-01-01

Background Low-density lipoprotein (LDL) plays a central role in cardiovascular disease (CVD) development. In LDL chromatographically resolved according to charge, the most electronegative subfraction–L5–is the only subfraction that induces atherogenic responses in cultured vascular cells. Furthermore, increasing evidence has shown that plasma L5 levels are elevated in individuals with high cardiovascular risk. We hypothesized that LDL electronegativity is a novel index for predicting CVD. Methods In 30 asymptomatic individuals with metabolic syndrome (MetS) and 27 healthy control subjects, we examined correlations between plasma L5 levels and the number of MetS criteria fulfilled, CVD risk factors, and CVD risk according to the Framingham risk score. Results L5 levels were significantly higher in MetS subjects than in control subjects (21.9±18.7 mg/dL vs. 11.2±10.7 mg/dL, P:0.01). The Jonckheere trend test revealed that the percent L5 of total LDL (L5%) and L5 concentration increased with the number of MetS criteria (P<0.001). L5% correlated with classic CVD risk factors, including waist circumference, body mass index, waist-to-height ratio, smoking status, blood pressure, and levels of fasting plasma glucose, triglyceride, and high-density lipoprotein. Stepwise regression analysis revealed that fasting plasma glucose level and body mass index contributed to 28% of L5% variance. The L5 concentration was associated with CVD risk and contributed to 11% of 30-year general CVD risk variance when controlling the variance of waist circumference. Conclusion Our findings show that LDL electronegativity was associated with multiple CVD risk factors and CVD risk, suggesting that the LDL electronegativity index may have the potential to be a novel index for predicting CVD. Large-scale clinical trials are warranted to test the reliability of this hypothesis and the clinical importance of the LDL electronegativity index. PMID:25203525

Gender disparity in LDL-induced cardiovascular damage and the protective role of estrogens against electronegative LDL

PubMed Central

2014-01-01

Background Increased levels of the most electronegative type of LDL, L5, have been observed in the plasma of patients with metabolic syndrome (MetS) and ST-segment elevation myocardial infarction and can induce endothelial dysfunction. Because men have a higher predisposition to developing coronary artery disease than do premenopausal women, we hypothesized that LDL electronegativity is increased in men and promotes endothelial damage. Methods L5 levels were compared between middle-aged men and age-matched, premenopausal women with or without MetS. We further studied the effects of gender-influenced LDL electronegativity on aortic cellular senescence and DNA damage in leptin receptor–deficient (db/db) mice by using senescence-associated–β-galactosidase and γH2AX staining, respectively. We also studied the protective effects of 17β-estradiol and genistein against electronegative LDL–induced senescence in cultured bovine aortic endothelial cells (BAECs). Results L5 levels were higher in MetS patients than in healthy subjects (P < 0.001), particularly in men (P = 0.001). LDL isolated from male db/db mice was more electronegative than that from male or female wild-type mice. In addition, LDL from male db/db mice contained abundantly more apolipoprotein CIII and induced more BAEC senescence than did female db/db or wild-type LDL. In the aortas of db/db mice but not wild-type mice, we observed cellular senescence and DNA damage, and the effect was more significant in male than in female db/db mice. Pretreatment with 17β-estradiol or genistein inhibited BAEC senescence induced by male or female db/db LDL and downregulated the expression of lectin-like oxidized LDL receptor-1 and tumor necrosis factor-alpha protein. Conclusion The gender dichotomy of LDL-induced cardiovascular damage may underlie the increased propensity to coronary artery disease in men. PMID:24666525

Complex transition metal hydrides: linear correlation of countercation electronegativity versus T-D bond lengths.

PubMed

Humphries, T D; Sheppard, D A; Buckley, C E

2015-06-30

For homoleptic 18-electron complex hydrides, an inverse linear correlation has been established between the T-deuterium bond length (T = Fe, Co, Ni) and the average electronegativity of the metal countercations. This relationship can be further employed towards aiding structural solutions and predicting physical properties of novel complex transition metal hydrides.

Design and Preliminary Performance Testing of Electronegative Gas Plasma Thruster

NASA Technical Reports Server (NTRS)

Liu, Thomas M.; Schloeder, Natalie R.; Walker, Mitchell L. R.; Polzin, Kurt A.; Dankanich, John W.; Aanesland, Ane

2014-01-01

In classical gridded electrostatic ion thrusters, positively charged ions are generated from a plasma discharge of noble gas propellant and accelerated to provide thrust. To maintain overall charge balance on the propulsion system, a separate electron source is required to neutralize the ion beam as it exits the thruster. However, if high-electronegativity propellant gases (e.g., sulfur hexafluoride) are instead used, a plasma discharge can result consisting of both positively and negatively charged ions. Extracting such electronegative plasma species for thrust generation (e.g., with time-varying, bipolar ion optics) would eliminate the need for a separate neutralizer cathode subsystem. In addition for thrusters utilizing a RF plasma discharge, further simplification of the ion thruster power system may be possible by also using the RF power supply to bias the ion optics. Recently, the PEGASES (Plasma propulsion with Electronegative gases) thruster prototype successfully demonstrated proof-of-concept operations in alternatively accelerating positively and negatively charged ions from a RF discharge of a mixture of argon and sulfur hexafluoride.i In collaboration with NASA Marshall Space Flight Center (MSFC), the Georgia Institute of Technology High-Power Electric Propulsion Laboratory (HPEPL) is applying the lessons learned from PEGASES design and testing to develop a new thruster prototype. This prototype will incorporate design improvements and undergo gridless operational testing and diagnostics checkout at HPEPL in April 2014. Performance mapping with ion optics will be conducted at NASA MSFC starting in May 2014. The proposed paper discusses the design and preliminary performance testing of this electronegative gas plasma thruster prototype.

Relating polarizability to volume, ionization energy, electronegativity, hardness, moments of momentum, and other molecular properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blair, Shamus A.; Thakkar, Ajit J., E-mail: ajit@unb.ca

2014-08-21

Semiquantitative relationships between the mean static dipole polarizability and other molecular properties such as the volume, ionization energy, electronegativity, hardness, and moments of momentum are explored. The relationships are tested using density functional theory computations on the 1641 neutral, ground-state, organic molecules in the TABS database. The best polarizability approximations have median errors under 5%.

Relating polarizability to volume, ionization energy, electronegativity, hardness, moments of momentum, and other molecular properties.

PubMed

Blair, Shamus A; Thakkar, Ajit J

2014-08-21

Semiquantitative relationships between the mean static dipole polarizability and other molecular properties such as the volume, ionization energy, electronegativity, hardness, and moments of momentum are explored. The relationships are tested using density functional theory computations on the 1641 neutral, ground-state, organic molecules in the TABS database. The best polarizability approximations have median errors under 5%.

Highly efficient SO2 capture through tuning the interaction between anion-functionalized ionic liquids and SO2.

PubMed

Wang, Congmin; Zheng, Junjie; Cui, Guokai; Luo, Xiaoyan; Guo, Yan; Li, Haoran

2013-02-11

A strategy to improve SO(2) capture through tuning the electronegativity of the interaction site in ILs has been presented. Two types of imidazolium ionic liquids that include less electronegative sulfur or carbon sites were used for the capture of SO(2), which exhibit extremely highly available capacity, rapid absorption rate and excellent reversibility.

Calculation of surface enthalpy of solids from an ab initio electronegativity based model: case of ice.

PubMed

Douillard, J M; Henry, M

2003-07-15

A very simple route to calculation of the surface energy of solids is proposed because this value is very difficult to determine experimentally. The first step is the calculation of the attractive part of the electrostatic energy of crystals. The partial charges used in this calculation are obtained by using electronegativity equalization and scales of electronegativity and hardness deduced from physical characteristics of the atom. The lattice energies of the infinite crystal and of semi-infinite layers are then compared. The difference is related to the energy of cohesion and then to the surface energy. Very good results are obtained with ice, if one compares with the surface energy of liquid water, which is generally considered a good approximation of the surface energy of ice.

LDL electronegativity index: a potential novel index for predicting cardiovascular disease.

PubMed

Ivanova, Ekaterina A; Bobryshev, Yuri V; Orekhov, Alexander N

2015-01-01

High cardiovascular risk conditions are frequently associated with altered plasma lipoprotein profile, such as elevated low-density lipoprotein (LDL) and LDL cholesterol and decreased high-density lipoprotein. There is, however, accumulating evidence that specific subclasses of LDL may play an important role in cardiovascular disease development, and their relative concentration can be regarded as a more relevant risk factor. LDL particles undergo multiple modifications in plasma that can lead to the increase of their negative charge. The resulting electronegative LDL [LDL(-)] subfraction has been demonstrated to be especially atherogenic, and became a subject of numerous recent studies. In this review, we discuss the physicochemical properties of LDL(-), methods of its detection, atherogenic activity, and relevance of the LDL electronegativity index as a potential independent predictor of cardiovascular risk.

Arbitrary amplitude ion-acoustic solitary waves in electronegative plasmas with electrons featuring Tsallis distribution

NASA Astrophysics Data System (ADS)

Ghebache, Siham; Tribeche, Mouloud

2017-10-01

The problem of arbitrary amplitude ion-acoustic solitary waves (IASWs), which accompany electronegative plasmas having positive ions, negative ions, and nonextensive electrons is addressed. The energy integral equation with a new Sagdeev potential is analyzed to examine the existence regions of the IASWs. Different types of electronegative plasmas inspired from the experimental studies of Ichiki et al. (2001) are discussed. Our results show that in such plasmas IASWs, the amplitude and nature of which depend sensitively on the mass and density ratio of the positive and negative ions as well as the q-nonextensive parameter, can exist. Interestingly, one finds that our plasma model supports the coexistence of smooth rarefactive and spiky compressive IASWs. Our results complement and provide new insights on previously published findings on this problem.

LDL electronegativity index: a potential novel index for predicting cardiovascular disease

PubMed Central

Ivanova, Ekaterina A; Bobryshev, Yuri V; Orekhov, Alexander N

2015-01-01

High cardiovascular risk conditions are frequently associated with altered plasma lipoprotein profile, such as elevated low-density lipoprotein (LDL) and LDL cholesterol and decreased high-density lipoprotein. There is, however, accumulating evidence that specific subclasses of LDL may play an important role in cardiovascular disease development, and their relative concentration can be regarded as a more relevant risk factor. LDL particles undergo multiple modifications in plasma that can lead to the increase of their negative charge. The resulting electronegative LDL [LDL(–)] subfraction has been demonstrated to be especially atherogenic, and became a subject of numerous recent studies. In this review, we discuss the physicochemical properties of LDL(–), methods of its detection, atherogenic activity, and relevance of the LDL electronegativity index as a potential independent predictor of cardiovascular risk. PMID:26357481

The Development Of New Space Charge Compensation Methods For Multi-Components Ion Beam Extracted From ECR Ion Source at IMP

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, L.; Zhao, H.W.; Cao, Y.

2005-03-15

Two new space charge compensation methods developed in IMP are discussed in this paper. There are negative high voltage electrode method (NHVEM) and electronegative charge gas method (EGM). Some valuable experimental data have been achieved, especially using electronegative gas method in O6+ and O7+ dramatic and stable increasing of ion current was observed.

Increased LDL electronegativity in chronic kidney disease disrupts calcium homeostasis resulting in cardiac dysfunction.

PubMed

Chang, Kuan-Cheng; Lee, An-Sheng; Chen, Wei-Yu; Lin, Yen-Nien; Hsu, Jing-Fang; Chan, Hua-Chen; Chang, Chia-Ming; Chang, Shih-Sheng; Pan, Chia-Chi; Sawamura, Tatsuya; Chang, Chi-Tzong; Su, Ming-Jai; Chen, Chu-Huang

2015-07-01

Chronic kidney disease (CKD), an independent risk factor for cardiovascular disease, is associated with abnormal lipoprotein metabolism. We examined whether electronegative low-density lipoprotein (LDL) is mechanistically linked to cardiac dysfunction in patients with early CKD. We compared echocardiographic parameters between patients with stage 2 CKD (n = 88) and normal controls (n = 89) and found that impaired relaxation was more common in CKD patients. Reduction in estimated glomerular filtration rate was an independent predictor of left ventricular relaxation dysfunction. We then examined cardiac function in a rat model of early CKD induced by unilateral nephrectomy (UNx) by analyzing pressure-volume loop data. The time constant of isovolumic pressure decay was longer and the maximal velocity of pressure fall was slower in UNx rats than in controls. When we investigated the mechanisms underlying relaxation dysfunction, we found that LDL from CKD patients and UNx rats was more electronegative than LDL from their respective controls and that LDL from UNx rats induced intracellular calcium overload in H9c2 cardiomyocytes in vitro. Furthermore, chronic administration of electronegative LDL, which signals through lectin-like oxidized LDL receptor-1 (LOX-1), induced relaxation dysfunction in wild-type but not LOX-1(-/-) mice. In in vitro and in vivo experiments, impaired cardiac relaxation was associated with increased calcium transient resulting from nitric oxide (NO)-dependent nitrosylation of SERCA2a due to increases in inducible NO synthase expression and endothelial NO synthase uncoupling. In conclusion, LDL becomes more electronegative in early CKD. This change disrupts SERCA2a-regulated calcium homeostasis, which may be the mechanism underlying cardiorenal syndrome. Copyright © 2015 Elsevier Ltd. All rights reserved.

Relating Bond Angles of Dihalo- and Tetrahydro--Methanes, -Silanes, and -Germanes to Electronegativities

ERIC Educational Resources Information Center

Kirschenbaum, Louis J.; Ruekberg, Ben

2012-01-01

Our previous work correlated bond angles of group V and group VI hydrides (AH[subscript 3]E and AH[subscript 2]E[subscript 2], respectively, where E represents a lone electron pair) to the electronegativities of the atoms using the fraction of s character to relate the two. Here we have extended the correlation to the AH[subscript 2]X[subscript 2]…

A novel method of estimation of lipophilicity using distance-based topological indices: dominating role of equalized electronegativity.

PubMed

Agrawal, Vijay K; Gupta, Madhu; Singh, Jyoti; Khadikar, Padmakar V

2005-03-15

Attempt is made to propose yet another method of estimating lipophilicity of a heterogeneous set of 223 compounds. The method is based on the use of equalized electronegativity along with topological indices. It was observed that excellent results are obtained in multiparametric regression upon introduction of indicator parameters. The results are discussed critically on the basis various statistical parameters.

Symmetry laws improve electronegativity equalization by orders of magnitude and call for a paradigm shift in conceptual density functional theory.

PubMed

von Szentpály, László

2015-03-05

The strict Wigner-Witmer symmetry constraints on chemical bonding are shown to determine the accuracy of electronegativity equalization (ENE) to a high degree. Bonding models employing the electronic chemical potential, μ, as the negative of the ground-state electronegativity, χ(GS), frequently collide with the Wigner-Witmer laws in molecule formation. The violations are presented as the root of the substantially disturbing lack of chemical potential equalization (CPE) in diatomic molecules. For the operational chemical potential, μ(op), the relative deviations from CPE fall between -31% ≤ δμ(op) ≤ +70%. Conceptual density functional theory (cDFT) cannot claim to have operationally (not to mention, rigorously) proven and unified the CPE and ENE principles. The solution to this limitation of cDFT and the symmetry violations is found in substituting μ(op) (i) by Mulliken's valence-state electronegativity, χ(M), for atoms and (ii) its new generalization, the valence-pair-affinity, α(VP), for diatomic molecules. Mulliken's χ(M) is equalized into the α(VP) of the bond, and the accuracy of ENE is orders of magnitude better than that of CPE using μ(op). A paradigm shift replacing the dominance of ground states by emphasizing valence states seems to be in order for conceptual DFT.

Modeling electronegative plasma discharge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lichtenberg, A.J.; Lieberman, M.A.

Macroscopic analytic models for a three-component electronegative gas discharge are developed. Assuming the negative ions to be in Boltzmann equilibrium, a positive ion ambipolar diffusion equation is derived. The discharge consists of an electronegative core and electropositive edges. The electron density in the core is nearly uniform, allowing a parabolic approximation to the plasma profile to be employed. The resulting equilibrium equations are solved analytically and matched to a constant mobility transport model of an electropositive edge plasma. The solutions are compared to a simulation of a parallel-plane r.f. driven oxygen plasma for p = 50 mTorr and n{sub eo}=more » 2.4 x 10{sup 15} m{sup -3}. The ratio {alpha}{sub o} of central negative ion density to electron density, and the electron temperature T{sub e}, found in the simulation, are in reasonable agreement with the values calculated from the model. The model is extended to: (1) low pressures, where a variable mobility model is used in the electropositive edge region; and (2) high {alpha}{sub o} in which the edge region disappears. The inclusion of a second positive ion species, which can be very important in describing electronegative discharges used for materials processing, is a possible extension of the model.« less

Atomic selectivity in dissociative electron attachment to dihalobenzenes.

PubMed

Kim, Namdoo; Sohn, Taeil; Lee, Sang Hak; Nandi, Dhananjay; Kim, Seong Keun

2013-10-21

We investigated electron attachment to three dihalobenzene molecules, bromochlorobenzene (BCB), bromoiodobenzene (BIB) and chloroiodobenzene (CIB), by molecular beam photoelectron spectroscopy. The most prominent product of electron attachment in the anion mass spectra was the atomic fragment of the less electronegative halogen of the two, i.e., Br(-) for BCB and I(-) for BIB and CIB. Photoelectron spectroscopy and ab initio calculations suggested that the approaching electron prefers to attack the less electronegative atom, a seemingly counterintuitive finding but consistent with the mass spectrometric result. For the iodine-containing species BIB and CIB, the photoelectron spectrum consists of bands from both the molecular anion and atomic I(-), the latter of which is produced by photodissociation of the former. Molecular orbital analysis revealed that a large degree of orbital energy reordering takes place upon electron attachment. These phenomena were shown to be readily explained by simple molecular orbital theory and the electronegativity of the halogen atoms.

Effect of substituents on polarizability and hyperpolarizability values of benzimidazole metal complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Praveen, P. A.; Babu, R. Ramesh, E-mail: rampap2k@yahoo.co.in

2016-05-23

In this report, the polarizability and first and second order hyperpolarizability values of bis benzimidazole Zn(II)-2R and bis benzimidazole Cd(II)-2R complexes, with different electron donating moieties R (R= Cl, Br, I, Acetate) were calculated using time dependent Hartree-Fock (TDHF) formalism embedded in MOPAC2012 package. Further the role of substituents on polarizability and hyperpolarizability values is investigated for the first time by analyzing the frontier molecular orbitals of the complexes with respect to the electronegativity of the substituents. It is found that the increase in electronegativity of the substituents correspondingly increases the energy gap of the molecules, which in turn reducesmore » the polarizability values of both Zn and Cd benzimidazole complexes. Similarly, increase in electronegativity reduces the electric quadrupole moments of both the metal complexes, which in turn reduces the hyperpolarizability values.« less

A valence bond study of three-center four-electron pi bonding: electronegativity vs electroneutrality.

PubMed

DeBlase, Andrew; Licata, Megan; Galbraith, John Morrison

2008-12-18

Three-center four-electron (3c4e) pi bonding systems analogous to that of the ozone molecule have been studied using modern valence bond theory. Molecules studied herein consist of combinations of first row atoms C, N, and O with the addition of H atoms where appropriate in order to preserve the 3c4e pi system. Breathing orbital valence bond (BOVB) calculations were preformed at the B3LYP/6-31G**-optimized geometries in order to determine structural weights, pi charge distributions, resonance energies, and pi bond energies. It is found that the most weighted VB structure depends on atomic electronegativity and charge distribution, with electronegativity as the dominant factor. By nature, these systems are delocalized, and therefore, resonance energy is the main contributor to pi bond energies. Molecules with a single dominant VB structure have low resonance energies and therefore low pi bond energies.

Ion acoustic solitons in an electronegative plasma with electron trapping and nonextensivity effects

NASA Astrophysics Data System (ADS)

Ali Shan, S.

2018-03-01

The impact of electron trapping and nonextensivity on the low frequency ion acoustic solitary waves in an electronegative plasma is investigated. The energy integral equation with the Sagdeev truncated approach is derived, which is then solved with the help of suitable parameters and necessary conditions to get the solitary structures. The minimum Mach (M) number needed to calculate the solitary structures is found to be varying under the impact of trapping efficiency determining factor β and entropic index q. The results have been illustrated with the help of physically acceptable parameters and the amplitude of nonlinear solitary structures is found to be modified significantly because of electron trapping efficiency β and entropic index q. This study has been made with reference to Laboratory observation, which can also be helpful in Space and astrophysical plasmas where electronegative plasmas have been reported.

Behavior of collisional sheath in electronegative plasma with q-nonextensive electron distribution

NASA Astrophysics Data System (ADS)

Borgohain, Dima Rani; Saharia, K.

2018-03-01

Electronegative plasma sheath is addressed in a collisional unmagnetized plasma consisting of q-nonextensive electrons, Boltzmann distributed negative ions and cold fluid positive ions. Considering the positive ion-neutral collisions and ignoring the effects of ionization and collisions between negative species and positive ions (neutrals), a modified Bohm sheath criterion and hence floating potential are derived by using multifluid model. Using the modified Bohm sheath criterion, the sheath characteristics such as spatial profiles of density, potential and net space charge density have been numerically investigated. It is found that increasing values of q-nonextensivity, electronegativity and collisionality lead to a decrease of the sheath thickness and an increase of the sheath potential and the net space charge density. With increasing values of the electron temperature to negative ion temperature ratio, the sheath thickness increases and the sheath potential as well as the net space charge density in the sheath region decreases.

General Purpose Electronegativity Relaxation Charge Models Applied to CoMFA and CoMSIA Study of GSK-3 Inhibitors.

PubMed

Tsareva, Daria A; Osolodkin, Dmitry I; Shulga, Dmitry A; Oliferenko, Alexander A; Pisarev, Sergey A; Palyulin, Vladimir A; Zefirov, Nikolay S

2011-03-14

Two fast empirical charge models, Kirchhoff Charge Model (KCM) and Dynamic Electronegativity Relaxation (DENR), had been developed in our laboratory previously for widespread use in drug design research. Both models are based on the electronegativity relaxation principle (Adv. Quantum Chem. 2006, 51, 139-156) and parameterized against ab initio dipole/quadrupole moments and molecular electrostatic potentials, respectively. As 3D QSAR studies comprise one of the most important fields of applied molecular modeling, they naturally have become the first topic to test our charges and thus, indirectly, the assumptions laid down to the charge model theories in a case study. Here these charge models are used in CoMFA and CoMSIA methods and tested on five glycogen synthase kinase 3 (GSK-3) inhibitor datasets, relevant to our current studies, and one steroid dataset. For comparison, eight other different charge models, ab initio through semiempirical and empirical, were tested on the same datasets. The complex analysis including correlation and cross-validation, charges robustness and predictability, as well as visual interpretability of 3D contour maps generated was carried out. As a result, our new electronegativity relaxation-based models both have shown stable results, which in conjunction with other benefits discussed render them suitable for building reliable 3D QSAR models. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hybridization trends for main group elements and expanding the Bent's rule beyond carbon: more than electronegativity.

PubMed

Alabugin, Igor V; Bresch, Stefan; Manoharan, Mariappan

2014-05-22

Trends in hybridization were systematically analyzed through the combination of DFT calculations with NBO analysis for the five elements X (X = B, C, N, O, and F) in 75 HnX-YHm compounds, where Y spans the groups 13-17 of the periods 2-4. This set of substrates probes the flexibility of the hybridization at five atoms X through variations in electronegativity, polarizability, and orbital size of Y. The results illustrate the scope and limitations of the Bent's rule, the classic correlation between electronegativity and hybridization, commonly used in analyzing structural effects in carbon compounds. The rehybridization effects are larger for fluorine- and oxygen-bonds than they are in the similar bonds to carbon. For bonds with the larger elements Y of the lower periods, trends in orbital hybridization depend strongly on both electronegativity and orbital size. For charged species, the effects of substituent orbital size in the more polarizable bonds to heavier elements show a particularly strong response to the charge introduction at the central atom. In the final section, we provide an example of the interplay between hybridization effects with molecular structure and reactivity. In particular, the ability to change hybridization without changes in polarization provides an alternative way to control structure and reactivity, as illustrated by the strong correlation of strain in monosubstituted cyclopropanes with hybridization in the bond to the substituent.

The noble gases: how their electronegativity and hardness determines their chemistry.

PubMed

Furtado, Jonathan; De Proft, Frank; Geerlings, Paul

2015-02-26

The establishment of an internally consistent scale of noble gas electronegativities is a long-standing problem. In the present study, the problem is attacked via the Mulliken definition, which in recent years gained widespread use to its natural appearance in the context of conceptual density functional theory. Basic ingredients of this scale are the electron affinity and the ionization potential. Whereas the latter can be computed routinely, the instability of the anion makes the judicious choice of computational technique for evaluating electron affinities much more tricky. We opted for Puiatti's approach, extrapolating the energy of high ε solvent stabilized anions to the ε = 1 (gas phase) case. The results give negative electron affinity values, monotonically increasing (except for helium which is an outlier in most of the story) to almost zero at eka-radon in agreement with high level calculations. The stability of the B3LYP results is successfully tested both via improving the level of theory (CCSD(T)) and expanding the basis set. Combined with the ionization energies (in good agreement with experiment), an electronegativity scale is obtained displaying (1) a monotonic decrease of χ when going down the periodic table, (2) top values not for the noble gases but for the halogens, as opposed to most (extrapolation) procedures of existing scales, invariably placing the noble gases on top, and (3) noble gases having electronegativities close to the chalcogens. In the accompanying hardness scale (hardly, if ever, discussed in the literature) the noble gases turn out to be by far the farthest the hardest elements, again with a continuous decrease with increasing Z. Combining χ value of the halogens and the noble gases the Ng(δ+)F(δ-) bond polarity emerging from ab initio calculations naturally emerges. In conclusion, the chemistry of the noble gases is for a large part determined by their extreme hardness, equivalent to a high resistance to change in its electronic population coupled to their high electronegativity.

Prediction of boiling points of organic compounds by QSPR tools.

PubMed

Dai, Yi-min; Zhu, Zhi-ping; Cao, Zhong; Zhang, Yue-fei; Zeng, Ju-lan; Li, Xun

2013-07-01

The novel electro-negativity topological descriptors of YC, WC were derived from molecular structure by equilibrium electro-negativity of atom and relative bond length of molecule. The quantitative structure-property relationships (QSPR) between descriptors of YC, WC as well as path number parameter P3 and the normal boiling points of 80 alkanes, 65 unsaturated hydrocarbons and 70 alcohols were obtained separately. The high-quality prediction models were evidenced by coefficient of determination (R(2)), the standard error (S), average absolute errors (AAE) and predictive parameters (Qext(2),RCV(2),Rm(2)). According to the regression equations, the influences of the length of carbon backbone, the size, the degree of branching of a molecule and the role of functional groups on the normal boiling point were analyzed. Comparison results with reference models demonstrated that novel topological descriptors based on the equilibrium electro-negativity of atom and the relative bond length were useful molecular descriptors for predicting the normal boiling points of organic compounds. Copyright © 2013 Elsevier Inc. All rights reserved.

Use of infrared spectroscopy for the determination of electronegativity of rare earth elements.

PubMed

Frost, Ray L; Erickson, Kristy L; Weier, Matt L; McKinnon, Adam R; Williams, Peter A; Leverett, Peter

2004-07-01

Infrared spectroscopy has been used to study a series of synthetic agardite minerals. Four OH stretching bands are observed at around 3568, 3482, 3362, and 3296 cm(-1). The first band is assigned to zeolitic, non-hydrogen-bonded water. The band at 3296 cm(-1) is assigned to strongly hydrogen-bonded water with an H bond distance of 2.72 A. The water in agardites is better described as structured water and not as zeolitic water. Two bands at around 999 and 975 cm(-1) are assigned to OH deformation modes. Two sets of AsO symmetric stretching vibrations were found and assigned to the vibrational modes of AsO(4) and HAsO(4) units. Linear relationships between positions of infrared bands associated with bonding to the OH units and the electronegativity of the rare earth elements were derived, with correlation coefficients >0.92. These linear functions were then used to calculate the electronegativity of Eu, for which a value of 1.1808 on the Pauling scale was found.

On electron heating in a low pressure capacitively coupled oxygen discharge

NASA Astrophysics Data System (ADS)

Gudmundsson, J. T.; Snorrason, D. I.

2017-11-01

We use the one-dimensional object-oriented particle-in-cell Monte Carlo collision code oopd1 to explore the charged particle densities, the electronegativity, the electron energy probability function, and the electron heating mechanism in a single frequency capacitively coupled oxygen discharge, when the applied voltage amplitude is varied. We explore discharges operated at 10 mTorr, where electron heating within the plasma bulk (the electronegative core) dominates, and at 50 mTorr, where sheath heating dominates. At 10 mTorr, the discharge is operated in a combined drift-ambipolar and α-mode, and at 50 mTorr, it is operated in the pure α-mode. At 10 mTorr, the effective electron temperature is high and increases with increased driving voltage amplitude, while at 50 mTorr, the effective electron temperature is much lower, in particular, within the electronegative core, where it is roughly 0.2-0.3 eV, and varies only a little with the voltage amplitude.

Explanation of the barrier heights of graphene Schottky contacts by the MIGS-and-electronegativity concept

NASA Astrophysics Data System (ADS)

Mönch, Winfried

2016-09-01

Graphene-semiconductor contacts exhibit rectifying properties and, in this respect, they behave in exactly the same way as a "conventional" metal-semiconductor or Schottky contacts. It will be demonstrated that, as often assumed, the Schottky-Mott rule does not describe the reported barrier heights of graphene-semiconductor contacts. With "conventional" Schottky contacts, the same conclusion was reached already in 1940. The physical reason is that the Schottky-Mott rule considers no interaction between the metal and the semiconductor. The barrier heights of "conventional" Schottky contacts were explained by the continuum of metal-induced gap states (MIGSs), where the differences of the metal and semiconductor electronegativities describe the size and the sign of the intrinsic electric-dipoles at the interfaces. It is demonstrated that the MIGS-and-electronegativity concept unambiguously also explains the experimentally observed barrier heights of graphene Schottky contacts. This conclusion includes also the barrier heights reported for MoS2 Schottky contacts with "conventional" metals as well as with graphene.

Evolución en el tiempo de las relaciones Masa-Luminosidad y Corrección Bolométrica y Temperatura Efectiva contra Índice de Color

NASA Astrophysics Data System (ADS)

Miloni, L. A.; Camperi, J. A.

Analizamos la evolución que en los últimos 70 años han tenido las relaciones M-L, BC vs CI y Teff vs CI. Se discuten las causas de esa evolución, se trata de incorporar los valores más modernos disponibles discutiendo su calidad y se deducen las relaciones que actualmente deberían ser las más confiables. Destacamos los puntos en los que estas relaciones continúan estando pobremente definidas y sería deseable mejorar en el futuro próximo.

Exploring the Reactivity Trends in the E2 and SN2 Reactions of X(-) + CH3CH2Cl (X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3).

PubMed

Wu, Xiao-Peng; Sun, Xiao-Ming; Wei, Xi-Guang; Ren, Yi; Wong, Ning-Bew; Li, Wai-Kee

2009-06-09

The reactivity order of 12 anions toward ethyl chloride has been investigated by using the G2(+) method, and the competitive E2 and SN2 reactions are discussed and compared. The reactions studied are X(-) + CH3CH2Cl → HX + CH2═CH2 + Cl(-) and X(-) + CH3CH2Cl → CH3CH2X + Cl(-), with X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3. Our results indicate that there is no general and straightforward relationship between the overall barriers and the proton affinity (PA) of X(-); instead, discernible linear correlations only exist for the X's within the same group of the periodic table. Similar correlations are also found with the electronegativity of central atoms in X, deformation energy of the E2 transition state (TS), and the overall enthalpy of reaction. It is revealed that the electronegativity will significantly affect the barrier height, and a more electronegative X will stabilize the E2 and SN2 transition states. Multiple linear regression analysis shows that there is a reasonable linear correlation between E2 (or SN2) overall barriers and the linear combination of PA of X(-) and electronegativity of the central atom.

Effect of the electronegativity on the electrosorption selectivity of anions during capacitive deionization.

PubMed

Sun, Zhumei; Chai, Liyuan; Liu, Mingshi; Shu, Yude; Li, Qingzhu; Wang, Yunyan; Qiu, Dingfan

2018-03-01

The effect of electronegativity on the electrosorption selectivity of anions during capacitive deionization was investigated via a combination of experimental and theoretical studies. A model was developed based on chemical thermodynamics and the classic Stern's model to reveal the role of the anode potential and to describe electrosorption selectivity behavior during capacitive deionization. The effects of the anode potential on the adsorption of Cl - and ReO 4 - were studied and the obtained data were used to validate the model. Using the validated model, the effects of the anode potential and electronegativity of various anions, including Cl - , ReO 4 - , SO 4 2- and NO 3 - were assessed. The experimental results for the electrosorption of Cl - and ReO 4 - corresponded well with the developed model. The electrosorption capacity demonstrates a logarithmic relationship with the anode potential. The model showed that the electronegativity significantly affects the selectivity. In a mixed Cl - , ReO 4 - , SO 4 2- and NO 3 - solution, ReO 4 - was preferentially adsorbed over the other three anions, and the following selectivity was exhibited: ReO 4 -  > NO 3 -  > Cl -  > SO 4 2- . The results showed that the effect of flow rates on the electrosorption selectivity can be considered negligible when the flow rates are higher than 112 mL min -1 . The anions selectivity can be further enhanced by increasing the anode potential, and electrosorption selectivity is no appreciable decline after 6 experiments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electronegativity, charge transfer, crystal field strength, and the point charge model revisited.

PubMed

Tanner, Peter A; Ning, Lixin

2013-02-21

Although the optical spectra of LnCl(6)(3-) systems are complex, only two crystal field parameters, B(40) and B(60), are required to model the J-multiplet crystal field splittings in octahedral symmetry. It is found that these parameters exhibit R(-5) and R(-7) dependence, respectively, upon the ionic radius Ln(3+)(VI), but not upon the Ln-Cl distance. More generally, the crystal field strengths of LnX(6) systems (X = Br, Cl, F, O) exhibit linear relationships with ligand electronegativity, charge transfer energy, and fractional ionic character of the Ln-X bond.

Numerical simulations used for a validity check on the laser induced photo-detachment diagnostic method in electronegative plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oudini, N.; Taccogna, F.; Bendib, A.

2014-06-15

Laser photo-detachment is used as a method to measure or determine the negative ion density and temperature in electronegative plasmas. In essence, the method consists of producing an electropositive channel (negative ion free region) via pulsed laser photo-detachment within an electronegative plasma bulk. Electrostatic probes placed in this channel measure the change in the electron density. A second pulse might be used to track the negative ion recovery. From this, the negative ion density and temperature can be determined. We study the formation and relaxation of the electropositive channel via a two-dimensional Particle-In-Cell/Mote Carlo collision model. The simulation is mainlymore » carried out in a Hydrogen plasma with an electronegativity of α = 1, with a parametric study for α up to 20. The temporal and spatial evolution of the plasma potential and the electron densities shows the formation of a double layer (DL) confining the photo-detached electrons within the electropositive channel. This DL evolves into two fronts that move in the opposite directions inside and outside of the laser spot region. As a consequence, within the laser spot region, the background and photo-detached electron energy distribution function relaxes/thermalizes via collisionless effects such as Fermi acceleration and Landau damping. Moreover, the simulations show that collisional effects and the DL electric field strength might play a non-negligible role in the negative ion recovery within the laser spot region, leading to a two-temperature negative ion distribution. The latter result might have important effects in the determination of the negative ion density and temperature from laser photo detachment diagnostic.« less

Asymmetry and Electronegativity in the Electron Capture Activation of the Se-Se Bond: σ*(Se-Se) vs σ*(Se-X).

PubMed

Gámez, José A; Yáñez, Manuel

2010-10-12

The effects of electron capture on the structure of XSeSeX' diselenide derivatives in which the substituents attached to the selenium atoms have different electronegativities have been investigated at different levels of theory, namely, DFT, MP2, CCSD, G2, and CASSCF/CASPT2. An analysis of the bonding changes upon electron attachment shows that when the diselenides bear low-electronegativity substituents, the Se-Se bond becomes activated upon electron capture, as previous studies have shown. However, this is no longer the case for very electronegative substituents, where this bond remains practically unaltered and is the Se-X bond the one which becomes strongly activated through a preferential population of the σ*(Se-X) antibonding orbital rather than the σ*(Se-Se) one. When this is the case, several anionic species are also encountered, namely, stretched, bent, and book structures. The present findings are similar to those obtained for a series of analogous disulfide compounds, which points out that these results are not unique and could be extrapolated to a wider range of compounds than the ones covered here. The Se-Se (Se-X) linkage in CH3SeSeOH, CH3SeSeF, FSeSeOH, and FSeSeF bears some of the characteristics of the so-called charge-shift bonds, with a clear charge fluctuation between both selenium atoms. This is more evident in their anions where the bonding reflects the important contribution of the ionic resonant forms Se-Se(-) ↔ (-)Se-Se vs the covalent component Se∴Se. This resonance changes with the nature of the substituents but also depends on the asymmetry of the substitution.

Hammett equation and generalized Pauling's electronegativity equation.

PubMed

Liu, Lei; Fu, Yao; Liu, Rui; Li, Rui-Qiong; Guo, Qing-Xiang

2004-01-01

Substituent interaction energy (SIE) was defined as the energy change of the isodesmic reaction X-spacer-Y + H-spacer-H --> X-spacer-H + H-spacer-Y. It was found that this SIE followed a simple equation, SIE(X,Y) = -ksigma(X)sigma(Y), where k was a constant dependent on the system and sigma was a certain scale of electronic substituent constant. It was demonstrated that the equation was applicable to disubstituted bicyclo[2.2.2]octanes, benzenes, ethylenes, butadienes, and hexatrienes. It was also demonstrated that Hammett's equation was a derivative form of the above equation. Furthermore, it was found that when spacer = nil the above equation was mathematically the same as Pauling's electronegativity equation. Thus it was shown that Hammett's equation was a derivative form of the generalized Pauling's electronegativity equation and that a generalized Pauling's electronegativity equation could be utilized for diverse X-spacer-Y systems. In addition, the total electronic substituent effects were successfully separated into field/inductive and resonance effects in the equation SIE(X,Y) = -k(1)F(X)F(Y) - k(2)R(X)R(Y) - k(3)(F(X)R(Y) + R(X)F(Y)). The existence of the cross term (i.e., F(X)R(Y) and R(X)F(Y)) suggested that the field/inductive effect was not orthogonal to the resonance effect because the field/inductive effect from one substituent interacted with the resonance effect from the other. Further studies on multi-substituted systems suggested that the electronic substituent effects should be pairwise and additive. Hence, the SIE in a multi-substituted system could be described using the equation SIE(X1, X2, ..., Xn) = Sigma(n-1)(i=1)Sigma(n)(j=i+1)k(ij)sigma(X)isigma(X)j.

Numerical simulations used for a validity check on the laser induced photo-detachment diagnostic method in electronegative plasmas

NASA Astrophysics Data System (ADS)

Oudini, N.; Taccogna, F.; Bendib, A.; Aanesland, A.

2014-06-01

Laser photo-detachment is used as a method to measure or determine the negative ion density and temperature in electronegative plasmas. In essence, the method consists of producing an electropositive channel (negative ion free region) via pulsed laser photo-detachment within an electronegative plasma bulk. Electrostatic probes placed in this channel measure the change in the electron density. A second pulse might be used to track the negative ion recovery. From this, the negative ion density and temperature can be determined. We study the formation and relaxation of the electropositive channel via a two-dimensional Particle-In-Cell/Mote Carlo collision model. The simulation is mainly carried out in a Hydrogen plasma with an electronegativity of α = 1, with a parametric study for α up to 20. The temporal and spatial evolution of the plasma potential and the electron densities shows the formation of a double layer (DL) confining the photo-detached electrons within the electropositive channel. This DL evolves into two fronts that move in the opposite directions inside and outside of the laser spot region. As a consequence, within the laser spot region, the background and photo-detached electron energy distribution function relaxes/thermalizes via collisionless effects such as Fermi acceleration and Landau damping. Moreover, the simulations show that collisional effects and the DL electric field strength might play a non-negligible role in the negative ion recovery within the laser spot region, leading to a two-temperature negative ion distribution. The latter result might have important effects in the determination of the negative ion density and temperature from laser photo detachment diagnostic.

The Nature of the Idealized Triple Bonds Between Principal Elements and the σ Origins of Trans-Bent Geometries-A Valence Bond Study.

PubMed

Ploshnik, Elina; Danovich, David; Hiberty, Philippe C; Shaik, Sason

2011-04-12

We describe herein a valence bond (VB) study of 27 triply bonded molecules of the general type X≡Y, where X and Y are main element atoms/fragments from groups 13-15 in the periodic table. The following conclusions were derived from the computational data: (a) Single π-bond and double π-bond energies for the entire set correlate with the "molecular electronegativity", which is the sum of the X and Y electronegativites for X≡Y. The correlation with the molecular electronegativity establishes a simple rule of periodicity: π-bonding strength generally increases from left to right in a period and decreases down a column in the periodic table. (b) The σ frame invariably prefers trans bending, while π-bonding gets destabilized and opposes the trans distortion. In HC≡CH, the π-bonding destabilization overrides the propensity of the σ frame to distort, while in the higher row molecules, the σ frame wins out and establishes trans-bent molecules with 2(1)/2 bonds, in accord with recent experimental evidence based on solid state (29)Si NMR of the Sekiguchi compound. Thus, in the trans-bent molecules "less bonds pay more". (c) All of the π bonds show significant bonding contributions from the resonance energy due to covalent-ionic mixing. This quantity is shown to correlate linearly with the corresponding "molecular electronegativity" and to reflect the mechanism required to satisfy the equilibrium condition for the bond. The π bonds for molecules possessing high molecular electronegativity are charge-shift bonds, wherein bonding is dominated by the resonance energy of the covalent and ionic forms, rather than by either form by itself.

Modeling the magnetic properties of lanthanide complexes: relationship of the REC parameters with Pauling electronegativity and coordination number.

PubMed

Baldoví, José J; Gaita-Ariño, Alejandro; Coronado, Eugenio

2015-07-28

In a previous study, we introduced the Radial Effective Charge (REC) model to study the magnetic properties of lanthanide single ion magnets. Now, we perform an empirical determination of the effective charges (Zi) and radial displacements (Dr) of this model using spectroscopic data. This systematic study allows us to relate Dr and Zi with chemical factors such as the coordination number and the electronegativities of the metal and the donor atoms. This strategy is being used to drastically reduce the number of free parameters in the modeling of the magnetic and spectroscopic properties of f-element complexes.

Beyond electronegativity and local hardness: Higher-order equalization criteria for determination of a ground-state electron density.

PubMed

Ayers, Paul W; Parr, Robert G

2008-08-07

Higher-order global softnesses, local softnesses, and softness kernels are defined along with their hardness inverses. The local hardness equalization principle recently derived by the authors is extended to arbitrary order. The resulting hierarchy of equalization principles indicates that the electronegativity/chemical potential, local hardness, and local hyperhardnesses all are constant when evaluated for the ground-state electron density. The new equalization principles can be used to test whether a trial electron density is an accurate approximation to the true ground-state density and to discover molecules with desired reactive properties, as encapsulated by their chemical reactivity indicators.

Metal-atom Interactions and Clustering in Organic Semiconductor Systems

NASA Astrophysics Data System (ADS)

Tomita, Yoko; Park, Tea-uk; Nakayama, Takashi

2017-07-01

The interatomic interactions and clustering of metal atoms have been studied by first-principles calculations in graphene, pentacene, and polyacetylene as representative organic systems. It is shown that long-range repulsive Coulomb interaction appears between metal atoms with small electronegativity such as Al due to their ionization on host organic molecules, inducing their scattered distribution in organic systems. On the other hand, metal atoms with large electronegativity such as Au are weakly bonded to organic molecules, easily diffuse in molecular solids, and prefer to combine with each other owing to their short-range strong metallic-bonding interaction, promoting metal cluster generation in organic systems.

Pauling's electronegativity equation and a new corollary accurately predict bond dissociation enthalpies and enhance current understanding of the nature of the chemical bond.

PubMed

Matsunaga, Nikita; Rogers, Donald W; Zavitsas, Andreas A

2003-04-18

Contrary to other recent reports, Pauling's original electronegativity equation, applied as Pauling specified, describes quite accurately homolytic bond dissociation enthalpies of common covalent bonds, including highly polar ones, with an average deviation of +/-1.5 kcal mol(-1) from literature values for 117 such bonds. Dissociation enthalpies are presented for more than 250 bonds, including 79 for which experimental values are not available. Some previous evaluations of accuracy gave misleadingly poor results by applying the equation to cases for which it was not derived and for which it should not reproduce experimental values. Properly interpreted, the results of the equation provide new and quantitative insights into many facets of chemistry such as radical stabilities, factors influencing reactivity in electrophilic aromatic substitutions, the magnitude of steric effects, conjugative stabilization in unsaturated systems, rotational barriers, molecular and electronic structure, and aspects of autoxidation. A new corollary of the original equation expands its applicability and provides a rationale for previously observed empirical correlations. The equation raises doubts about a new bonding theory. Hydrogen is unique in that its electronegativity is not constant.

a Computational Approach to Explore Protein Translocation Through Type III Secretion Apparatus

NASA Astrophysics Data System (ADS)

Rathinavelan, Thenmalarchelvi; Im, Wonpil

2010-01-01

Many Gram-negative bacteria initiate infections by injecting effector proteins into host cells through the type III secretion apparatus (TTSA) that is comprised of a basal body, a needle, and a tip. The needle channel is formed by the assembly of a single needle protein. To explore the export mechanisms of MxiH needle protein through the needle of Shigella flexneri, an essential step during needle assembly, we have performed steered molecular dynamics simulations in implicit solvent. Interestingly, the electronegative channel interior creates an energy barrier for MxiH to enter the channel, while the same may facilitate the ejection of the effectors into host cells. Structurally-known basal regions and ATPase underneath the basal region have also such electronegative interior, while effector proteins have considerable electronegative patches on their surfaces. Based on these observations, we propose a repulsive electrostatic mechanism for protein translocation through the TTSA. This mechanism is supported by the suggestion that an ATPase is required for protein translocation through these nanomachines, which may provide the energy to overcome the initial electrostatic energy barrier. A similar mechanism may be applicable to macromolecular channels in other secretion systems or viruses through which proteins or nucleic acids are transported.

Electronic behaviour of Au-Pt alloys and the 4f binding energy shift anomaly in Au bimetallics- X-ray spectroscopy studies

NASA Astrophysics Data System (ADS)

Wang, Dongniu; Cui, Xiaoyu; Xiao, Qunfeng; Hu, Yongfeng; Wang, Zhiqiang; Yiu, Y. M.; Sham, T. K.

2018-06-01

The electronic structure and charge redistribution of 6s conduction charge and 5d charge in Au and Pt alloys, Au9Pt and AuPt9 have been investigated using a charge compensation model. It is found that, both the Au and Pt 4f binding energy (BE) exhibits a negative shift in the alloys relatively to the pure metal in apparent disagreement with electroneutrality considerations (Au is the most electronegative metallic element); more interestingly, the negative Au 4f BE shift in Au-Pt alloy is in contrast to previous observations for a large number of Au bimetallic systems with more electropositive hosts in which the more electropositive the host„ the more positive the Au 4f BE shift. This anomaly is counter intuitive to electronegativity considerations. This dilemma was resolved by the charge compensation model in which both electronegativity and charge neutrality can be satisfied and the overall charge flow δ, onto Au is small and positive and δ arises from charge flow of 6s conduction charge, Δnc onto Au site, which is partially compensated by the depletion of 6d charge Δnd at the Au site (δ = Δnc+ Δnd ˜0.1 >0). The much larger Coulomb interaction between 4f and 5d than that between 4f and 6s results in positive 4f BE shifts. The Au 4f BE shift in Au-Pt alloys together with 193Au Mössbauer data were used in the charge compensation model analysis which shows that the model is still valid in that the Au 4f shift in Au-Pt alloy arises from mainly conduction charge gain with little depletion of d charge at the Au site. The model also works for Pt. The Au and Pt 5d character in the alloys have been examined with valence band spectra which show both maintain their d characteristic in dilute alloys with Pt d piling up at the Fermi level, and the top of the Au valence band being pushed toward the Fermi level; this is confirmed with DFT densities of state calculations. When Pt is diluted in Au, it gains d charge as evident from the reduction in whiteline intensity at the Pt L3-edge XANES. What emerges from this work is a picture in which the s-d charge compensation in Au bimetallic alloys is triggered by electronegativity difference between Au and the host. For Au-Pt and Au-Pd systems, the difference in electronegativity is very small, conduction charge transfer dominates, and the Au 4f shift is negative whereas in most Au bimetallics, the larger the electronegativity difference, the larger the compensation and the larger the Au 4f shifts.

Electronegative Gas Thruster

NASA Technical Reports Server (NTRS)

Dankanich, John; Polzin, Kurt; Walker, Mitchell

2015-01-01

The project is an international collaboration and academic partnership to mature an innovative electric propulsion thruster concept to Technology Research Level-3 (TRL-3) through direct thrust measurement. The project includes application assessment of the technology ranging from small spacecraft to high power. The Plasma propulsion with Electronegative GASES(PEGASES) basic proof of concept has been matured to TRL-2 by Ane Aanesland of Laboratoire de Physique des Plasma at Ecole Polytechnique. The concept has advantages through eliminating the neutralizer requirement and should yield longer life and lower cost over conventional gridded ion engines. The objective of this research is to validate the proof of concept through the first direct thrust measurements and mature the concept to TRL-3.

Electronegative plasma diagnostic by laser photo-detachment combined with negatively biased Langmuir probe

NASA Astrophysics Data System (ADS)

Oudini, N.; Sirse, N.; Taccogna, F.; Ellingboe, A. R.; Bendib, A.

2018-05-01

We propose a new technique for diagnosing negative ion properties using Langmuir probe assisted pulsed laser photo-detachment. While the classical technique uses a laser pulse to convert negative ions into electron-atom pairs and a positively biased Langmuir probe tracking the change of electron saturation current, the proposed method uses a negatively biased Langmuir probe to track the temporal evolution of positive ion current. The negative bias aims to avoid the parasitic electron current inherent to probe tip surface ablation. In this work, we show through analytical and numerical approaches that, by knowing electron temperature and performing photo-detachment at two different laser wavelengths, it is possible to deduce plasma electronegativity (ratio of negative ion to electron densities) α, and anisothermicity (ratio of electron to negative ion temperatures) γ-. We present an analytical model that links the change in the collected positive ion current to plasma electronegativity and anisothermicity. Particle-In-Cell simulation is used as a numerical experiment covering a wide range of α and γ- to test the new analysis technique. The new technique is sensitive to α in the range 0.5 < α < 10 and yields γ- for large α, where negative ion flux affects the probe sheath behavior, typically α > 1.

Electronegative Gas Thruster - Direct Thrust Measurement Project

NASA Technical Reports Server (NTRS)

Dankanich, John (Principal Investigator); Aanesland, Ane; Polzin, Kurt; Walker, Mitchell

2015-01-01

This effort is an international collaboration and academic partnership to mature an innovative electric propulsion (EP) thruster concept to TRL 3 through direct thrust measurement. The initial target application is for Small Satellites, but can be extended to higher power. The Plasma propulsion with Electronegative GASES (PEGASES) concept simplifies ion thruster operation, eliminates a neutralizer requirement and should yield longer life capabilities and lower cost implementation over conventional gridded ion engines. The basic proof-of concept has been demonstrated and matured to TRL 2 over the past several years by researchers at the Laboratoire de Physique des Plasma in France. Due to the low maturity of the innovation, there are currently no domestic investments in electronegative gas thrusters anywhere within NASA, industry or academia. The end product of this Center Innovation Fund (CIF) project will be a validation of the proof-of-concept, maturation to TRL 3 and technology assessment report to summarize the potential for the PEGASES concept to supplant the incumbent technology. Information exchange with the foreign national will be one-way with the exception of the test results. Those test results will first go through a standard public release ITAR/export control review, and the results will be presented in a public technical forum, and the results will be presented in a public technical forum.

A Repulsive Electrostatic Mechanism for Protein Export through the Type III Secretion Apparatus

PubMed Central

Rathinavelan, Thenmalarchelvi; Zhang, Lingling; Picking, Wendy L.; Weis, David D.; De Guzman, Roberto N.; Im, Wonpil

2010-01-01

Abstract Many Gram-negative bacteria initiate infections by injecting effector proteins into host cells through the type III secretion apparatus, which is comprised of a basal body, a needle, and a tip. The needle channel is formed by the assembly of a single needle protein. To explore the export mechanisms of MxiH needle protein through the needle of Shigella flexneri, an essential step during needle assembly, we have performed steered molecular dynamics simulations in implicit solvent. The trajectories reveal a screwlike rotation motion during the export of nativelike helix-turn-helix conformations. Interestingly, the channel interior with excessive electronegative potential creates an energy barrier for MxiH to enter the channel, whereas the same may facilitate the ejection of the effectors into host cells. Structurally known basal regions and ATPase underneath the basal region also have electronegative interiors. Effector proteins also have considerable electronegative potential patches on their surfaces. From these observations, we propose a repulsive electrostatic mechanism for protein translocation through the type III secretion apparatus. Based on this mechanism, the ATPase activity and/or proton motive force could be used to energize the protein translocation through these nanomachines. A similar mechanism may be applicable to macromolecular channels in other secretion systems or viruses through which proteins or nucleic acids are transported. PMID:20141759

Enhancing the performance of NaNbO3 triboelectric nanogenerators by dielectric modulation and electronegative modification

NASA Astrophysics Data System (ADS)

Lai, Meihui; Cheng, Lu; Xi, Yi; Wu, Yinghui; Hu, Chengguo; Guo, Hengyu; Du, Bolun; Liu, Guanlin; Liu, Qipeng; Liu, Ruchuan

2018-01-01

Increasing the triboelectric charge density on the friction layer of polydimethylsiloxane (PDMS) is a basic approach towards improving the output performance of a triboelectric nanogenerator (TENG). Most previous work focuses on the surface structure or dielectric properties, nonetheless, a few studies have focused on electronegative modification. NaNbO3-PDMS TENG (N-TENG) devices are fabricated by dispersing cubic NaNbO3, which is a lead-free piezoelectric material with molecular oxygen dangling bonds on the surface of the crystal, into the PDMS at different mass ratios. When the mass ratio is 7 wt%, the maximum output performance of the N-TENG is obtained. The open-circuit voltage is 550 V, the short-circuit current is 16 µA, and the effective power densities reach up to 5.5 W m-2 at a load resistance of ~100 MΩ. The N-TENG has been used to assemble self-powered electronic watches and illuminate commercial light-emitting diodes, respectively. Its fundamental mechanism has also been discussed in detail from the perspective of dielectric modulation and electronegative modification. This N-TENG technology is revealed to be a splendid candidate for application in large-scale device fabrication, flexible sensors and biological devices thanks to its easy fabrication process, low consumption, high output power density and biocompatibility.

Role of Metal Electronegativity in the Dehydrogenation Thermodynamics and Kinetics of Composite Metal Borohydride-LiNH2 Hydrogen Storage Materials.

PubMed

Bai, Ying; Pei, Ziwei; Wu, Feng; Wu, Chuan

2018-03-21

The composites of M(BH 4 ) n -LiNH 2 (1/2 n molar ratio, n = 1 or 2, M = Ca, Mg, Li) were synthesized by liquid ball milling. Samples were characterized by X-ray diffraction, thermogravimetry-differential thermal analysis-mass spectroscopy (TG-DTA-MS), and kinetic models (Achar differential/Coats-Redfern integral method). The higher-electronegativity metal M in M(BH 4 ) n -4LiNH 2 (M = Ca, Mg) samples not only enables [BH 4 ] - group to release easily, so as to facilitate the interaction of [BH 4 ] - and [NH 2 ] - groups, but also restrains the NH 3 release and slightly decreases the onset dehydrogenation temperature concluded by TG-MS. Moreover, in stage 1 (200-350 °C), the kinetics performances of M(BH 4 ) n -4LiNH 2 (M = Ca, Mg) samples are distinctly improved, that is, the activation energies of them are reduced by ca. 30% compared to those of sample LiBH 4 -2LiNH 2 . The outstanding contribution of the replacement of M(BH 4 ) n with high-electronegativity metal ion is to both improve the kinetics performance by changing the kinetics mechanism and decrease the temperature range of the initial dehydrogenation region.

One-dimensional Ar-SF{sub 6} hydromodel at low-pressure in e-beam generated plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrov, George M., E-mail: george.petrov@nrl.navy.mil; Boris, David R.; Petrova, Tzvetelina B.

2016-03-15

A one-dimensional steady-state hydrodynamic model of electron beam generated plasmas produced in Ar-SF{sub 6} mixtures at low pressure in a constant magnetic field was developed. Simulations were performed for a range of SF{sub 6} partial pressures at constant 30 mTorr total gas pressure to determine the spatial distribution of species densities and fluxes. With the addition of small amount of SF{sub 6} (∼1%), the confining electrostatic field sharply decreases with respect to the pure argon case. This effect is due to the applied magnetic field inhibiting electron diffusion. The hallmark of electronegative discharge plasmas, positive ion—negative ion core and positivemore » ion—electron edge, was not observed. Instead, a plasma with large electronegativity (∼100) is formed throughout the volume, and only a small fraction (≈30%) of the parent SF{sub 6} molecules were dissociated to F{sub 2}, SF{sub 2}, and SF{sub 4}. Importantly, F radical densities were found to be very low, on the order of the ion density. Model predictions for the electron density, ion density, and plasma electronegativity are in good agreement with experimental data over the entire range of SF{sub 6} concentrations investigated.« less

Hydration of Li+ -ion in atom-bond electronegativity equalization method-7P water: a molecular dynamics simulation study.

PubMed

Li, Xin; Yang, Zhong-Zhi

2005-02-22

We have carried out molecular dynamics simulations of a Li(+) ion in water over a wide range of temperature (from 248 to 368 K). The simulations make use of the atom-bond electronegativity equalization method-7P water model, a seven-site flexible model with fluctuating charges, which has accurately reproduced many bulk water properties. The recently constructed Li(+)-water interaction potential through fitting to the experimental and ab initio gas-phase binding energies and to the measured structures for Li(+)-water clusters is adopted in the simulations. ABEEM was proposed and developed in terms of partitioning the electron density into atom and bond regions and using the electronegativity equalization method (EEM) and the density functional theory (DFT). Based on a combination of the atom-bond electronegativity equalization method and molecular mechanics (ABEEM/MM), a new set of water-water and Li(+)-water potentials, successfully applied to ionic clusters Li(+)(H(2)O)(n)(n=1-6,8), are further investigated in an aqueous solution of Li(+) in the present paper. Two points must be emphasized in the simulations: first, the model allows for the charges on the interacting sites fluctuating as a function of time; second, the ABEEM-7P model has applied the parameter k(lp,H)(R(lp,H)) to explicitly describe the short-range interaction of hydrogen bond in the hydrogen bond interaction region, and has a new description for the hydrogen bond. The static, dynamic, and thermodynamic properties have been studied in detail. In addition, at different temperatures, the structural properties such as radial distribution functions, and the dynamical properties such as diffusion coefficients and residence times of the water molecules in the first hydration shell of Li(+), are also simulated well. These simulation results show that the ABEEM/MM-based water-water and Li(+)-water potentials appear to be robust giving the overall characteristic hydration properties in excellent agreement with experiments and other molecular dynamics simulations on similar system.

Electronegative Low-density Lipoprotein Increases Coronary Artery Disease Risk in Uremia Patients on Maintenance Hemodialysis

PubMed Central

Chang, Chiz-Tzung; Wang, Guei-Jane; Kuo, Chin-Chi; Hsieh, Ju-Yi; Lee, An-Sean; Chang, Chia-Ming; Wang, Chun-Cheng; Shen, Ming-Yi; Huang, Chiu-Ching; Sawamura, Tatsuya; Yang, Chao-Yuh; Stancel, Nicole; Chen, Chu-Huang

2016-01-01

Abstract Electronegative low-density lipoprotein (LDL) is a recognized factor in the pathogenesis of coronary artery disease (CAD) in the general population, but its role in the development of CAD in uremia patients is unknown. L5 is the most electronegative subfraction of LDL isolated from human plasma. In this study, we examined the distribution of L5 (L5%) and its association with CAD risk in uremia patients. The LDL of 39 uremia patients on maintenance hemodialysis and 21 healthy controls was separated into 5 subfractions, L1–L5, with increasing electronegativity. We compared the distribution and composition of plasma L5 between uremia patients and controls, examined the association between plasma L5% and CAD risk in uremia patients, and studied the effects of L5 from uremia patients on endothelial function. Compared to controls, uremia patients had significantly increased L5% (P < 0.001) and L5 that was rich in apolipoprotein C3 and triglycerides. L5% was significantly higher in uremia patients with CAD (n = 10) than in those without CAD (n = 29) (P < 0.05). Independent of other major CAD risk factors, the adjusted odds ratio for CAD was 1.88 per percent increase in plasma L5% (95% CI, 1.01–3.53), with a near-linear dose–response relationship. Compared with controls, uremia patients had decreased flow-mediated vascular dilatation. In ex vivo studies with preconstricted rat thoracic aortic rings, L5 from uremia patients inhibited acetylcholine-induced relaxation. In cultured human endothelial cells, L5 inhibited endothelial nitric oxide synthase activation and induced endothelial dysfunction. Our findings suggest that elevated plasma L5% may induce endothelial dysfunction and play an important role in the increased risk of CAD in uremia patients. PMID:26765403

Langmuir probe analysis in electronegative plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bredin, Jerome, E-mail: jerome.bredin@lpp.polytechnique.fr; Chabert, Pascal; Aanesland, Ane

2014-12-15

This paper compares two methods to analyze Langmuir probe data obtained in electronegative plasmas. The techniques are developed to allow investigations in plasmas, where the electronegativity α{sub 0} = n{sub –}/n{sub e} (the ratio between the negative ion and electron densities) varies strongly. The first technique uses an analytical model to express the Langmuir probe current-voltage (I-V) characteristic and its second derivative as a function of the electron and ion densities (n{sub e}, n{sub +}, n{sub –}), temperatures (T{sub e}, T{sub +}, T{sub –}), and masses (m{sub e}, m{sub +}, m{sub –}). The analytical curves are fitted to the experimental data bymore » adjusting these variables and parameters. To reduce the number of fitted parameters, the ion masses are assumed constant within the source volume, and quasi-neutrality is assumed everywhere. In this theory, Maxwellian distributions are assumed for all charged species. We show that this data analysis can predict the various plasma parameters within 5–10%, including the ion temperatures when α{sub 0} > 100. However, the method is tedious, time consuming, and requires a precise measurement of the energy distribution function. A second technique is therefore developed for easier access to the electron and ion densities, but does not give access to the ion temperatures. Here, only the measured I-V characteristic is needed. The electron density, temperature, and ion saturation current for positive ions are determined by classical probe techniques. The electronegativity α{sub 0} and the ion densities are deduced via an iterative method since these variables are coupled via the modified Bohm velocity. For both techniques, a Child-Law sheath model for cylindrical probes has been developed and is presented to emphasize the importance of this model for small cylindrical Langmuir probes.« less

Synthesis of new visible light active photocatalysts of Ba(In(1/3)Pb(1/3)M'(1/3))O3 (M' = Nb, Ta): a band gap engineering strategy based on electronegativity of a metal component.

PubMed

Hur, Su Gil; Kim, Tae Woo; Hwang, Seong-Ju; Park, Hyunwoong; Choi, Wonyong; Kim, Sung Jin; Kim, Sun Jin; Choy, Jin-Ho

2005-08-11

We have synthesized new, efficient, visible light active photocatalysts through the incorporation of highly electronegative non-transition metal Pb or Sn ions into the perovskite lattice of Ba(In(1/3)Pb(1/3)M'(1/3))O3 (M = Sn, Pb; M' = Nb, Ta). X-ray diffraction, X-ray absorption spectroscopic, and energy dispersive spectroscopic microprobe analyses reveal that tetravalent Pb or Sn ions exist in the B-site of the perovskite lattice, along with In and Nb/Ta ions. According to diffuse UV-vis spectroscopic analysis, the Pb-containing quaternary metal oxides Ba(In(1/3)Pb(1/3)M'(1/3))O3 possess a much narrower band gap (E(g) approximately 1.48-1.50 eV) when compared to the ternary oxides Ba(In(1/2)M'(1/2))O3 (E(g) approximately 2.97-3.30 eV) and the Sn-containing Ba(In(1/3)Sn(1/3)M'(1/3))O3 derivatives (E(g) approximately 2.85-3.00 eV). Such a variation of band gap energy upon the substitution is attributable to the broadening of the conduction band caused by the dissimilar electronegativities of the B-site cations. In contrast to the ternary or the Sn-substituted quaternary compounds showing photocatalytic activity under UV-vis irradiation, the Ba(In(1/3)Pb(1/3)M'(1/3))O3 compounds induce an efficient photodegradation of 4-chlorophenol under visible light irradiation (lambda > 420 nm). The present results highlight that the substitution of electronegative non-transition metal cations can provide a very powerful way of developing efficient visible light harvesting photocatalysts through tuning of the band structure of a semiconductive metal oxide.

Crown oxygen-doping graphene with embedded main-group metal atoms

NASA Astrophysics Data System (ADS)

Wu, Liyuan; Wang, Qian; Yang, Chuanghua; Quhe, Ruge; Guan, Pengfei; Lu, Pengfei

2018-02-01

Different main-group metal atoms embedded in crown oxygen-doping graphene (metal@OG) systems are studied by the density functional theory. The binding energies and electronic structures are calculated by using first-principles calculations. The binding energy of metal@OG system mainly depends on the electronegativity of the metal atom. The lower the value of the electronegativity, the larger the binding energy, indicating the more stable the system. The electronic structure of metal@OG arouses the emergence of bandgap and shift of Dirac point. It is shown that interaction between metal atom and crown oxygen-doping graphene leads to the graphene's stable n-doping, and the metal@OG systems are stable semiconducting materials, which can be used in technological applications.

Group electronegativity for prediction of materials hardness.

PubMed

Li, Keyan; Yang, Peng; Niu, Lingxiao; Xue, Dongfeng

2012-06-28

We have developed a method to predict the hardness of materials containing ultrastrong anionic polyhedra, dense atomic clusters, and layers stacked through van der Waals bonds on the basis of group electronegativity. By considering these polyhedra, clusters, and layers as groups that behave as rigid unities like superatoms bonding to other atoms or groups, the hardness values of materials such as oxysalts, T-carbon, and graphite were quantitatively calculated, and the results are consistent with the available experiments. We found that the hardness of materials containing these artificial groups is determined by the bonds between the groups and other atoms or groups, rather than by the weakest bonds. This work sheds light on the nature of materials hardness and the design of novel inorganic crystal materials.

On the electrophilic character of molecules through its relation with electronegativity and chemical hardness.

PubMed

Islam, Nazmul; Ghosh, Dulal C

2012-01-01

Electrophilicity is an intrinsic property of atoms and molecules. It probably originates logistically with the involvement in the physical process of electrostatics of soaked charge in electronic shells and the screened nuclear charge of atoms. Motivated by the existing view of conceptual density functional theory that similar to electronegativity and hardness equalization, there should be a physical process of equalization of electrophilicity during the chemical process of formation of hetero nuclear molecules, we have developed a new theoretical scheme and formula for evaluating the electrophilicity of hetero nuclear molecules. A comparative study with available bench marking reveals that the hypothesis of electrophilicity and equalization, and the present method of evaluating equalized electrophilicity, are scientifically promising.

On the Electrophilic Character of Molecules Through Its Relation with Electronegativity and Chemical Hardness

PubMed Central

Islam, Nazmul; Ghosh, Dulal C.

2012-01-01

Electrophilicity is an intrinsic property of atoms and molecules. It probably originates logistically with the involvement in the physical process of electrostatics of soaked charge in electronic shells and the screened nuclear charge of atoms. Motivated by the existing view of conceptual density functional theory that similar to electronegativity and hardness equalization, there should be a physical process of equalization of electrophilicity during the chemical process of formation of hetero nuclear molecules, we have developed a new theoretical scheme and formula for evaluating the electrophilicity of hetero nuclear molecules. A comparative study with available bench marking reveals that the hypothesis of electrophilicity and equalization, and the present method of evaluating equalized electrophilicity, are scientifically promising. PMID:22408445

Lattice parameters and stability of the spinel compounds in relation to the ionic radii and electronegativities of constituting chemical elements.

PubMed

Brik, Mikhail G; Suchocki, Andrzej; Kamińska, Agata

2014-05-19

A thorough consideration of the relation between the lattice parameters of 185 binary and ternary spinel compounds, on one side, and ionic radii and electronegativities of the constituting ions, on the other side, allowed for establishing a simple empirical model and finding its linear equation, which links together the above-mentioned quantities. The derived equation gives good agreement between the experimental and modeled values of the lattice parameters in the considered group of spinels, with an average relative error of about 1% only. The proposed model was improved further by separate consideration of several groups of spinels, depending on the nature of the anion (oxygen, sulfur, selenium/tellurium, nitrogen). The developed approach can be efficiently used for prediction of lattice constants for new isostructural materials. In particular, the lattice constants of new hypothetic spinels ZnRE2O4, CdRE2S4, CdRE2Se4 (RE = rare earth elements) are predicted in the present Article. In addition, the upper and lower limits for the variation of the ionic radii, electronegativities, and their certain combinations were established, which can be considered as stability criteria for the spinel compounds. The findings of the present Article offer a systematic overview of the structural properties of spinels and can serve as helpful guides for synthesis of new spinel compounds.

Electronegative LDL-mediated cardiac electrical remodeling in a rat model of chronic kidney disease

PubMed Central

Lee, An-Sheng; Chen, Wei-Yu; Chan, Hua-Chen; Chung, Ching-Hu; Peng, Hsien-Yu; Chang, Chia-Ming; Su, Ming-Jai; Chen, Chu-Huang; Chang, Kuan-Cheng

2017-01-01

The mechanisms underlying chronic kidney disease (CKD)–associated higher risks for life-threatening ventricular tachyarrhythmias remain poorly understood. In rats subjected to unilateral nephrectomy (UNx), we examined cardiac electrophysiological remodeling and relevant mechanisms predisposing to ventricular arrhythmias. Adult male Sprague-Dawley rats underwent UNx (n = 6) or sham (n = 6) operations. Eight weeks later, the UNx group had higher serum blood urea nitrogen and creatinine levels and a longer electrocardiographic QTc interval than did the sham group. Patch-clamp studies revealed epicardial (EPI)-predominant prolongation of the action potential duration (APD) at 50% and 90% repolarization in UNx EPI cardiomyocytes compared to sham EPI cardiomyocytes. A significant reduction of the transient outward potassium current (Ito) in EPI but not in endocardial (ENDO) cardiomyocytes of UNx rats led to a decreased transmural gradient of Ito. The reduction of Ito currents in UNx EPI cardiomyocytes was secondary to downregulation of KChIP2 but not Kv4.2, Kv4.3, and Kv1.4 protein expression. Incubation of plasma electronegative low-density lipoprotein (LDL) from UNx rats with normal EPI and ENDO cardiomyocytes recapitulated the electrophysiological phenotype of UNx rats. In conclusion, CKD disrupts the physiological transmural gradient of Ito via downregulation of KChIP2 proteins in the EPI region, which may promote susceptibility to ventricular tachyarrhythmias. Electronegative LDL may underlie downregulation of KChIP2 in CKD. PMID:28094801

Influence of transition metal electronegativity on the oxygen storage capacity of perovskite oxides.

PubMed

Liu, Lu; Taylor, Daniel D; Rodriguez, Efrain E; Zachariah, Michael R

2016-08-16

The selection of highly efficient oxygen carriers (OCs) is a key step necessary for the practical development of chemical looping combustion (CLC). In this study, a series of ABO3 perovskites, where A = La, Ba, Sr, Ca and B = Cr, Mn, Fe, Co, Ni, Cu, are synthesized and tested in a fixed bed reactor for reactivity and stability as OCs with CH4 as the fuel. We find that the electronegativity of the transition metal on the B-site (λB), is a convenient descriptor for oxygen storage capacity (OSC) of our perovskite samples. By plotting OSC for total methane oxidation against λB, we observe an inverted volcano plot relationship. These results could provide useful guidelines for perovskite OC design and their other energy related applications.

Characteristics of Electronegative Plasma Sheath with q-Nonextensive Electron Distribution

NASA Astrophysics Data System (ADS)

Borgohain, D. R.; Saharia, K.

2018-01-01

The characteristics of sheath in a plasma system containing q-nonextensive electrons, cold fluid ions, and Boltzmann-distributed negative ions are investigated. A modified Bohm sheath criterion is derived by using the Sagdeev pseudopotential technique. It is found that the proposed Bohm velocity depends on the degree of nonextensivity ( q), negative ion temperature to nonextensive electron temperature ratio (σ), and negative ion density ( B). Using the modified Bohm sheath criterion, the sheath characteristics, such as the spatial distribution of the potential, positive ion velocity, and density profile, have been numerically investigated, which clearly shows the effect of negative ions, as well as the nonextensive distribution of electrons. It is found that, as the nonextensivity parameter and the electronegativity increases, the electrostatic sheath potential increases sharply and the sheath width decreases.

Can the electronegativity equalization method predict spectroscopic properties?

PubMed

Verstraelen, T; Bultinck, P

2015-02-05

The electronegativity equalization method is classically used as a method allowing the fast generation of atomic charges using a set of calibrated parameters and provided knowledge of the molecular structure. Recently, it has started being used for the calculation of other reactivity descriptors and for the development of polarizable and reactive force fields. For such applications, it is of interest to know whether the method, through the inclusion of the molecular geometry in the Taylor expansion of the energy, would also allow sufficiently accurate predictions of spectroscopic data. In this work, relevant quantities for IR spectroscopy are considered, namely the dipole derivatives and the Cartesian Hessian. Despite careful calibration of parameters for this specific task, it is shown that the current models yield insufficiently accurate results. Copyright © 2013 Elsevier B.V. All rights reserved.

Electronegative nonlinear oscillating modes in plasmas

NASA Astrophysics Data System (ADS)

Panguetna, Chérif Souleman; Tabi, Conrad Bertrand; Kofané, Timoléon Crépin

2018-02-01

The emergence of nonlinear modulated waves is addressed in an unmagnetized electronegative plasma made of Boltzmann electrons, Boltzmann negative ions and cold mobile positive ions. The reductive perturbation method is used to reduce the dynamics of the whole system to a cubic nonlinear Schrödinger equation, whose the nonlinear and dispersion coefficients, P and Q, are function of the negative ion parameters, namely the negative ion concentration ratio (α) and the electron-to-negative ion temperature ratio (σn). It is observed that these parameters importantly affect the formation of modulated ion-acoustic waves, either as exact solutions or via the activation of modulational instability. Especially, the theory of modulational instability is used to show the correlation between the parametric analysis and the formation of modulated solitons, obtained here as bright envelopes and kink-wave solitons.

Bonded Radii and the Contraction of the Electron Density of the Oxygen Atom by Bonded Interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gibbs, Gerald V.; Ross, Nancy L.; Cox, David F.

2013-02-21

The bonded radii for more than 550 bonded pairs of atoms, comprising more than 50 crystals, determined from experimental and theoretical electron density distributions, are compared with the effective ionic, ri(M), and crystal radii, rc(M), for metal atoms, M, bonded to O atoms. At odds with the fixed ionic radius of 1.40 Å, assumed for the O atom in the compilation of the ionic radii, the bonded radius for the atom, rb(O), is not fixed but displays a relatively wide range of values as the O atom is progressively polarized by the M-O bonded interactions: as such, rb(O) decreases systematicallymore » from 1.40 Å (the Pauling radius of the oxide anion) as bond lengths decrease when bonded to an electropositive atom like sodium, to 0.64 Å (Bragg’s atomic radius of the O atom) when bonded to an electronegative atom like nitrogen. Both rb(M) and rb(O) increase in tandum with the increasing coordination number of the M atom. The bonded radii of the M atoms are highly correlated with both ri(M) and rc(M), but they both depart systematically from rb(M) and become smaller as the electronegativity of the M atom increases and the M-O bond length decreases. The well-developed correlations between both sets of radii and rb(M) testifies to the relative precision of both sets of radii and the fact that both sets are highly correlated the M-O bond 1 lengths. On the other hand, the progressive departure of rb(O) from the fixed ionic radius of the O atom with the increasing electronegativity of the bonded M atom indicates that any compilation of sets of ionic radii, assuming that the radius for the oxygen atom is fixed in value, is problematical and impacts on the accuracy of the resulting sets of ionic and crystal radii thus compiled. The assumption of a fixed O atom radius not only results in a negative ionic radii for several atoms, but it also results in values of rb(M) that are much as ~ 0.6 Å larger than the ri(M) and rc(M) values, respectively, particularly for the more electronegative M atoms. On the other hand, the ionic radii are in closer agreement with rb(M) for the more electropositive atoms. Notwithstanding that ionic radii are typically smaller than bonded radii, particularly for the more electronegative atoms, they have been used with considerable success in understanding and rationalizing problems and properties in crystal chemistry primarily because both ionic and crystal radii are highly correlated on a one-to-one basis with both the bonded radii and the associated M-O bond lengths. The lack of agreement between the effective ionic and crystal radii and the bonded radii for the more shared bonded interactions is ascribed to the progressive increase in the polarization of the O atom by the bonded atoms with a concomitant decrease in its radius, a factor that was neglected in the compilation of ionic and crystal radii for fluorides, oxides, sulfides and nitrides. This accounts for ionic radii for these materials being smaller than the bonded radii for the more electronegative atoms.« less

Chemistry Notes.

ERIC Educational Resources Information Center

School Science Review, 1983

1983-01-01

Presents background information, laboratory procedures, classroom materials/activities, and chemistry experiments. Topics include sublimation, electronegativity, electrolysis, experimental aspects of strontianite, halide test, evaluation of present and future computer programs in chemistry, formula building, care of glass/saturated calomel…

Sub-micron filter

DOEpatents

Tepper, Frederick [Sanford, FL; Kaledin, Leonid [Port Orange, FL

2009-10-13

Aluminum hydroxide fibers approximately 2 nanometers in diameter and with surface areas ranging from 200 to 650 m.sup.2/g have been found to be highly electropositive. When dispersed in water they are able to attach to and retain electronegative particles. When combined into a composite filter with other fibers or particles they can filter bacteria and nano size particulates such as viruses and colloidal particles at high flux through the filter. Such filters can be used for purification and sterilization of water, biological, medical and pharmaceutical fluids, and as a collector/concentrator for detection and assay of microbes and viruses. The alumina fibers are also capable of filtering sub-micron inorganic and metallic particles to produce ultra pure water. The fibers are suitable as a substrate for growth of cells. Macromolecules such as proteins may be separated from each other based on their electronegative charges.

Nanosize electropositive fibrous adsorbent

DOEpatents

Tepper, Frederick; Kaledin, Leonid

2005-01-04

Aluminum hydroxide fibers approximately 2 nanometers in diameter and with surface areas ranging from 200 to 650 m.sup.2 /g have been fount to be highly electropositive. When dispersed in water they are able to attach to and retain electronegative particles. When combined into a composite filter with other fibers or particles they can filter bacteria and nano size particulates such as viruses and colloidal particles at high flux through the filter. Such filters can be used for purification and sterilization of water, biological, medical and pharmaceutical fluids, and as a collector/concentrator for detection and assay of mirobes and viruses. The alumina fibers are also capable of filtering sub-micron inorganic and metallic particles to produce ultra pure water. The fibers are suitable as a substrate for growth of cells. Macromolicules such as proteins may be separated from each other based on their electronegative charges.

Electronegativity estimator built on QTAIM-based domains of the bond electron density.

PubMed

Ferro-Costas, David; Pérez-Juste, Ignacio; Mosquera, Ricardo A

2014-05-15

The electron localization function, natural localized molecular orbitals, and the quantum theory of atoms in molecules have been used all together to analyze the bond electron density (BED) distribution of different hydrogen-containing compounds through the definition of atomic contributions to the bonding regions. A function, gAH , obtained from those contributions is analyzed along the second and third periods of the periodic table. It exhibits periodic trends typically assigned to the electronegativity (χ), and it is also sensitive to hybridization variations. This function also shows an interesting S shape with different χ-scales, Allred-Rochow's being the one exhibiting the best monotonical increase with regard to the BED taken by each atom of the bond. Therefore, we think this χ can be actually related to the BED distribution. Copyright © 2014 Wiley Periodicals, Inc.

A Relativity Enhanced, Medium-Strong Au(I)···H-N Hydrogen Bond in a Protonated Phenylpyridine-Gold(I) Thiolate.

PubMed

Berger, Raphael J F; Schoiber, Jürgen; Monkowius, Uwe

2017-01-17

Gold is an electron-rich metal with a high electronegativity comparable to that of sulfur. Hence, hydrogen bonds of the Au(I)···H-E (E = electronegative element) type should be possible, but their existence is still under debate. Experimental results are scarce and often contradictory. As guidance for possible preparative work, we have theoretically investigated (ppyH)Au(SPh) (ppy = 2-phenylpyridine) bearing two monoanionic ligands which are not strongly electronegative at the same time to further increase the charge density on the gold(I) atom. The protonated pyridine nitrogen atom in ppy is geometrically ideally suited to place a proton in close proximity to the gold atom in a favorable geometry for a classical hydrogen bond arrangement. Indeed, the results of the calculations indicate that the hydrogen bonded conformation of (ppyH)Au(SPh) represents a minimum geometry with bond metrics in the expected range for medium-strong hydrogen bonds [r(N-H) = 1.043 Å, r(H···Au) = 2.060 Å, a(N-H···Au) = 141.4°]. The energy difference between the conformer containing the H···Au bond and another conformer without a hydrogen bond amounts to 7.8 kcal mol -1 , which might serve as an estimate of the hydrogen bond strength. Spectroscopic properties were calculated, yielding further characteristics of such hydrogen bonded gold species.

Development of an Electron-capture Technique Specific for Explosives Detection

DOT National Transportation Integrated Search

1974-07-01

This document contains information on the design, fabrication, and testing of a prototype detector specific for explosives which employs electron-capture sensors. The technique used exploits the observation that the electronegative vapors from explos...

Application of enhanced electronegative multimodal chromatography as the primary capture step for immunoglobulin G purification.

PubMed

Wang, Yanli; Chen, Quan; Xian, Mo; Nian, Rui; Xu, Fei

2018-06-01

In recent studies, electronegative multimodal chromatography with Eshmuno HCX was demonstrated to be a highly promising recovery step for direct immunoglobulin G (IgG) capture from undiluted cell culture fluid. In this study, the binding properties of HCX to IgG at different pH/salt combinations were systematically studied, and its purification performance was significantly enhanced by lowering the washing pH and conductivity after high capacity binding of IgG under its optimal conditions. A single polishing step gave an end-product with non-histone host cell protein (nh-HCP) below 1 ppm, DNA less than 1 ppb, which aggregates less than 0.5% and an overall IgG recovery of 86.2%. The whole non-affinity chromatography based two-column-step process supports direct feed loading without buffer adjustment, thus extraordinarily boosting the overall productivity and cost-savings.

Effect of electronegative additives on physical properties and chemical activity of gas discharge plasma

NASA Astrophysics Data System (ADS)

Kuznetsov, D. L.; Filatov, I. E.; Uvarin, V. V.

2018-01-01

Effect of electronegative additives (oxygen O2, sulfur dioxide SO2, carbon disulfide CS2, and carbon tetrachloride CCl4) on physical properties and chemical activity of plasma formed by pulsed corona discharge and by non-self-sustained discharge supported by pulsed electron beam in atmospheric pressure gas mixtures was investigated. It is shown that a decrease in discharge current depends on a sort of the additive and on its concentration. The reason is the difference in rate constants of electron attachment processes for the above molecules. In experiments on volatile organic compounds (VOCs) conversion in air by streamer corona it is obtained that an addition of CCl4 both decreases the discharge current amplitude and increases the VOCs conversion degree. An installation for investigation of electron attachment processes and for study of toxic impurities conversion in plasma formed by non-self-sustained discharge initiated by pulsed nanosecond electron beam is created.

Surface energy of talc and chlorite: Comparison between electronegativity calculation and immersion results.

PubMed

Douillard, Jean-Marc; Salles, Fabrice; Henry, Marc; Malandrini, Harold; Clauss, Frédéric

2007-01-15

The surface energies of talc and chlorite is computed using a simple model, which uses the calculation of the electrostatic energy of the crystal. It is necessary to calculate the atomic charges. We have chosen to follow Henry's model of determination of partial charges using scales of electronegativity and hardness. The results are in correct agreement with a determination of the surface energy obtained from an analysis of the heat of immersion data. Both results indicate that the surface energy of talc is lower than the surface energy of chlorite, in agreement with observed behavior of wettability. The influence of Al and Fe on this phenomenon is discussed. Surface energy of this type of solids seems to depend more strongly on the geometry of the crystal than on the type of atoms pointing out of the surface; i.e., the surface energy depends more on the physics of the system than on its chemistry.

Evaluating the use of electronegativity in band alignment models through the experimental slope parameter of lanthanum aluminate heterostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Z. Q.; Chim, W. K.; Chiam, S. Y

2011-11-01

In this work, photoelectron spectroscopy is used to characterize the band alignment of lanthanum aluminate heterostructures which possess a wide range of potential applications. It is found that our experimental slope parameter agrees with theory using the metal-induced gap states model while the interface induced gap states (IFIGS) model yields unsatisfactory results. We show that this discrepancy can be attributed to the correlation between the dielectric work function and the electronegativity in the IFIGS model. It is found that the original trend, as established largely by metals, may not be accurate for larger band gap materials. By using a newmore » correlation, our experimental data shows good agreement of the slope parameter using the IFIGS model. This correlation, therefore, plays a crucial role in heterostructures involving wider bandgap materials for accurate band alignment prediction using the IFIGS model.« less

X2Y2 isomers: tuning structure and relative stability through electronegativity differences (X = H, Li, Na, F, Cl, Br, I; Y = O, S, Se, Te).

PubMed

El-Hamdi, Majid; Poater, Jordi; Bickelhaupt, F Matthias; Solà, Miquel

2013-03-04

We have studied the XYYX and X2YY isomers of the X2Y2 species (X = H, Li, Na, F, Cl, Br, I; Y = O, S, Se, Te) using density functional theory at the ZORA-BP86/QZ4P level. Our computations show that, over the entire range of our model systems, the XYYX isomers are more stable than the X2YY forms except for X = F and Y = S and Te, for which the F2SS and F2TeTe isomers are slightly more stable. Our results also point out that the Y-Y bond length can be tuned quite generally through the X-Y electronegativity difference. The mechanism behind this electronic tuning is the population or depopulation of the π* in the YY fragment.

Ionocovalency and Applications 1. Ionocovalency Model and Orbital Hybrid Scales

PubMed Central

Zhang, Yonghe

2010-01-01

Ionocovalency (IC), a quantitative dual nature of the atom, is defined and correlated with quantum-mechanical potential to describe quantitatively the dual properties of the bond. Orbiotal hybrid IC model scale, IC, and IC electronegativity scale, XIC, are proposed, wherein the ionicity and the covalent radius are determined by spectroscopy. Being composed of the ionic function I and the covalent function C, the model describes quantitatively the dual properties of bond strengths, charge density and ionic potential. Based on the atomic electron configuration and the various quantum-mechanical built-up dual parameters, the model formed a Dual Method of the multiple-functional prediction, which has much more versatile and exceptional applications than traditional electronegativity scales and molecular properties. Hydrogen has unconventional values of IC and XIC, lower than that of boron. The IC model can agree fairly well with the data of bond properties and satisfactorily explain chemical observations of elements throughout the Periodic Table. PMID:21151444

Optimized and parallelized implementation of the electronegativity equalization method and the atom-bond electronegativity equalization method.

PubMed

Vareková, R Svobodová; Koca, J

2006-02-01

The most common way to calculate charge distribution in a molecule is ab initio quantum mechanics (QM). Some faster alternatives to QM have also been developed, the so-called "equalization methods" EEM and ABEEM, which are based on DFT. We have implemented and optimized the EEM and ABEEM methods and created the EEM SOLVER and ABEEM SOLVER programs. It has been found that the most time-consuming part of equalization methods is the reduction of the matrix belonging to the equation system generated by the method. Therefore, for both methods this part was replaced by the parallel algorithm WIRS and implemented within the PVM environment. The parallelized versions of the programs EEM SOLVER and ABEEM SOLVER showed promising results, especially on a single computer with several processors (compact PVM). The implemented programs are available through the Web page http://ncbr.chemi.muni.cz/~n19n/eem_abeem.

Singularity and Bohm criterion in hot positive ion species in the electronegative ion sources

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aslaninejad, Morteza; Yasserian, Kiomars

2016-05-15

The structure of the discharge for a magnetized electronegative ion source with two species of positive ions is investigated. The thermal motion of hot positive ions and the singularities involved with it are taken into account. By analytical solution of the neutral region, the location of the singular point and also the values of the plasma parameter such as electric potential and ion density at the singular point are obtained. A generalized Bohm criterion is recovered and discussed. In addition, for the non-neutral solution, the numerical method is used. In contrast with cold ion plasma, qualitative changes are observed. Themore » parameter space region within which oscillations in the density and potential can be observed has been scanned and discussed. The space charge behavior in the vicinity of edge of the ion sources has also been discussed in detail.« less

Tuning of Terahertz Resonances of Pyridyl Benzamide Derivatives by Electronegative Atom Substitution

NASA Astrophysics Data System (ADS)

Dash, Jyotirmayee; Ray, Shaumik; Devi, Nirmala; Basutkar, Nitin; Gonnade, Rajesh G.; Ambade, Ashootosh V.; Pesala, Bala

2018-05-01

N-(pyridin-2-yl) benzamide (Ph2AP)-based organic molecules with prominent terahertz (THz) signatures (less than 5 THz) have been synthesized. The THz resonances are tuned by substituting the most electronegative atom, fluorine, at ortho (2F-Ph2AP), meta (3F-Ph2AP), and para (4F-Ph2AP) positions in a Ph2AP molecule. Substitution of fluorine helps in varying the charge distribution of the atoms forming hydrogen bond and hence strength of the hydrogen bond is varied which helps in tuning the THz resonances. The tuning of lower THz resonances of 2F-Ph2AP, 3F-Ph2AP, and 4F-Ph2AP has been explained in terms of compliance constant (relaxed force constant). Four-molecule cluster simulations have been carried out using Gaussian09 software to calculate the compliance constant of the hydrogen bonds. Crystal structure simulations of the above molecules using CRYSTAL14 software have been carried out to understand the origin of THz resonances. It has been observed that THz resonances are shifted to higher frequencies with stronger hydrogen bonds. The study shows that 3F-Ph2AP and 4F-Ph2AP have higher hydrogen bond strength and hence the THz resonances originating due to stretching of intermolecular hydrogen bonds have been shifted to higher frequencies compared to 2F-Ph2AP. The methodology presented here will help in designing novel organic molecules by substituting various electronegative atoms in order to achieve prominent THz resonances.

Synthesis and Thermoelectric Properties of Charge-Compensated SyPdxCo4-xSb12 Skutterudites.

PubMed

Wan, Shun; Qiu, Pengfei; Huang, Xiangyang; Song, Qingfeng; Bai, Shengqiang; Shi, Xun; Chen, Lidong

2018-01-10

Recently, the electronegative elements (e.g., S, Se, Cl, and Br) filled skutterudites have attracted great attention in thermoelectric community. Via doping of some electron donors at the Sb sites, these electronegative elements can be filled into the voids of CoSb 3 forming thermodynamically stable compounds, which greatly extends the scope of filled skutterudites. In this study, we show that doping appropriate elements at the Co sites can also stabilize the electronegative elements in the voids of CoSb 3 . A series of S y Pd x Co 4-x Sb 12 compounds were successfully fabricated by a traditional solid state reaction method combined with a spark plasma sintering technique. The phase composition and electrical and thermal transport properties were systematically characterized, and the related mechanisms were deeply discussed. It is found that the charge compensation between Pd doping and S filling is the main reason for the formation of thermodynamically stable S y Pd x Co 4-x Sb 12 compounds. Filling S element in the voids of CoSb 3 provides additional holes to reduce the carrier concentration while scarcely affecting the carrier mobility. However, doping Pd at the Co sites not only changes the carrier scattering mechanism but also deteriorates the carrier mobility. Low lattice thermal conductivities are observed in these S y Pd x Co 4-x Sb 12 compounds, which are attributed to the low resonant frequency of the S element. Finally, a maximal figure of merit of 0.85 is obtained for S 0.05 Pd 0.25 Co 3.75 Sb 12 at 700 K.

Dominant role of local dipolar interactions in phosphate binding to a receptor cleft with an electronegative charge surface: equilibrium, kinetic, and crystallographic studies.

PubMed

Ledvina, P S; Tsai, A L; Wang, Z; Koehl, E; Quiocho, F A

1998-12-01

Stringent specificity and complementarity between the receptor, a periplasmic phosphate-binding protein (PBP) with a two-domain structure, and the completely buried and dehydrated phosphate are achieved by hydrogen bonding or dipolar interactions. We recently found that the surface charge potential of the cleft between the two domains that contains the anion binding site is intensely electronegative. This novel finding prompted the study reported here of the effect of ionic strength on the equilibrium and rapid kinetics of phosphate binding. To facilitate this study, Ala197, located on the edge of the cleft, was replaced by a Trp residue (A197W PBP) to generate a fluorescence reporter group. The A197W PBP-phosphate complex retains wild-type Kd and X-ray structure beyond the replacement residue. The Kd (0.18 microM) at no salt is increased by 20-fold at greater than 0.30 M NaCl. Stopped-flow fluorescence kinetic studies indicate a two-step binding process: (1) The phosphate (L) binds, at near diffusion-controlled rate, to the open cleft form (Po) of PBP to produce an intermediate, PoL. This rate decreases with increasing ionic strength. (2) The intermediate isomerizes to the closed-conformation form, PcL. The results indicate that the high specificity, affinity, and rate of phosphate binding are not influenced by the noncomplementary electronegative surface potential of the cleft. That binding depends almost entirely on local dipolar interactions with the receptor has important ramification in electrostatic interactions in protein structures and in ligand recognition.

Correlation between structural stability of LiBH4 and cation electronegativity in metal borides: an experimental insight for catalyst design.

PubMed

Cai, Weitong; Yang, Yuanzheng; Tao, Pingjun; Ouyang, Liuzhang; Wang, Hui

2018-04-03

Nanosized metal borides MBx (M = Mg, Ti, Fe, Si) are found to play an important role in enhancing the hydrogen storage performance of LiBH4 in this work. The hydrogen storage behavior and mechanism of these modified systems are investigated through TPD-MS, XRD, FTIR and SEM characterization methods. By introducing these metal borides into LiBH4 through ball milling, the systems display three dehydrogenation stages disclosing their similarity and distinction. The 1st stage starts at 190 °C, the 2nd stage ranges from 280 °C to 400 °C and the 3rd stage ends at 550 °C with a peak at round 440 °C similar to that of pristine LiBH4. Distinguishing features exist at the 2nd stage revealing the effectiveness of MBx in an order of MgB2 < TiB2 < FeB < SiB4. Significantly, reversibility up to 9.7 wt% is achieved from LiBH4 with assistance of SiB4. The catalytic effect of MBx is influenced by the Pauling electronegativity of M in MBx and the interfacial contact characteristic between LiBH4 and MBx. The larger electronegativity leads to an enhanced catalytic effect and consequently lower temperature at the major stage. In contrast to the components in the solid state, the molten LiBH4 promotes a catalytic effect due to a superior interfacial contact. These results provide an insight into designing high-performance catalysts applied to LiBH4 as a hydrogen storage material.

Development of a novel method for simultaneous concentration of viruses and protozoa from a single water sample.

PubMed

Haramoto, Eiji; Katayama, Hiroyuki; Asami, Mari; Akiba, Michihiro

2012-06-01

A novel method, electronegative membrane-vortex (EMV) method, was developed for simultaneous concentration of viruses and protozoa from a single water sample. Viruses and protozoa in a water sample were mixed with a cation solution and adsorbed on an electronegative membrane. Concentrated virus and protozoa samples were obtained as supernatant and pellet fractions, respectively, by vigorous vortex mixing of the membrane and centrifugation of the eluted material. The highest recovery efficiencies of model microbes from river water and tap water by this EMV method were obtained using a mixed cellulose ester membrane with a pore size of 0.45 μm (Millipore) as the electronegative membrane and MgCl(2) as the cation solution. The recovery was 27.7-86.5% for poliovirus, 25.7-68.3% for coliphage Qβ, 28.0-60.0% for Cryptosporidium oocysts, and 35.0-53.0% for Giardia cysts. The EMV method detected successfully indigenous viruses and protozoa in wastewater and river water samples from the Kofu basin, Japan, showing an overall positive rate of 100% (43/43) for human adenovirus, 79% (34/43) for norovirus GI, 65% (28/43) for norovirus GII, 23% (10/43) for Cryptosporidium oocysts, and 60% (26/43) for Giardia cysts. By direct DNA sequencing, a total of four genotypes (AI, AII, B, and G) of Giardia intestinalis were identified in the water samples, indicating that the river water was contaminated with feces from various mammals, including humans. Copyright © 2012 Elsevier B.V. All rights reserved.

Human Relations Activities for the Single Parent To Develop More Effective Parent/Child Relations. Bilingual Guide = Actividades sobre relaciones humanas para ayudar al padre-soltero o madre-soltera a desarrollar una relacion efectiva entre padre e hijo Guia bilingue.

ERIC Educational Resources Information Center

Peterson, Susan

Written in English and Spanish, this bilingual guide offers 10 activities which single parents can use to improve their relationships with their children. Objectives of activities include: (1) developing children's responsibility for work tasks in the home; (2) improving sibling relationships; (3) discussing emergencies with children; (4)…

SOME CHEMICAL PROPERTIES UNDERLYING ARSENIC'S BIOLOGICAL ACTIVITY

EPA Science Inventory

ABSTRACT

In this paper some of the chemical properties of arsenicals (atomic
and molecular orbitals, electronegativity, valence state, changes between
valence state, nucleophilicity, the hard/soft acid/base principle) that may
account for some of the b...

A Report of Undergraduates' Bonding Misconceptions.

ERIC Educational Resources Information Center

Nicoll, Gayle

2001-01-01

Describes misconceptions related to electronegativity, bonding, geometry, and microscopic representations that undergraduate students hold. Investigates the stability of misconceptions as a function of educational level, indicating that some students' misconceptions relating to bonding are resistant to change despite increased chemistry education.…

The Concept of Oxidation States in Metal Complexes

ERIC Educational Resources Information Center

Steinborn, Dirk

2004-01-01

The concepts of oxidation numbers when applied means electrons that are shared between atoms in molecules are assigned to a specific atom. Oxidation numbers are assigned from the Lewis structure of a molecule, with knowledge of the electronegativities of elements.

Electronegativity equalization method: parameterization and validation for organic molecules using the Merz-Kollman-Singh charge distribution scheme.

PubMed

Jirousková, Zuzana; Vareková, Radka Svobodová; Vanek, Jakub; Koca, Jaroslav

2009-05-01

The electronegativity equalization method (EEM) was developed by Mortier et al. as a semiempirical method based on the density-functional theory. After parameterization, in which EEM parameters A(i), B(i), and adjusting factor kappa are obtained, this approach can be used for calculation of average electronegativity and charge distribution in a molecule. The aim of this work is to perform the EEM parameterization using the Merz-Kollman-Singh (MK) charge distribution scheme obtained from B3LYP/6-31G* and HF/6-31G* calculations. To achieve this goal, we selected a set of 380 organic molecules from the Cambridge Structural Database (CSD) and used the methodology, which was recently successfully applied to EEM parameterization to calculate the HF/STO-3G Mulliken charges on large sets of molecules. In the case of B3LYP/6-31G* MK charges, we have improved the EEM parameters for already parameterized elements, specifically C, H, N, O, and F. Moreover, EEM parameters for S, Br, Cl, and Zn, which have not as yet been parameterized for this level of theory and basis set, we also developed. In the case of HF/6-31G* MK charges, we have developed the EEM parameters for C, H, N, O, S, Br, Cl, F, and Zn that have not been parameterized for this level of theory and basis set so far. The obtained EEM parameters were verified by a previously developed validation procedure and used for the charge calculation on a different set of 116 organic molecules from the CSD. The calculated EEM charges are in a very good agreement with the quantum mechanically obtained ab initio charges. 2008 Wiley Periodicals, Inc.

A Semimetal Nanowire Rectifier: Balancing Quantum Confinement and Surface Electronegativity.

PubMed

Sanchez-Soares, Alfonso; Greer, James C

2016-12-14

For semimetal nanowires with diameters on the order of 10 nm, a semimetal-to-semiconductor transition is observed due to quantum confinement effects. Quantum confinement in a semimetal lifts the degeneracy of the conduction and valence bands in a "zero" gap semimetal or shifts energy levels with a "negative" overlap to form conduction and valence bands. For semimetal nanowires with diameters less than 10 nm, the band gap energy can be significantly larger than the thermal energy at room temperature resulting in a new class of semiconductors suitable for nanoelectronics. As a nanowire's diameter is reduced, its surface-to-volume ratio increases rapidly leading to an increased impact of surface chemistry on its electronic structure. Energy level shifts to states in the vicinity of the Fermi energy with varying surface electronegativity are shown to be comparable in magnitude to quantum confinement effects arising in nanowires with diameters of a few nanometer; these two effects can counteract one another leading to semimetallic behavior at nanowire cross sections at which confinement effects would otherwise dominate. Abruptly changing the surface terminating species along the length of a nanowire can lead to an abrupt change in the surface electronegativity. This can result in the formation of a semimetal-semiconductor junction within a monomaterial nanowire without impurity doping nor requiring the formation of a heterojunction. Using density functional theory in tandem with a Green's function approach to determine electronic structure and charge transport, respectively, current rectification is calculated for such a junction. Current rectification ratios of the order of 10 3 -10 5 are predicted at applied biases as low as 300 mV. It is concluded that rectification can be achieved at essentially molecular length scales with conventional biasing, while rivaling the performance of macroscopic semiconductor diodes.

Periodic trends in bond dissociation energies. A theoretical study.

PubMed

Mó, Otilia; Yáñez, Manuel; Eckert-Maksić, Mirjana; Maksić, Zvonimir B; Alkorta, Ibón; Elguero, José

2005-05-19

Bond dissociation energies (BDEs) of all possible A-X single bonds involving the first- and second-row atoms, from Li to Cl, where the free valences are saturated by hydrogens, have been estimated through the use of the G3-theory and at the B3LYP/6-311+G(3df,2pd)//B3LYP/6-31G(2df,p) DFT level of theory. BDEs exhibit a periodical behavior. The A-X (A = Li, Be, B, Na, Mg, Al, and Si) BDEs show a steady increase along the first and the second row of the periodic table as a function of the atomic number Z(X). For A-X bonds involving electronegative atoms (A = C, N, O, F, P, S, and Cl) the bond energies achieve a maximum around Z(X) = 5. The same behavior is observed when BDEs are plotted against the electronegativity chi(X) of the atom X. Thus, for A-X bonds (A = Li, Be, B, Na, Mg, Al, Si), the BDEs for a fixed A increases, grosso modo, as the electronegativity differences between X and A increase, with some exceptions, which reflect the differences in the relaxation energies of the radicals produced upon the bond cleavage. A similar trend, albeit less pronounced, is found for single A-X bonds, where A = C, N, O, F, P, S, and Cl. However, there is an additional feature embodied in the enhancement of the strength of the A-boron bonds due to the ability of boron to act as a strong electron acceptor. The trends in bond lengths and charge densities at the bond critical points are in line with the aforementioned behavior.

Lewis Structure Representation of Free Radicals Similar to ClO

ERIC Educational Resources Information Center

Hirsch, Warren; Kobrak, Mark

2007-01-01

The study describes the Lewis structure representation of various free radicals, which are quite similar to the ClO radical and its isoelectronic analogues. The analysis of the periodic trends of these radicals shows that oxygen is the most electronegative atom among them.

Songs about Cancer, Gene Expression, and the Biochemistry of Photosynthesis

ERIC Educational Resources Information Center

Heineman, Richard H.

2018-01-01

These three biology songs can be used for educational purposes to teach about biochemical concepts. They touch on three different topics: (1) cancer progression and germ cells, (2) gene expression, promoters, and repressors, and (3) electronegativity and the biochemical basis of photosynthesis.

Antigenic and allergenic characterization of the enzymes alcalase and savinase by crossed immunoelectrophoresis and crossed radioimmunoelectrophoresis.

PubMed

Arlian, L G; Vyszenski-Moher, D L; Merski, J A; Ritz, H L; Nusair, T L; Wilson, E R

1990-01-01

Alcalase and savinase, produced by Bacillus species, are proteolytic enzymes that are used in laundry products and are known to cause respiratory allergy. Antigenic and allergenic characteristics of alcalase and savinase and their potential cross-reactivity were evaluated using crossed immunoelectrophoresis and crossed radioimmunoelectrophoresis. Alcalase exhibited two distinct antigens; one electropositive and one electronegative. The electropositive antigen exhibited some retrograde anodic mobility when coupled with antiserum components. Savinase exhibited one electropositive and two electronegative antigens. The antigens of the two enzymes were clearly different from each other, the three savinase antigens exhibiting greater electrophoretic mobility than the two alcalase antigens. In crossed radioimmunoelectrophoresis studies, only the electropositive antigen of alcalase, its retrograde complex, and the electropositive antigen of savinase bound IgE from the sera of individuals who were skin test positive to one or both enzymes. No evidence of cross-reactivity was observed in heterologous and tandem crossed immunoelectrophoresis studies and heterologous microimmunodiffusion reactions.

On the role of metastable states in low pressure oxygen discharges

NASA Astrophysics Data System (ADS)

Gudmundsson, J. T.; Hannesdóttir, H.

2017-03-01

We use the one-dimensional object-oriented particle-in-cell Monte Carlo collision code oopd1 to explore the spatio-temporal evolution of the electron heating mechanism in a capacitively coupled oxygen discharge in the pressure range 10 - 200 mTorr. The electron heating is most significant in the sheath vicinity during the sheath expansion phase. We explore how including and excluding detachment by the singlet metastable states O2(a1 Δg) and O2(b1Σ+g) influences the heating mechanism, the effective electron temperature and electronegativity, in the oxygen discharge. We demonstrate that the detachment processes have a significant influence on the discharge properties, in particular for the higher pressures. At 10 mTorr the time averaged electron heating shows mainly ohmic heating in the plasma bulk (the electronegative core) and at higher pressures there is no ohmic heating in the plasma bulk, that is electron heating in the sheath regions dominates.

Photo-detachment of negative ions in Ar-CO2 dc discharge employing Langmuir probe

NASA Astrophysics Data System (ADS)

Rodríguez, Jannet; Yousif, Farook Bashir; Fuentes, Beatriz E.; Vázquez, Federico; Rivera, Marco; López-Patiño, J.; Figueroa, Aldo; Martínez, Horacio

2018-05-01

The electronegativity of the A r - C O 2 gas mixture was investigated, and the total relative negative oxygen ion density O2- + O- in the bulk of a dc discharge has been determined employing Langmuir probe assisted laser photo-detachment. The relative electron density and absolute temperature were obtained for the mixture at discharge powers between 200 and 3000 mW and pressures between 0.2 and 0.6 mbar, employing the collisional radiative model for several Ar gas mixtures. The absolute metastable number density for 1s3 and 1s5 levels was measured, and both showed an increasing trend as a function of pressure and power. The absolute number density of the 1s5 level was found to be higher than that of the 1s3 level. Electronegativity was found to decrease as a function of power and as a function of the increasing Ar percentage in the gas mixture.

[Quantitative structure-gas chromatographic retention relationship of polycyclic aromatic sulfur heterocycles using molecular electronegativity-distance vector].

PubMed

Li, Zhenghua; Cheng, Fansheng; Xia, Zhining

2011-01-01

The chemical structures of 114 polycyclic aromatic sulfur heterocycles (PASHs) have been studied by molecular electronegativity-distance vector (MEDV). The linear relationships between gas chromatographic retention index and the MEDV have been established by a multiple linear regression (MLR) model. The results of variable selection by stepwise multiple regression (SMR) and the powerful predictive abilities of the optimization model appraised by leave-one-out cross-validation showed that the optimization model with the correlation coefficient (R) of 0.994 7 and the cross-validated correlation coefficient (Rcv) of 0.994 0 possessed the best statistical quality. Furthermore, when the 114 PASHs compounds were divided into calibration and test sets in the ratio of 2:1, the statistical analysis showed our models possesses almost equal statistical quality, the very similar regression coefficients and the good robustness. The quantitative structure-retention relationship (QSRR) model established may provide a convenient and powerful method for predicting the gas chromatographic retention of PASHs.

Two-dimensional modulated ion-acoustic excitations in electronegative plasmas

NASA Astrophysics Data System (ADS)

Panguetna, Chérif S.; Tabi, Conrad B.; Kofané, Timoléon C.

2017-09-01

Two-dimensional modulated ion-acoustic waves are investigated in an electronegative plasma. Through the reductive perturbation expansion, the governing hydrodynamic equations are reduced to a Davey-Stewartson system with two-space variables. The latter is used to study the modulational instability of ion-acoustic waves along with the effect of plasma parameters, namely, the negative ion concentration ratio (α) and the electron-to-negative ion temperature ratio (σn). A parametric analysis of modulational instability is carried out, where regions of plasma parameters responsible for the emergence of modulated ion-acoustic waves are discussed, with emphasis on the behavior of the instability growth rate. Numerically, using perturbed plane waves as initial conditions, parameters from the instability regions give rise to series of dromion solitons under the activation of modulational instability. The sensitivity of the numerical solutions to plasma parameters is discussed. Some exact solutions in the form one- and two-dromion solutions are derived and their response to the effect of varying α and σn is discussed as well.

Roles of cations, electronegativity difference, and anionic interlayer interactions in the metallic versus nonmetallic character of Zintl phases related to arsenic.

PubMed

Alemany, Pere; Llunell, Miquel; Canadell, Enric

2008-10-01

A first-principles Density Functional Theory study of several layered solids structurally related to rhombohedral arsenic has been carried out. The electronic structures of rhombohedral arsenic, CaSi(2), CaAl(2)Si(2), KSnSb, and SrSn(2)As(2) are discussed in detail, emphasizing on the origins of their metallic or nonmetallic behaviours. It is found that all of these systems are metallic except KSnSb. Electronegativity differences between the elements in the anionic sublattice and/or direct interlayer interactions play the main role in controlling the conductivity behavior. CaSi(2) exhibits a peculiar feature since the cation directly influences the conductivity but is not essential for its appearance. Cation-anion interactions are shown to have an important covalent contribution, but despite this fact and the metallic character found for most of these phases, the Zintl approach still provides a valid approximation to their electronic structure. (c) 2008 Wiley Periodicals, Inc.

Electron capture activation of the disulfide bond. The role of the asymmetry and electronegativity.

PubMed

Gámez, José A; Serrano-Andrés, Luis; Yáñez, Manuel

2010-02-07

The effects of electron capture on the structure of XSSX' disulfide derivatives in which the substituents attached to the sulfur atoms have different electronegativites have been investigated at different levels of theory, namely DFT, MP2, QCISD and CASSCF/CASPT2. Although it has been generally assumed that electron attachment to disulfide derivatives leads to a systematic and significant activation of the S-S bond, our results show that this is the case only when the substituents X or X' have low electronegativity. Otherwise, the S-S bond in the anion remains practically unperturbed and only the S-X bond is largely activated or even broken, because the extra electron occupies the sigma*(S-X) rather than the sigma*(S-S) antibonding orbital. Our results also show that S-S activation yields a system with a unique anion, whereas when the S-X activation is significant, two stable anionic species, stretched and bent, are formed.

Effects of ligand electronegativity on recoupled pair bonds with application to sulfurane precursors.

PubMed

Lindquist, Beth A; Woon, David E; Dunning, Thom H

2014-07-31

Recoupled pair bonds (RPBs) are conditional bonds-they only form for selected central atoms and ligands. A complete theoretical description of RPBs requires an understanding of the properties of the central atom and ligands that enable such bonds to be formed. In this work, we show that ligand electronegativity is positively correlated with recoupled pair bond strength for a variety of ligands interacting with the 3p(2) pair of sulfur. We also describe substituent (X) effects on the SF(a(4)Σ(-)) state by investigating X2SF species. These effects generally mirror those observed for covalently bound analogues, but we found that recoupled pair bonding can lead to breakdowns in the expected relationships among bond length, strength, and force constant for some of these species. Finally, we compare the properties of two molecules of practical interest that are bound by recoupled pair bonds: the dimethyl sulfur fluoride and hydroxide radicals (DMS-F and DMS-OH).

Rapid calculation of accurate atomic charges for proteins via the electronegativity equalization method.

PubMed

Ionescu, Crina-Maria; Geidl, Stanislav; Svobodová Vařeková, Radka; Koča, Jaroslav

2013-10-28

We focused on the parametrization and evaluation of empirical models for fast and accurate calculation of conformationally dependent atomic charges in proteins. The models were based on the electronegativity equalization method (EEM), and the parametrization procedure was tailored to proteins. We used large protein fragments as reference structures and fitted the EEM model parameters using atomic charges computed by three population analyses (Mulliken, Natural, iterative Hirshfeld), at the Hartree-Fock level with two basis sets (6-31G*, 6-31G**) and in two environments (gas phase, implicit solvation). We parametrized and successfully validated 24 EEM models. When tested on insulin and ubiquitin, all models reproduced quantum mechanics level charges well and were consistent with respect to population analysis and basis set. Specifically, the models showed on average a correlation of 0.961, RMSD 0.097 e, and average absolute error per atom 0.072 e. The EEM models can be used with the freely available EEM implementation EEM_SOLVER.

QSPR model for bioconcentration factors of nonpolar organic compounds using molecular electronegativity distance vector descriptors.

PubMed

Qin, Li-Tang; Liu, Shu-Shen; Liu, Hai-Ling

2010-02-01

A five-variable model (model M2) was developed for the bioconcentration factors (BCFs) of nonpolar organic compounds (NPOCs) by using molecular electronegativity distance vector (MEDV) to characterize the structures of NPOCs and variable selection and modeling based on prediction (VSMP) to select the optimum descriptors. The estimated correlation coefficient (r (2)) and the leave-one-out cross-validation correlation coefficients (q (2)) of model M2 were 0.9271 and 0.9171, respectively. The model was externally validated by splitting the whole data set into a representative training set of 85 chemicals and a validation set of 29 chemicals. The results show that the main structural factors influencing the BCFs of NPOCs are -cCc, cCcc, -Cl, and -Br (where "-" refers to a single bond and "c" refers to a conjugated bond). The quantitative structure-property relationship (QSPR) model can effectively predict the BCFs of NPOCs, and the predictions of the model can also extend the current BCF database of experimental values.

The effect of perfluorination on the aromaticity of benzene and heterocyclic six-membered rings.

PubMed

Wu, Judy I; Pühlhofer, Frank G; Schleyer, Paul von Ragué; Puchta, Ralph; Kiran, Boggavarapu; Mauksch, Michael; Hommes, Nico J R van Eikema; Alkorta, Ibon; Elguero, José

2009-06-18

Despite having six highly electronegative F's, perfluorobenzene C(6)F(6) is as aromatic as benzene. Ab initio block-localized wave function (BLW) computations reveal that both C(6)F(6) and benzene have essentially the same extra cyclic resonance energies (ECREs). Localized molecular orbital (LMO)-nucleus-independent chemical shifts (NICS) grids demonstrates that the F's induce only local paratropic contributions that are not related to aromaticity. Thus, all of the fluorinated benzenes (C(6)F(n)H((6-n)), n = 1-6) have similar ring-LMO-NICS(pi zz) values. However, 1,3-difluorobenzene 2b and 1,3,5-trifluorobenzene 3c are slightly less aromatic than their isomers due to a greater degree of ring charge alternation. Isoelectronic C(5)H(5)Y heterocycles (Y = BH(-), N, NH(+)) are as aromatic as benzene, based on their ring-LMO-NICS(pi zz) and ECRE values, unless extremely electronegative heteroatoms (e.g., Y = O(+)) are involved.

Rapid prediction of chemical metabolism by human UDP-glucuronosyltransferase isoforms using quantum chemical descriptors derived with the electronegativity equalization method.

PubMed

Sorich, Michael J; McKinnon, Ross A; Miners, John O; Winkler, David A; Smith, Paul A

2004-10-07

This study aimed to evaluate in silico models based on quantum chemical (QC) descriptors derived using the electronegativity equalization method (EEM) and to assess the use of QC properties to predict chemical metabolism by human UDP-glucuronosyltransferase (UGT) isoforms. Various EEM-derived QC molecular descriptors were calculated for known UGT substrates and nonsubstrates. Classification models were developed using support vector machine and partial least squares discriminant analysis. In general, the most predictive models were generated with the support vector machine. Combining QC and 2D descriptors (from previous work) using a consensus approach resulted in a statistically significant improvement in predictivity (to 84%) over both the QC and 2D models and the other methods of combining the descriptors. EEM-derived QC descriptors were shown to be both highly predictive and computationally efficient. It is likely that EEM-derived QC properties will be generally useful for predicting ADMET and physicochemical properties during drug discovery.

Negative ion spectrometry for detecting nitrated explosives

NASA Technical Reports Server (NTRS)

Boettger, H. G.; Yinon, J.

1975-01-01

Ionization procedure is modified to produce mainly negative ions by electron capture. Peaks of negative ions are monitored conventionally. Nitrated organic materials could be identified directly from sample sniff inlet stream by suitably modified mass spectrometer because of unique electronegativity which nitro group imparts to organic material.

The How and Why of Chemical Reactions

ERIC Educational Resources Information Center

Schubert, Leo

1970-01-01

Presents a discussion of some of the fundamental concepts in thermodynamics and quantum mechanics including entropy, enthalpy, free energy, the partition function, chemical kinetics, transition state theory, the making and breaking of chemical bonds, electronegativity, ion sizes, intermolecular energies and of their role in explaining the nature…

Provocative Opinion: Can Chemistry be Learned Without Understanding?

ERIC Educational Resources Information Center

Sanderson, R. T.

1974-01-01

Voices the opinion that clearer and more useful explanations of common chemistry are needed to facilitate understanding. Presents examples from the realms of atomic structure, periodic table, history of chemistry, valence, electronegativity, electrode potentials, covalent bonds, polar covalence, bond energy, and causes of chemical change. (GS)

Effect of p–d hybridization, structural distortion and cation electronegativity on electronic properties of ZnSnX{sub 2} (X=P, As, Sb) chalcopyrite semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mishra, S.; Ganguli, B., E-mail: biplabg@nitrkl.ac.in

2013-04-15

Significant effects of p–d hybridization, structural distortion and cation-electro-negativity are found on band gap in ZnSnX{sub 2} (X=P, As, Sb). Our study suggests these compounds to be direct band gap semiconductors with band gaps of 1.23, 0.68 and 0.19 eV respectively. Lattice constants, tetragonal distortion (η), anion displacement, bond lengths and bulk moduli are calculated by Density Functional Theory based on Tight binding Linear Muffin-Tin orbital method. Our result of structural properties is in good agreement with the available experimental and other theoretical results. Calculated band gaps also agree well with the experimental works within LDA limitation. Unlike other semiconductorsmore » in the group II–IV–V{sub 2}, there is a reduction in the band gap of 0.22, 0.20 and 0.24 eV respectively in ZnSnX{sub 2} (X=P, As, Sb) due to p–d hybridization. Structural distortion decreases band gap by 0.20, 0.12 and 0.10 eV respectively. We find that cation electronegativity effect is responsible for increasing the band gap relative to their binary analogs GaInP{sub 2}, InGaAs{sub 2} and GaInSb{sub 2} respectively and increment are 0.13, 0.04 and 0.13 eV respectively. - Graphical abstract: One unit cell of ZnSnX{sub 2} (X=P, As, Sb) chalcopyrite semiconductor. Semiconductors ZnSnX{sub 2} (X=P, As, Sb) are found to be direct band gap semiconductors with band gaps 1.23, 0.68 and 0.19 eV respectively. The quantitative estimate of effects of p–d hybridization, structural distortion and cation electronegativity shows band gaps change significantly due to these effects. Highlights: ► ZnSnX{sub 2} (X=P, As, Sb) are direct band gap semiconductors. ► These have band gaps of 1.23 eV, 0.68 eV and 0.19 eV respectively. ► The band gap reduction due to p–d hybridization is 13.41%, 18.51% and 40% respectively. ► Band gap reduction due to structural distortion is 12.12%, 11.11% and 16.66% respectively. ► Band gap increases 8.38%, 3.70% and 21.31% respectively due to cation electronegativity.« less

How We Teach Molecular Structure to Freshmen.

ERIC Educational Resources Information Center

Hurst, Michael O.

2002-01-01

Currently molecular structure is taught in general chemistry using three theories, this being based more on historical development rather than logical pedagogy. Electronegativity is taught with a confusing mixture of definitions that do not correspond to modern practice. Valence bond theory and VSEPR are used together in a way that often confuses…

Lithium-tellurium bimetallic cell has increased voltage

NASA Technical Reports Server (NTRS)

Cairns, E. J.; Rogers, G. L.; Shimotake, H.

1968-01-01

Lithium-tellurium secondary cell with a fused lithium halide electrolyte, tested in the temperature range 467 degrees to 500 degrees C, showed improvement over the sodium bismuth cell. The voltage of this bimetallic cell was increased by using the more electropositive anode material, lithium, and the more electronegative cathode material, tellurium.

Six Pillars of Organic Chemistry

ERIC Educational Resources Information Center

Mullins, Joseph J.

2008-01-01

This article describes an approach to teaching organic chemistry, which is to have students build their knowledge of organic chemistry upon a strong foundation of the fundamental concepts of the subject. Specifically, the article focuses upon a core set of concepts that I call "the six pillars of organic chemistry": electronegativity, polar…

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 31 Money and Finance:Treasury 3 2011-07-01 2011-07-01 false Uranium feed; natural uranium feed...) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.317 Uranium feed; natural uranium feed. The term uranium feed or natural uranium feed means natural uranium in the form of UF6 suitable for uranium...

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 31 Money and Finance: Treasury 3 2010-07-01 2010-07-01 false Uranium feed; natural uranium feed...) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.317 Uranium feed; natural uranium feed. The term uranium feed or natural uranium feed means natural uranium in the form of UF6 suitable for uranium...

Process for continuous production of metallic uranium and uranium alloys

DOEpatents

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.

Process for continuous production of metallic uranium and uranium alloys

DOEpatents

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.

Method for converting uranium oxides to uranium metal

DOEpatents

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.

The Energy of Substituted Ethanes. Asymmetry Orbitals

PubMed Central

Salem, Lionel; Hoffmann, Roald; Otto, Peter

1973-01-01

The leading terms in the energy of a general substituted ethane are derived in explicit form as a function of the torsional angle θ, the substituent electronegativities, and their mutual overlaps. The energy is found to be the sum of all four overlaps between pairs of asymmetry orbitals, and satisfies the requisite symmetry properties. PMID:16592060

Expanded Definition of the Oxidation State

ERIC Educational Resources Information Center

Loock, Hans-Peter

2011-01-01

A proposal to define the oxidation state of an atom in a compound as the hypothetical charge of the corresponding atomic ion that is obtained by heterolytically cleaving its bonds such that the atom with the higher electronegativity in a bond is allocated all electrons in the bond. Bonds between like atoms are cleaved homolytically. This…

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pallan, Pradeep S.; Prakash, Thazha P.; Li, Feng

Crystal structures of A-form and B-form DNA duplexes containing 2'-S-methyl-uridines reveal that the modified residues adopt a RNA-like C3'-endo pucker, illustrating that the replacement of electronegative oxygen at the 2'-carbon of RNA by sulfur does not appear to fundamentally alter the conformational preference of the sugar in the oligonucleotide context and sterics trump stereoelectronics.

Novel approach for modifying microporous filters for virus concentration from water.

PubMed Central

Preston, D R; Vasudevan, T V; Bitton, G; Farrah, S R; Morel, J L

1988-01-01

Electronegative microporous filters composed of epoxyfiberglass (Filterite) were treated with cationic polymers to enhance their virus-adsorbing properties. This novel and inexpensive approach to microporous filter modification entails soaking filters in an aqueous solution of a cationic polymer such as polyethyleneimine (PEI) for 2 h at room temperature and then allowing the filters to air dry overnight on absorbent paper towels. PEI-treated filters were evaluated for coliphage (MS2, T2, and phi X174) and enterovirus (poliovirus type 1 and coxsackievirus type B5) adsorption from buffer at pH 3.5 to 9.0 and for indigenous coliphages from unchlorinated secondary effluent at ambient pH. Adsorbed viruses were recovered with 3% beef extract (pH 9). Several other cationic polymers were used to modify epoxyfiberglass filters and were evaluated for their ability to concentrate viruses from water. Zeta potentials of disrupted filter material indicated that electronegative epoxyfiberglass filters were made more electropositive when treated with cationic polymers. In general, epoxyfiberglass filters treated with cationic polymers were found to adsorb a greater percentage of coliphages and enteroviruses than were untreated filters. PMID:2843091

Synthesis and properties of ApU analogues containing 2'-halo-2'-deoxyadenosines. Effects of 2' substituents on oligonucleotide conformation.

PubMed

Uesugi, S; Kaneyasu, T; Ikehara, M

1982-11-09

Five A-U analogues containing deoxyadenosine or 2'-halo-2'-deoxyadenosines, which are known to have widely different C3'-endo conformer populations according to their electronegativities of the halogen substituents, dAfl-U, dAcl-U, dAbr-U, dAio-U, and dA-U, were synthesized chemically. Characterization of these dimers has been performed by UV absorption, circular dichroism, and proton nuclear magnetic resonance spectroscopy. The results show that the dimers containing 2'-halo-2'-deoxyadenosines have stacked conformations with a geometry similar to that of A-U and the degree of stacking decreases in the order dAfl-U greater than dAcl-U greater than dAbr-U greater than dAio-U. dAcl-U is assumed to have the same degree of stacking as A-U. dA-U takes a more stacked conformation than does dAio-U, but the mode of stacking is different from those of the other dimers. The effects of the 2' substituents on dimer conformation are discussed in terms of electronegativity, molecular size, and hydrophobicity.

Nature of the chemical bond and prediction of radiation tolerance in pyrochlore and defect fluorite compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lumpkin, Gregory R.; Institute of Materials and Engineering Science, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234; Pruneda, Miguel

2007-04-15

The radiation tolerance of synthetic pyrochlore and defect fluorite compounds has been studied using ion irradiation. We show that the results can be quantified in terms of the critical temperature for amorphization, structural parameters, classical Pauling electronegativity difference, and disorder energies. Our results demonstrate that radiation tolerance is correlated with a change in the structure from pyrochlore to defect fluorite, a smaller unit cell dimension, and lower cation-anion disorder energy. Radiation tolerance is promoted by an increase in the Pauling cation-anion electronegativity difference or, in other words, an increase in the ionicity of the chemical bonds. A further analysis ofmore » the data indicates that, of the two possible cation sites in ideal pyrochlore, the smaller B-site cation appears to play the major role in bonding. This result is supported by ab initio calculations of the structure and bonding, showing a correlation between the Mulliken overlap populations of the B-site cation and the critical temperature. - Graphical abstract: Three-dimensional representation of the predicted critical amorphization temperature in pyrochlores.« less

Hydrogen bonding between hydrides of the upper-right part of the periodic table

NASA Astrophysics Data System (ADS)

Simončič, Matjaž; Urbic, Tomaz

2018-05-01

One of the most important electrostatic interactions between molecules is most definitely the hydrogen bond. Understanding the basis of this interaction may offer us the insight needed to understand its effect on the macroscopic scale. Hydrogen bonding is for example the reason for anomalous properties in compounds like water and naturally life as we know it. The strength of the bond depends on numerous factors, among them the electronegativity of participating atoms. In this work we calculated the strength of hydrogen bonds between hydrides of the upper-right part of the periodic table (C, N, O, F, P, S, Cl, As, Se, Br) using quantum-chemical methods. The aim was to determine what influences the strength of strong and weak hydrogen bonds in simple hydrides. Various relationships were checked. A relation between the strength of the bond and the electronegativity of the participating atoms was found. We also observed a correlation between the strength of hydrogen bonds and the inter-atomic distances, along with the dependence on the charge transfer on the atom of the donor. We also report characteristic geometries of different dimers.

Global Model of Time-Modulated Electronegative Discharges for Neutral Radical and Electron Temperature Control

NASA Astrophysics Data System (ADS)

Kim, Sungjin; Lieberman, M. A.; Lichtenberg, A. J.

2003-10-01

Control and reduction of neutral radical flux/ion flux ratio and electron temperature Te is required for next generation etching in the microelectronics industry. We investigate time-modulated power for these purposes using a volume-averaged (global) oxygen discharge model, We consider pressures of 10-50 mTorr and plasma densities of 10^10-10^11 cm-3. In this regime, the discharge is found to be weakly electronegative. The modulation period and the duty ratio (on-time/period) are varied to determine the optimum conditions for reduction of FR= O-atom flux/ion flux and T_e. Two chambers with different height/diameter ratios (<< 1, and unity) are examined to determine the influence of the surface-area/volume ratio. At a fixed duty ratio, both FR and Te are found to have minimum values as the pulse period is varied, with the minimum value decreasing as the duty ratio decreases. Significant reductions in FR and Te are found. Support provided by Lam Research, NSF Grant ECS-0139956, California industries, and UC-SMART Contract SM99-10051.

Atomic Charge Parameters for the Finite Difference Poisson-Boltzmann Method Using Electronegativity Neutralization.

PubMed

Yang, Qingyi; Sharp, Kim A

2006-07-01

An optimization of Rappe and Goddard's charge equilibration (QEq) method of assigning atomic partial charges is described. This optimization is designed for fast and accurate calculation of solvation free energies using the finite difference Poisson-Boltzmann (FDPB) method. The optimization is performed against experimental small molecule solvation free energies using the FDPB method and adjusting Rappe and Goddard's atomic electronegativity values. Using a test set of compounds for which experimental solvation energies are available and a rather small number of parameters, very good agreement was obtained with experiment, with a mean unsigned error of about 0.5 kcal/mol. The QEq atomic partial charge assignment method can reflect the effects of the conformational changes and solvent induction on charge distribution in molecules. In the second section of the paper we examined this feature with a study of the alanine dipeptide conformations in water solvent. The different contributions to the energy surface of the dipeptide were examined and compared with the results from fixed CHARMm charge potential, which is widely used for molecular dynamics studies.

Prediction of chromatographic relative retention time of polychlorinated biphenyls from the molecular electronegativity distance vector.

PubMed

Liu, Shu-Shen; Liu, Yan; Yin, Da-Qian; Wang, Xiao-Dong; Wang, Lian-Sheng

2006-02-01

Using the molecular electronegativity distance vector (MEDV) descriptors derived directly from the molecular topological structures, the gas chromatographic relative retention times (RRTs) of 209 polychlorinated biphenyls (PCBs) on the SE-54 stationary phase were predicted. A five-variable regression equation with the correlation coefficient of 0.9964 and the root mean square errors of 0.0152 was developed. The descriptors included in the equation represent degree of chlorination (nCl), nonortho index (Ino), and interactions between three pairs of atom types, i.e., atom groups -C= and -C=, -C= and >C=, -C= and -Cl. It has been proved that the retention times of all 209 PCB congeners can be accurately predicted as long as there are more than 50 calibration compounds. In the same way, the MEDV descriptors are also used to develop the five- or six-variable models of RRTs of PCBs on other 18 stationary phases and the correlation coefficients in both modeling stage and LOO cross-validation step are not lower than 0.99 except two models.

Compactness Aromaticity of Atoms in Molecules

PubMed Central

Putz, Mihai V.

2010-01-01

A new aromaticity definition is advanced as the compactness formulation through the ratio between atoms-in-molecule and orbital molecular facets of the same chemical reactivity property around the pre- and post-bonding stabilization limit, respectively. Geometrical reactivity index of polarizability was assumed as providing the benchmark aromaticity scale, since due to its observable character; with this occasion new Hydrogenic polarizability quantum formula that recovers the exact value of 4.5 a03 for Hydrogen is provided, where a0 is the Bohr radius; a polarizability based–aromaticity scale enables the introduction of five referential aromatic rules (Aroma 1 to 5 Rules). With the help of these aromatic rules, the aromaticity scales based on energetic reactivity indices of electronegativity and chemical hardness were computed and analyzed within the major semi-empirical and ab initio quantum chemical methods. Results show that chemical hardness based-aromaticity is in better agreement with polarizability based-aromaticity than the electronegativity-based aromaticity scale, while the most favorable computational environment appears to be the quantum semi-empirical for the first and quantum ab initio for the last of them, respectively. PMID:20480020

Electronegativity calculation of bulk modulus and band gap of ternary ZnO-based alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Keyan; Kang, Congying; Xue, Dongfeng, E-mail: dongfeng@ciac.jl.cn

2012-10-15

In this work, the bulk moduli and band gaps of M{sub x}Zn{sub 1−x}O (M = Be, Mg, Ca, Cd) alloys in the whole composition range were quantitatively calculated by using the electronegativity-related models for bulk modulus and band gap, respectively. We found that the change trends of bulk modulus and band gap with an increase of M concentration x are same for Be{sub x}Zn{sub 1−x}O and Cd{sub x}Zn{sub 1−x}O, while the change trends are reverse for Mg{sub x}Zn{sub 1−x}O and Ca{sub x}Zn{sub 1−x}O. It was revealed that the bulk modulus is related to the valence electron density of atoms whereasmore » the band gap is strongly influenced by the detailed chemical bonding behaviors of constituent atoms. The current work provides us a useful guide to compositionally design advanced alloy materials with both good mechanical and optoelectronic properties.« less

Polarizability effects on the structure and dynamics of ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cavalcante, Ary de Oliveira, E-mail: arycavalcante@ufam.edu.br; Departamento de Química, Universidade Federal do Amazonas, Av. Rodrigo Octávio, 6200, Coroado, Manaus, AM; Ribeiro, Mauro C. C.

2014-04-14

Polarization effects on the structure and dynamics of ionic liquids are investigated using molecular dynamics simulations. Four different ionic liquids were simulated, formed by the anions Cl{sup −} and PF{sub 6}{sup −}, treated as single fixed charge sites, and the 1-n-alkyl-3-methylimidazolium cations (1-ethyl and 1-butyl-), which are polarizable. The partial charge fluctuation of the cations is provided by the electronegativity equalization model (EEM) and a complete parameter set for the cations electronegativity (χ) and hardness (J) is presented. Results obtained from a non-polarizable model for the cations are also reported for comparison. Relative to the fixed charged model, the equilibriummore » structure of the first solvation shell around the imidazolium cations shows that inclusion of EEM polarization forces brings cations closer to each other and that anions are preferentially distributed above and below the plane of the imidazolium ring. The polarizable model yields faster translational and reorientational dynamics than the fixed charges model in the rotational-diffusion regime. In this sense, the polarizable model dynamics is in better agreement with the experimental data.« less

A model for the energy band gap of GaSbxAs1-x and InSbxAs1-x in the whole composition range

NASA Astrophysics Data System (ADS)

Zhao, Chuan-Zhen; Ren, He-Yu; Wei, Tong; Wang, Sha-Sha; Wang, Jun

2018-04-01

The band gap evolutions of GaSbxAs1-x and InSbxAs1-x in the whole composition range are investigated. It is found that the band gap evolutions of GaSbxAs1-x and InSbxAs1-x are determined by two factors. One is the impurity-host interaction in the As-rich and Sb-rich composition ranges. The other is the intraband coupling within the conduction band and separately within the valence band in the moderate composition range. Based on the band gap evolutions of GaSbxAs1-x and InSbxAs1-x, a model is established. In addition, it is found that the impurity-host interaction is determined by not only the mismatches in size and electronegativity between the introduced atoms in the host material and the anions of the host material, but also the difference in electronegativity between the introduced atoms in the host material and the cations of the host material.

Ion velocities in the presheath of electronegative, radio-frequency plasmas measured by low-energy cutoff

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sobolewski, Mark A.; Wang, Yicheng; Goyette, Amanda

2016-07-11

Simple kinematic considerations indicate that, under certain conditions in radio-frequency (rf) plasmas, the amplitude of the low-energy peak in ion energy distributions (IEDs) measured at an electrode depends sensitively on ion velocities upstream, at the presheath/sheath boundary. By measuring this amplitude, the velocities at which ions exit the presheath can be determined and long-standing controversies regarding presheath transport can be resolved. Here, IEDs measured in rf-biased, inductively coupled plasmas in CF{sub 4} gas determined the presheath exit velocities of all significant positive ions: CF{sub 3}{sup +}, CF{sub 2}{sup +}, CF{sup +}, and F{sup +}. At higher bias voltages, we detectedmore » essentially the same velocity for all four ions. For all ions, measured velocities were significantly lower than the Bohm velocity and the electropositive ion sound speed. Neither is an accurate boundary condition for rf sheaths in electronegative gases: under certain low-frequency, high-voltage criteria defined here, either yields large errors in predicted IEDs. These results indicate that many widely used sheath models will need to be revised.« less

Retinal findings in a patient of French ancestry with CABP4-related retinal disease.

PubMed

Smirnov, Vasily Mikhaïlovitch; Zeitz, Christina; Soumittra, Nagasamy; Audo, Isabelle; Defoort-Dhellemmes, Sabine

2018-04-01

CABP4-related retinal dysfunction is a cone-rod synaptic transmission disorder with electronegative electroretinogram (ERG) waveform. It is a rare retinal dysfunction that can be classified into the incomplete form of congenital stationary night blindness. Absent foveal reflex and overall foveal thinning were previously reported, but in most cases the fundus appearance was described as nearly normal. We report here peculiar macular changes in a patient of French ancestry harbouring CABP4 mutations. Complete ocular examination and full-field ERG were performed at the initial presentation and follow-up. Multimodal fundus imagining, including spectral-domain optical coherence tomography, colour, infrared reflectance and short-wavelength autofluorescence photographs, was performed during follow-up visits. A 7-month-old infant was addressed to our department for visual unresponsiveness and nystagmus. ERG had an electronegative waveform, even for light-adapted stimuli, thus supporting the diagnosis of photoreceptor-bipolar cell transmission disorder. Genetic investigations discovered a compound heterozygous mutation in CABP4: c.646C > T, p.Arg216*/c.673C > T, p.Arg225*. Multimodal fundus imaging, performed at follow-up visits, showed fine radial folds at the vitreomacular interface and dark foveal dots in both eyes. Optic coherence tomography revealed a focal foveal ellipsoid zone gap. Initial presentation was misleading with Leber congenital amaurosis. The electronegative ERG waveform reoriented the genetic investigations and thus establishing a correct diagnosis. To the best of our knowledge, the peculiar fundus changes observed in our patient were never reported before. We hypothesized that a foveal ellipsoid zone interruption discovered in our patient could reflect mostly a cone dysfunction. It was unclear whether the fine radial folds in both maculae were linked with high hyperopia or were an intrinsic feature of the retinal disease. CABP4-related retinal disease is a cone-rod system disorder with possible foveal abnormalities.

Spatiotemporal dynamics of charged species in the afterglow of plasmas containing negative ions.

PubMed

Kaganovich, I D; Ramamurthi, B N; Economou, D J

2001-09-01

The spatiotemporal evolution of charged species densities and wall fluxes during the afterglow of an electronegative discharge has been investigated. The decay of a plasma with negative ions consists of two stages. During the first stage of the afterglow, electrons dominate plasma diffusion and negative ions are trapped inside the vessel by the static electric field; the flux of negative ions to the walls is nearly zero. During this stage, the electron escape frequency increases considerably in the presence of negative ions, and can eventually approach free electron diffusion. During the second stage of the afterglow, electrons have disappeared, and positive and negative ions diffuse to the walls with the ion-ion ambipolar diffusion coefficient. Theories for plasma decay have been developed for equal and strongly different ion (T(i)) and electron (T(e)) temperatures. In the case T(i)=T(e), the species spatial profiles are similar and an analytic solution exists. When detachment is important in the afterglow (weakly electronegative gases, e.g., oxygen) the plasma decay crucially depends on the product of negative ion detachment frequency (gamma(d)) and diffusion time (tau(d)). If gamma(d)tau(d)>2, negative ions convert to electrons during their diffusion towards the walls. The presence of detached electrons results in "self-trapping" of the negative ions, due to emerging electric fields, and the negative ion flux to the walls is extremely small. In the case T(i)

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

Bioremediation of uranium contamination with enzymatic uranium reduction

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.

1992-01-01

Enzymatic uranium reduction by Desulfovibrio desulfuricans readily removed uranium from solution in a batch system or when D. desulfuricans was separated from the bulk of the uranium-containing water by a semipermeable membrane. Uranium reduction continued at concentrations as high as 24 mM. Of a variety of potentially inhibiting anions and metals evaluated, only high concentrations of copper inhibited uranium reduction. Freeze-dried cells, stored aerobically, reduced uranium as fast as fresh cells. D. desulfuricans reduced uranium in pH 4 and pH 7.4 mine drainage waters and in uraniumcontaining groundwaters from a contaminated Department of Energy site. Enzymatic uranium reduction has several potential advantages over other bioprocessing techniques for uranium removal, the most important of which are as follows: the ability to precipitate uranium that is in the form of a uranyl carbonate complex; high capacity for uranium removal per cell; the formation of a compact, relatively pure, uranium precipitate.

Release behavior of uranium in uranium mill tailings under environmental conditions.

PubMed

Liu, Bo; Peng, Tongjiang; Sun, Hongjuan; Yue, Huanjuan

2017-05-01

Uranium contamination is observed in sedimentary geochemical environments, but the geochemical and mineralogical processes that control uranium release from sediment are not fully appreciated. Identification of how sediments and water influence the release and migration of uranium is critical to improve the prevention of uranium contamination in soil and groundwater. To understand the process of uranium release and migration from uranium mill tailings under water chemistry conditions, uranium mill tailing samples from northwest China were investigated with batch leaching experiments. Results showed that water played an important role in uranium release from the tailing minerals. The uranium release was clearly influenced by contact time, liquid-solid ratio, particle size, and pH under water chemistry conditions. Longer contact time, higher liquid content, and extreme pH were all not conducive to the stabilization of uranium and accelerated the uranium release from the tailing mineral to the solution. The values of pH were found to significantly influence the extent and mechanisms of uranium release from minerals to water. Uranium release was monitored by a number of interactive processes, including dissolution of uranium-bearing minerals, uranium desorption from mineral surfaces, and formation of aqueous uranium complexes. Considering the impact of contact time, liquid-solid ratio, particle size, and pH on uranium release from uranium mill tailings, reducing the water content, decreasing the porosity of tailing dumps and controlling the pH of tailings were the key factors for prevention and management of environmental pollution in areas near uranium mines. Copyright © 2017 Elsevier Ltd. All rights reserved.

PRODUCTION OF URANIUM METAL BY CARBON REDUCTION

DOEpatents

Holden, R.B.; Powers, R.M.; Blaber, O.J.

1959-09-22

The preparation of uranium metal by the carbon reduction of an oxide of uranium is described. In a preferred embodiment of the invention a charge composed of carbon and uranium oxide is heated to a solid mass after which it is further heated under vacuum to a temperature of about 2000 deg C to produce a fused uranium metal. Slowly ccoling the fused mass produces a dendritic structure of uranium carbide in uranium metal. Reacting the solidified charge with deionized water hydrolyzes the uranium carbide to finely divide uranium dioxide which can be separated from the coarser uranium metal by ordinary filtration methods.

STRIPPING OF URANIUM FROM ORGANIC EXTRACTANTS

DOEpatents

Crouse, D.J. Jr.

1962-09-01

A liquid-liquid extraction method is given for recovering uranium values from uranium-containing solutions. Uranium is removed from a uranium-containing organic solution by contacting said organic solution with an aqueous ammonium carbonate solution substantially saturated in uranium values. A uranium- containing precipitate is thereby formed which is separated from the organic and aqueous phases. Uranium values are recovered from this separated precipitate. (AE C)

Process for electroslag refining of uranium and uranium alloys

DOEpatents

Lewis, P.S. Jr.; Agee, W.A.; Bullock, J.S. IV; Condon, J.B.

1975-07-22

A process is described for electroslag refining of uranium and uranium alloys wherein molten uranium and uranium alloys are melted in a molten layer of a fluoride slag containing up to about 8 weight percent calcium metal. The calcium metal reduces oxides in the uranium and uranium alloys to provide them with an oxygen content of less than 100 parts per million. (auth)

Detection of depleted uranium in urine of veterans from the 1991 Gulf War.

PubMed

Gwiazda, R H; Squibb, K; McDiarmid, M; Smith, D

2004-01-01

American soldiers involved in "friendly fire" accidents during the 1991 Gulf War were injured with depleted-uranium-containing fragments or possibly exposed to depleted uranium via other routes such as inhalation, ingestion, and/or wound contamination. To evaluate the presence of depleted uranium in these soldiers eight years later, the uranium concentration and depleted uranium content of urine samples were determined by inductively coupled plasma mass spectrometry in (a) depleted uranium exposed soldiers with embedded shrapnel, (b) depleted uranium exposed soldiers with no shrapnel, and (c) a reference group of deployed soldiers not involved in the friendly fire incidents. Uranium isotopic ratios measured in many urine samples injected directly into the inductively coupled plasma mass spectrometer and analyzed at a mass resolution m/delta m of 300 appeared enriched in 235U with respect to natural abundance (0.72%) due to the presence of an interference of a polyatomic molecule of mass 234.81 amu that was resolved at a mass resolution m/delta m of 4,000. The 235U abundance measured on uranium separated from these urines by anion exchange chromatography was clearly natural or depleted. Urine uranium concentrations of soldiers with shrapnel were higher than those of the two other groups, and 16 out of 17 soldiers with shrapnel had detectable depleted uranium in their urine. In depleted uranium exposed soldiers with no shrapnel, depleted uranium was detected in urine samples of 10 out of 28 soldiers. The median uranium concentration of urines with depleted uranium from soldiers without shrapnel was significantly higher than in urines with no depleted uranium, though substantial overlap in urine uranium concentrations existed between the two groups. Accordingly, assessment of depleted uranium exposure using urine must rely on uranium isotopic analyses, since urine uranium concentration is not an unequivocal indicator of depleted uranium presence in soldiers with no embedded shrapnel.

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 31 Money and Finance:Treasury 3 2013-07-01 2013-07-01 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...

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 31 Money and Finance:Treasury 3 2012-07-01 2012-07-01 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...

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 31 Money and Finance:Treasury 3 2014-07-01 2014-07-01 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...

Process for electrolytically preparing uranium metal

DOEpatents

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.

Process for electrolytically preparing uranium metal

DOEpatents

Haas, Paul A.

1989-08-01

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.

Decontamination of uranium-contaminated waste oil using supercritical fluid and nitric acid.

PubMed

Sung, Jinhyun; Kim, Jungsoo; Lee, Youngbae; Seol, Jeunggun; Ryu, Jaebong; Park, Kwangheon

2011-07-01

The waste oil used in nuclear fuel processing is contaminated with uranium because of its contact with materials or environments containing uranium. Under current law, waste oil that has been contaminated with uranium is very difficult to dispose of at a radioactive waste disposal site. To dispose of the uranium-contaminated waste oil, the uranium was separated from the contaminated waste oil. Supercritical R-22 is an excellent solvent for extracting clean oil from uranium-contaminated waste oil. The critical temperature of R-22 is 96.15 °C and the critical pressure is 49.9 bar. In this study, a process to remove uranium from the uranium-contaminated waste oil using supercritical R-22 was developed. The waste oil has a small amount of additives containing N, S or P, such as amines, dithiocarbamates and dialkyldithiophosphates. It seems that these organic additives form uranium-combined compounds. For this reason, dissolution of uranium from the uranium-combined compounds using nitric acid was needed. The efficiency of the removal of uranium from the uranium-contaminated waste oil using supercritical R-22 extraction and nitric acid treatment was determined.

Diffusive gradient in thin FILMS (DGT) compared with soil solution and labile uranium fraction for predicting uranium bioavailability to ryegrass.

PubMed

Duquène, L; Vandenhove, H; Tack, F; Van Hees, M; Wannijn, J

2010-02-01

The usefulness of uranium concentration in soil solution or recovered by selective extraction as unequivocal bioavailability indices for uranium uptake by plants is still unclear. The aim of the present study was to test if the uranium concentration measured by the diffusive gradient in thin films (DGT) technique is a relevant substitute for plant uranium availability in comparison to uranium concentration in the soil solution or uranium recovered by ammonium acetate. Ryegrass (Lolium perenne L. var. Melvina) is grown in greenhouse on a range of uranium spiked soils. The DGT-recovered uranium concentration (C(DGT)) was correlated with uranium concentration in the soil solution or with uranium recovered by ammonium acetate extraction. Plant uptake was better predicted by the summed soil solution concentrations of UO(2)(2+), uranyl carbonate complexes and UO(2)PO(4)(-). The DGT technique did not provide significant advantages over conventional methods to predict uranium uptake by plants. Copyright 2009 Elsevier Ltd. All rights reserved.

URANIUM LEACHING AND RECOVERY PROCESS

DOEpatents

McClaine, L.A.

1959-08-18

A process is described for recovering uranium from carbonate leach solutions by precipitating uranium as a mixed oxidation state compound. Uranium is recovered by adding a quadrivalent uranium carbon;te solution to the carbonate solution, adjusting the pH to 13 or greater, and precipitating the uranium as a filterable mixed oxidation state compound. In the event vanadium occurs with the uranium, the vanadium is unaffected by the uranium precipitation step and remains in the carbonate solution. The uranium-free solution is electrolyzed in the cathode compartment of a mercury cathode diaphragm cell to reduce and precipitate the vanadium.

Plutonium recovery from spent reactor fuel by uranium displacement

DOEpatents

Ackerman, John P.

1992-01-01

A process for separating uranium values and transuranic values from fission products containing rare earth values when the values are contained together in a molten chloride salt electrolyte. A molten chloride salt electrolyte with a first ratio of plutonium chloride to uranium chloride is contacted with both a solid cathode and an anode having values of uranium and fission products including plutonium. A voltage is applied across the anode and cathode electrolytically to transfer uranium and plutonium from the anode to the electrolyte while uranium values in the electrolyte electrolytically deposit as uranium metal on the solid cathode in an amount equal to the uranium and plutonium transferred from the anode causing the electrolyte to have a second ratio of plutonium chloride to uranium chloride. Then the solid cathode with the uranium metal deposited thereon is removed and molten cadmium having uranium dissolved therein is brought into contact with the electrolyte resulting in chemical transfer of plutonium values from the electrolyte to the molten cadmium and transfer of uranium values from the molten cadmium to the electrolyte until the first ratio of plutonium chloride to uranium chloride is reestablished.

Cellular localization of uranium in the renal proximal tubules during acute renal uranium toxicity.

PubMed

Homma-Takeda, Shino; Kitahara, Keisuke; Suzuki, Kyoko; Blyth, Benjamin J; Suya, Noriyoshi; Konishi, Teruaki; Terada, Yasuko; Shimada, Yoshiya

2015-12-01

Renal toxicity is a hallmark of uranium exposure, with uranium accumulating specifically in the S3 segment of the proximal tubules causing tubular damage. As the distribution, concentration and dynamics of accumulated uranium at the cellular level is not well understood, here, we report on high-resolution quantitative in situ measurements by high-energy synchrotron radiation X-ray fluorescence analysis in renal sections from a rat model of uranium-induced acute renal toxicity. One day after subcutaneous administration of uranium acetate to male Wistar rats at a dose of 0.5 mg uranium kg(-1) body weight, uranium concentration in the S3 segment of the proximal tubules was 64.9 ± 18.2 µg g(-1) , sevenfold higher than the mean renal uranium concentration (9.7 ± 2.4 µg g(-1) ). Uranium distributed into the epithelium of the S3 segment of the proximal tubules and highly concentrated uranium (50-fold above mean renal concentration) in micro-regions was found near the nuclei. These uranium levels were maintained up to 8 days post-administration, despite more rapid reductions in mean renal concentration. Two weeks after uranium administration, damaged areas were filled with regenerating tubules and morphological signs of tissue recovery, but areas of high uranium concentration (100-fold above mean renal concentration) were still found in the epithelium of regenerating tubules. These data indicate that site-specific accumulation of uranium in micro-regions of the S3 segment of the proximal tubules and retention of uranium in concentrated areas during recovery are characteristics of uranium behavior in the kidney. Copyright © 2015 John Wiley & Sons, Ltd.

Method of preparation of uranium nitride

DOEpatents

Kiplinger, Jaqueline Loetsch; Thomson, Robert Kenneth James

2013-07-09

Method for producing terminal uranium nitride complexes comprising providing a suitable starting material comprising uranium; oxidizing the starting material with a suitable oxidant to produce one or more uranium(IV)-azide complexes; and, sufficiently irradiating the uranium(IV)-azide complexes to produce the terminal uranium nitride complexes.

10 CFR 760.1 - Uranium leases on lands controlled by DOE. (Domestic Uranium Program Circular No. 760.1, formerly...

Code of Federal Regulations, 2011 CFR

2011-01-01

... 10 Energy 4 2011-01-01 2011-01-01 false Uranium leases on lands controlled by DOE. (Domestic Uranium Program Circular No. 760.1, formerly (AEC) Domestic Uranium Program Circular 8, 10 CFR 60.8). 760.1 Section 760.1 Energy DEPARTMENT OF ENERGY DOMESTIC URANIUM PROGRAM § 760.1 Uranium leases on lands...

10 CFR 760.1 - Uranium leases on lands controlled by DOE. (Domestic Uranium Program Circular No. 760.1, formerly...

Code of Federal Regulations, 2013 CFR

2013-01-01

... 10 Energy 4 2013-01-01 2013-01-01 false Uranium leases on lands controlled by DOE. (Domestic Uranium Program Circular No. 760.1, formerly (AEC) Domestic Uranium Program Circular 8, 10 CFR 60.8). 760.1 Section 760.1 Energy DEPARTMENT OF ENERGY DOMESTIC URANIUM PROGRAM § 760.1 Uranium leases on lands...

10 CFR 760.1 - Uranium leases on lands controlled by DOE. (Domestic Uranium Program Circular No. 760.1, formerly...

Code of Federal Regulations, 2012 CFR

2012-01-01

... 10 Energy 4 2012-01-01 2012-01-01 false Uranium leases on lands controlled by DOE. (Domestic Uranium Program Circular No. 760.1, formerly (AEC) Domestic Uranium Program Circular 8, 10 CFR 60.8). 760.1 Section 760.1 Energy DEPARTMENT OF ENERGY DOMESTIC URANIUM PROGRAM § 760.1 Uranium leases on lands...

10 CFR 760.1 - Uranium leases on lands controlled by DOE. (Domestic Uranium Program Circular No. 760.1, formerly...

Code of Federal Regulations, 2014 CFR

2014-01-01

... 10 Energy 4 2014-01-01 2014-01-01 false Uranium leases on lands controlled by DOE. (Domestic Uranium Program Circular No. 760.1, formerly (AEC) Domestic Uranium Program Circular 8, 10 CFR 60.8). 760.1 Section 760.1 Energy DEPARTMENT OF ENERGY DOMESTIC URANIUM PROGRAM § 760.1 Uranium leases on lands...

10 CFR 760.1 - Uranium leases on lands controlled by DOE. (Domestic Uranium Program Circular No. 760.1, formerly...

Code of Federal Regulations, 2010 CFR

2010-01-01

... 10 Energy 4 2010-01-01 2010-01-01 false Uranium leases on lands controlled by DOE. (Domestic Uranium Program Circular No. 760.1, formerly (AEC) Domestic Uranium Program Circular 8, 10 CFR 60.8). 760.1 Section 760.1 Energy DEPARTMENT OF ENERGY DOMESTIC URANIUM PROGRAM § 760.1 Uranium leases on lands...

PROCESS OF PRODUCING REFRACTORY URANIUM OXIDE ARTICLES

DOEpatents

Hamilton, N.E.

1957-12-01

A method is presented for fabricating uranium oxide into a shaped refractory article by introducing a uranium halide fluxing reagent into the uranium oxide, and then mixing and compressing the materials into a shaped composite mass. The shaped mass of uranium oxide and uranium halide is then fired at an elevated temperature so as to form a refractory sintered article. It was found in the present invention that the introduction of a uraninm halide fluxing agent afforded a fluxing action with the uranium oxide particles and that excellent cohesion between these oxide particles was obtained. Approximately 90% of uranium dioxide and 10% of uranium tetrafluoride represent a preferred composition.

31 CFR 540.309 - Natural uranium.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 31 Money and Finance:Treasury 3 2013-07-01 2013-07-01 false Natural uranium. 540.309 Section 540... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.309 Natural uranium. The term natural uranium means uranium found in...

31 CFR 540.309 - Natural uranium.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 31 Money and Finance:Treasury 3 2014-07-01 2014-07-01 false Natural uranium. 540.309 Section 540... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.309 Natural uranium. The term natural uranium means uranium found in...

31 CFR 540.309 - Natural uranium.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 31 Money and Finance:Treasury 3 2012-07-01 2012-07-01 false Natural uranium. 540.309 Section 540... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.309 Natural uranium. The term natural uranium means uranium found in...

Computational study of frontier orbitals, moments, chemical reactivity and thermodynamic parameters of sildenafil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sachdeva, Ritika, E-mail: ritika.sachdeva21@gmail.com; Kaur, Prabhjot; Singh, V. P.

2016-05-06

Analysis of frontier orbitals of sildenafil has been carried using Density Functional Theory. On the basis of HOMO-LUMO energy, values of global chemical reactivity descriptors such as electronegativity, chemical hardness, softness, chemical potential, electrophilicity index have been calculated. Calculated values of dipole moment, polarizability, hyperpolarizability have also been reported for sildenafil along with its thermodynamic parameters.

Alternating copolymerization of fluoroalkenes with carbon monoxide.

PubMed

Fujita, Tomoyuki; Nakano, Koji; Yamashita, Makoto; Nozaki, Kyoko

2006-02-15

The palladium-catalyzed alternating copolymerization of fluoroalkenes, represented as CH(2)=CH-CH(2)-C(n)F(2n+1), with CO was performed using (R,S)-BINAPHOS (2e) as a ligand. The CH(2)-C(n)F(2n+1) group is the most electronegative substituent ever reported for the copolymerization (Taft's sigma value of 0.90 for CH(2)CF(3)). The copolymer obtained from CH(2)=CH-CH(2)-C(8)F(17) (1a) existed as a mixture of polyspiroketal and polyketone, while that from CH(2)=CH-CH(2)-C(4)F(9) (1b) was a pure polyspiroketal, as was revealed by infrared and (13)C-CP/MAS NMR spectroscopies. The terminal structure of the polymer from 1b was confirmed by MALDI-TOF MS spectrometry. Detailed NMR studies suggested that the much higher reactivity with (R,S)-BINAPHOS (2e) than that with the conventional ligand DPPP (2a) can be attributed to the unique 1,2-insertion of the fluoroalkene into acylpalladium species. The existence of an electronegative substituent on the alpha-carbon of the palladium center is successfully avoided in the 1,2-insertion mechanism.

A Stable, Narrow-Gap Oxyfluoride Photocatalyst for Visible-Light Hydrogen Evolution and Carbon Dioxide Reduction.

PubMed

Kuriki, Ryo; Ichibha, Tom; Hongo, Kenta; Lu, Daling; Maezono, Ryo; Kageyama, Hiroshi; Ishitani, Osamu; Oka, Kengo; Maeda, Kazuhiko

2018-05-30

Mixed anion compounds such as oxynitrides and oxychalcogenides are recognized as potential candidates of visible-light-driven photocatalysts since, as compared with oxygen 2p orbitals, p orbitals of less electronegative anion (e.g., N 3- , S 2- ) can form a valence band that has more negative potential. In this regard, oxyfluorides appear unsuitable because of the higher electronegativity of fluorine. Here we show an exceptional case, an anion-ordered pyrochlore oxyfluoride Pb 2 Ti 2 O 5.4 F 1.2 that has a small band gap (ca. 2.4 eV). With suitable modification of Pb 2 Ti 2 O 5.4 F 1.2 by promoters such as platinum nanoparticles and a binuclear ruthenium(II) complex, Pb 2 Ti 2 O 5.4 F 1.2 worked as a stable photocatalyst for visible-light-driven H 2 evolution and CO 2 reduction. Density functional theory calculations have revealed that the unprecedented visible-light-response of Pb 2 Ti 2 O 5.4 F 1.2 arises from strong interaction between Pb-6s and O-2p orbitals, which is enabled by a short Pb-O bond in the pyrochlore lattice due to the fluorine substitution.

Alert-QSAR. Implications for Electrophilic Theory of Chemical Carcinogenesis

PubMed Central

Putz, Mihai V.; Ionaşcu, Cosmin; Putz, Ana-Maria; Ostafe, Vasile

2011-01-01

Given the modeling and predictive abilities of quantitative structure activity relationships (QSARs) for genotoxic carcinogens or mutagens that directly affect DNA, the present research investigates structural alert (SA) intermediate-predicted correlations ASA of electrophilic molecular structures with observed carcinogenic potencies in rats (observed activity, A = Log[1/TD50], i.e., ASA=f(X1SA,X2SA,…)). The present method includes calculation of the recently developed residual correlation of the structural alert models, i.e., ARASA=f(A−ASA,X1SA,X2SA,…). We propose a specific electrophilic ligand-receptor mechanism that combines electronegativity with chemical hardness-associated frontier principles, equality of ligand-reagent electronegativities and ligand maximum chemical hardness for highly diverse toxic molecules against specific receptors in rats. The observed carcinogenic activity is influenced by the induced SA-mutagenic intermediate effect, alongside Hansch indices such as hydrophobicity (LogP), polarizability (POL) and total energy (Etot), which account for molecular membrane diffusion, ionic deformation, and stericity, respectively. A possible QSAR mechanistic interpretation of mutagenicity as the first step in genotoxic carcinogenesis development is discussed using the structural alert chemoinformation and in full accordance with the Organization for Economic Co-operation and Development QSAR guidance principles. PMID:21954348

Rotational Spectrum of Saccharine

NASA Astrophysics Data System (ADS)

Alonso, Elena R.; Mata, Santiago; Alonso, José L.

2017-06-01

A significant step forward in the structure-activity relationships of sweeteners was the assignment of the AH-B moiety in sweeteners by Shallenberger and Acree. They proposed that all sweeteners contain an AH-B moiety, known as glucophore, in which A and B are electronegative atoms separated by a distance between 2.5 to 4 Å. H is a hydrogen atom attached to one of the electronegative atom by a covalent bond. For saccharine, one of the oldest artificial sweeteners widely used in food and drinks, two possible B moieties exist ,the carbonyl oxygen atom and the sulfoxide oxygen atom although there is a consensus of opinion among scientists over the assignment of AH-B moieties to HN-SO. In the present work, the solid of saccharine (m.p. 220°C) has been vaporized by laser ablation (LA) and its rotational spectrum has been analyzed by broadband CP-FTMW and narrowband MB-FTMW Fourier transform microwave techniques. The detailed structural information extracted from the rotational constants and ^{14}N nuclear quadrupole coupling constants provided enough information to ascribe the glucophore's AH and B sites of saccharine. R. S. Shallenberger, T. E. Acree. Nature 216, 480-482 Nov 1967. R. S. Shallenberger. Taste Chemistry; Blackie Academic & Professional, London, (1993).

Optimization of PECVD Chamber Cleans Through Fundamental Studies of Electronegative Fluorinated Gas Discharges.

NASA Astrophysics Data System (ADS)

Langan, John

1996-10-01

The predominance of multi-level metalization schemes in advanced integrated circuit manufacturing has greatly increased the importance of plasma enhanced chemical vapor deposition (PECVD) and in turn in-situ plasma chamber cleaning. In order to maintain the highest throughput for these processes the clean step must be as short as possible. In addition, there is an increasing desire to minimize the fluorinated gas usage during the clean, while maximizing its efficiency, not only to achieve lower costs, but also because many of the gases used in this process are global warming compounds. We have studied the fundamental properties of discharges of NF_3, CF_4, and C_2F6 under conditions relevant to chamber cleaning in the GEC rf reference cell. Using electrical impedance analysis and optical emission spectroscopy we have determined that the electronegative nature of these discharges defines the optimal processing conditions by controlling the power coupling efficiency and mechanisms of power dissipation in the discharge. Examples will be presented where strategies identified by these studies have been used to optimize actual manufacturing chamber clean processes. (This work was performed in collaboration with Mark Sobolewski, National Institute of Standards and Technology, and Brian Felker, Air Products and Chemicals, Inc.)

Implications of electron heating and non-uniformities in a VHF-CCP for sterilization of medical instruments

NASA Astrophysics Data System (ADS)

Stapelmann, Katharina; Fiebrandt, Marcel; Styrnoll, Tim; Baldus, Sabrina; Bibinov, Nikita; Awakowicz, Peter

2015-06-01

A capacitively coupled plasma driven at a frequency of 81.36 MHz from the VHF-band is investigated by means of optical emission spectroscopy (OES) and multipole resonance probe (MRP). The discharge is operated with hydrogen, yielding an electropositive discharge, as well as oxygen, yielding an electronegative discharge, and mixtures of both. Pressure is varied from p=5 Pa to p=25 Pa. Homogeneity of the discharge is investigated by CCD camera recordings as well as spatially resolved multipole resonance probe measurements. The results indicate the presence of electromagnetic edge effects as well as standing wave effects. Furthermore, a largely homogeneous discharge can be achieved with hydrogen as process gas at a pressure of p=5 -10 Pa. With increasing pressure as well as with increasing oxygen content, the discharge appears less homogeneously. The transition from an electropositive to an electronegative discharge leads to a change in electron heating mechanisms, with pronounced local maxima of electron density at the sheath edges. A comparison of OES and MRP results reveal a significant difference in electron density, which can be explained by a non-Maxwellian distribution function of electrons.

Structural and electronic properties of monolayer group III monochalcogenides

NASA Astrophysics Data System (ADS)

Demirci, S.; Avazlı, N.; Durgun, E.; Cahangirov, S.

2017-03-01

We investigate the structural, mechanical, and electronic properties of the two-dimensional hexagonal structure of group III-VI binary monolayers, M X (M =B , Al, Ga, In and X =O , S, Se, Te) using first-principles calculations based on the density functional theory. The structural optimization calculations and phonon spectrum analysis indicate that all of the 16 possible binary compounds are thermally stable. In-plane stiffness values cover a range depending on the element types and can be as high as that of graphene, while the calculated bending rigidity is found to be an order of magnitude higher than that of graphene. The obtained electronic band structures show that M X monolayers are indirect band-gap semiconductors. The calculated band gaps span a wide optical spectrum from deep ultraviolet to near infrared. The electronic structure of oxides (M O ) is different from the rest because of the high electronegativity of oxygen atoms. The dispersions of the electronic band edges and the nature of bonding between atoms can also be correlated with electronegativities of constituent elements. The unique characteristics of group III-VI binary monolayers can be suitable for high-performance device applications in nanoelectronics and optics.

A general representation scheme for crystalline solids based on Voronoi-tessellation real feature values and atomic property data

PubMed Central

Jalem, Randy; Nakayama, Masanobu; Noda, Yusuke; Le, Tam; Takeuchi, Ichiro; Tateyama, Yoshitaka; Yamazaki, Hisatsugu

2018-01-01

Abstract Increasing attention has been paid to materials informatics approaches that promise efficient and fast discovery and optimization of functional inorganic materials. Technical breakthrough is urgently requested to advance this field and efforts have been made in the development of materials descriptors to encode or represent characteristics of crystalline solids, such as chemical composition, crystal structure, electronic structure, etc. We propose a general representation scheme for crystalline solids that lifts restrictions on atom ordering, cell periodicity, and system cell size based on structural descriptors of directly binned Voronoi-tessellation real feature values and atomic/chemical descriptors based on the electronegativity of elements in the crystal. Comparison was made vs. radial distribution function (RDF) feature vector, in terms of predictive accuracy on density functional theory (DFT) material properties: cohesive energy (CE), density (d), electronic band gap (BG), and decomposition energy (Ed). It was confirmed that the proposed feature vector from Voronoi real value binning generally outperforms the RDF-based one for the prediction of aforementioned properties. Together with electronegativity-based features, Voronoi-tessellation features from a given crystal structure that are derived from second-nearest neighbor information contribute significantly towards prediction. PMID:29707064

A modified electronegativity equalization method for fast and accurate calculation of atomic charges in large biological molecules.

PubMed

Ouyang, Yongzhong; Ye, Fei; Liang, Yizeng

2009-08-07

To further extend the EEM approach to improve its accuracy, a new approach, in which the different connectivities and hybridized states are introduced to represent the different chemical environments, has been developed. The C, O and N atoms are distinguished between different hybridized states. Different states of hydrogen atoms are defined according to their different connectivities. Furthermore, the sp(2) carbons in the aromatic rings are also separated from the other sp(2) carbons. Geometries and NPA charges are calculated at the B3LYP/6-31G* level, and the effective electronegativity and hardness values could be calibrated with the help of a training set of 141 organic molecules using the Differential Evolution (DE) algorithm. The quality of the modified EEM charges is evaluated by comparison with the B3LYP/6-31G* charges calculated for a series of polypeptides, not contained in the training set. For further comparison, the atomic parameters of the original EEM without including chemical environments are recalibrated under the same conditions. It is found that the accuracy of the modified EEM method improves significantly as compared to that of the original EEM method.

Effect of embedded metal nanocrystals on the resistive switching characteristics in NiN-based resistive random access memory cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yun, Min Ju; Kim, Hee-Dong; Man Hong, Seok

2014-03-07

The metal nanocrystals (NCs) embedded-NiN-based resistive random access memory cells are demonstrated using several metal NCs (i.e., Pt, Ni, and Ti) with different physical parameters in order to investigate the metal NC's dependence on resistive switching (RS) characteristics. First, depending on the electronegativity of metal, the size of metal NCs is determined and this affects the operating current of memory cells. If metal NCs with high electronegativity are incorporated, the size of the NCs is reduced; hence, the operating current is reduced owing to the reduced density of the electric field around the metal NCs. Second, the potential wells aremore » formed by the difference of work function between the metal NCs and active layer, and the barrier height of the potential wells affects the level of operating voltage as well as the conduction mechanism of metal NCs embedded memory cells. Therefore, by understanding these correlations between the active layer and embedded metal NCs, we can optimize the RS properties of metal NCs embedded memory cells as well as predict their conduction mechanisms.« less

Molecular-dynamics simulations of alkaline-earth metal cations in water by atom-bond electronegativity equalization method fused into molecular mechanics.

PubMed

Yang, Zhong-Zhi; Li, Xin

2005-09-01

Intermolecular potential for alkaline-earth metal (Be(2+), Mg(2+), and Ca(2+)) cations in water has been derived using the atom-bond electronegativity equalization method fused into molecular mechanics (ABEEM/MM), and it is consistent with what was previously applied to the hydration study of the monovalent cations. Parameters for the effective interaction between a cation and a water molecule were determined, reproducing the ab initio results. The static, dynamic, and thermodynamic properties of Be(2+)(aq), Mg(2+)(aq), and Ca(2+)(aq) were studied using these potential parameters. Be(2+) requires a more complicated form of the potential function than Mg(2+) and Ca(2+) in order to obtain better fits. Strong influences of the twofold charged cations on the structures of the hydration shells and some other properties of aqueous ionic solutions are discussed and compared with the results of a previous study of monovalent cations in water. At the same time, comparative study of the hydration properties of each cation is also discussed. This work demonstrates that ABEEM/MM provides a useful tool in the exploration of the hydration of double-charged cations in water.

A general representation scheme for crystalline solids based on Voronoi-tessellation real feature values and atomic property data.

PubMed

Jalem, Randy; Nakayama, Masanobu; Noda, Yusuke; Le, Tam; Takeuchi, Ichiro; Tateyama, Yoshitaka; Yamazaki, Hisatsugu

2018-01-01

Increasing attention has been paid to materials informatics approaches that promise efficient and fast discovery and optimization of functional inorganic materials. Technical breakthrough is urgently requested to advance this field and efforts have been made in the development of materials descriptors to encode or represent characteristics of crystalline solids, such as chemical composition, crystal structure, electronic structure, etc. We propose a general representation scheme for crystalline solids that lifts restrictions on atom ordering, cell periodicity, and system cell size based on structural descriptors of directly binned Voronoi-tessellation real feature values and atomic/chemical descriptors based on the electronegativity of elements in the crystal. Comparison was made vs. radial distribution function (RDF) feature vector, in terms of predictive accuracy on density functional theory (DFT) material properties: cohesive energy (CE), density ( d ), electronic band gap (BG), and decomposition energy (Ed). It was confirmed that the proposed feature vector from Voronoi real value binning generally outperforms the RDF-based one for the prediction of aforementioned properties. Together with electronegativity-based features, Voronoi-tessellation features from a given crystal structure that are derived from second-nearest neighbor information contribute significantly towards prediction.

The frequency dependence of the discharge properties in a capacitively coupled oxygen discharge

NASA Astrophysics Data System (ADS)

Gudmundsson, J. T.; Snorrason, D. I.; Hannesdottir, H.

2018-02-01

We use the one-dimensional object-oriented particle-in-cell Monte Carlo collision code oopd1 to explore the evolution of the charged particle density profiles, electron heating mechanism, the electron energy probability function (EEPF), and the ion energy distribution in a single frequency capacitively coupled oxygen discharge, with driving frequency in the range 12-100 MHz. At a low driving frequency and low pressure (5 and 10 mTorr), a combination of stochastic (α-mode) and drift ambipolar (DA) heating in the bulk plasma (the electronegative core) is observed and the DA-mode dominates the time averaged electron heating. As the driving frequency or pressure are increased, the heating mode transitions into a pure α-mode, where electron heating in the sheath region dominates. At low pressure (5 and 10 mTorr), this transition coincides with a sharp decrease in electronegativity. At low pressure and low driving frequency, the EEPF is concave. As the driving frequency is increased, the number of low energy electrons increases and the relative number of higher energy electrons (>10 eV) increases. At high driving frequency, the EEPF develops a convex shape or becomes bi-Maxwellian.

First-principles calculations of the interaction between hydrogen and 3d alloying atom in nickel

NASA Astrophysics Data System (ADS)

Liu, Wenguan; Qian, Yuan; Zhang, Dongxun; Liu, Wei; Han, Han

2015-10-01

Knowledge of the behavior of hydrogen (H) in Ni-based alloy is essential for the prediction of Tritium behavior in Molten Salt Reactor. First-principles calculations were performed to investigate the interaction between H and 3d transition metal (TM) alloying atom in Ni-based alloy. H prefers the octahedral interstitial site to the tetrahedral interstitial site energetically. Most of the 3d TM elements (except Zn) attract H. The attraction to H in the Ni-TM-H system can be mainly attributed to the differences in electronegativity. With the large electronegativity, H and Ni gain electrons from the other TM elements, resulting in the enhanced Ni-H bonds which are the source of the attraction to H in the Ni-TM-H system. The obviously covalent-like Cr-H and Co-H bindings are also beneficial to the attraction to H. On the other hand, the repulsion to H in the Ni-Zn-H system is due to the stable electronic configuration of Zn. We mainly utilize the results calculated in 32-atom supercell which corresponds to the case of a relatively high concentration of hydrogen. Our results are in good agreement with the experimental ones.

Rapid Radiochemical Method for Isotopic Uranium in Building ...

EPA Pesticide Factsheets

Technical Fact Sheet Analysis Purpose: Qualitative analysis Technique: Alpha spectrometry Method Developed for: Uranium-234, uranium-235, and uranium-238 in concrete and brick samples Method Selected for: SAM lists this method for qualitative analysis of uranium-234, uranium-235, and uranium-238 in concrete or brick building materials. Summary of subject analytical method which will be posted to the SAM website to allow access to the method.

Plutonium recovery from spent reactor fuel by uranium displacement

DOEpatents

Ackerman, J.P.

1992-03-17

A process is described for separating uranium values and transuranic values from fission products containing rare earth values when the values are contained together in a molten chloride salt electrolyte. A molten chloride salt electrolyte with a first ratio of plutonium chloride to uranium chloride is contacted with both a solid cathode and an anode having values of uranium and fission products including plutonium. A voltage is applied across the anode and cathode electrolytically to transfer uranium and plutonium from the anode to the electrolyte while uranium values in the electrolyte electrolytically deposit as uranium metal on the solid cathode in an amount equal to the uranium and plutonium transferred from the anode causing the electrolyte to have a second ratio of plutonium chloride to uranium chloride. Then the solid cathode with the uranium metal deposited thereon is removed and molten cadmium having uranium dissolved therein is brought into contact with the electrolyte resulting in chemical transfer of plutonium values from the electrolyte to the molten cadmium and transfer of uranium values from the molten cadmium to the electrolyte until the first ratio of plutonium chloride to uranium chloride is reestablished.

16. VIEW OF THE ENRICHED URANIUM RECOVERY SYSTEM. ENRICHED URANIUM ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

16. VIEW OF THE ENRICHED URANIUM RECOVERY SYSTEM. ENRICHED URANIUM RECOVERY PROCESSED RELATIVELY PURE MATERIALS AND SOLUTIONS AND SOLID RESIDUES WITH RELATIVELY LOW URANIUM CONTENT. URANIUM RECOVERY INVOLVED BOTH SLOW AND FAST PROCESSES. (4/4/66) - Rocky Flats Plant, General Manufacturing, Support, Records-Central Computing, Southern portion of Plant, Golden, Jefferson County, CO

77 FR 51579 - Application for a License To Export High-Enriched Uranium

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-24

... NUCLEAR REGULATORY COMMISSION Application for a License To Export High-Enriched Uranium Pursuant.... Complex, July 30, 2012, August Uranium (93.35%). uranium-235 high-enriched 1, 2012, XSNM3726, 11006037. contained in 7.5 uranium in the kilograms uranium. form of broken metal to the Atomic Energy of Canada...

Deposit model for volcanogenic uranium deposits

USGS Publications Warehouse

Breit, George N.; Hall, Susan M.

2011-01-01

The International Atomic Energy Agency's tabulation of volcanogenic uranium deposits lists 100 deposits in 20 countries, with major deposits in Russia, Mongolia, and China. Collectively these deposits are estimated to contain uranium resources of approximately 500,000 tons of uranium, which amounts to 6 percent of the known global resources. Prior to the 1990s, these deposits were considered to be small (less than 10,000 tons of uranium) with relatively low to moderate grades (0.05 to 0.2 weight percent of uranium). Recent availability of information on volcanogenic uranium deposits in Asia highlighted the large resource potential of this deposit type. For example, the Streltsovskoye district in eastern Russia produced more than 100,000 tons of uranium as of 2005; with equivalent resources remaining. Known volcanogenic uranium deposits within the United States are located in Idaho, Nevada, Oregon, and Utah. These deposits produced an estimated total of 800 tons of uranium during mining from the 1950s through the 1970s and have known resources of 30,000 tons of uranium. The most recent estimate of speculative resources proposed an endowment of 200,000 tons of uranium.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siekhaus, W. J.; Teslich, N. E.; Weber, P. K.

Depleted uranium that included carbide inclusions was sputtered with 30-keV gallium ions or 16-kev cesium ions to depths much greater than the ions’ range, i.e. using steady-state sputtering. The recession of both the uranium’s and uranium carbide’s surfaces and the ion corresponding fluences were used to determine the steady-state target sputtering yields of both uranium and uranium carbide, i.e. 6.3 atoms of uranium and 2.4 units of uranium carbide eroded per gallium ion, and 9.9 uranium atoms and 3.65 units of uranium carbide eroded by cesium ions. The steady state surface composition resulting from the simultaneous gallium or cesium implantationmore » and sputter-erosion of uranium and uranium carbide were calculated to be U₈₆Ga₁₄, (UC)₇₀Ga₃₀ and U₈₁Cs₉, (UC)₇₉Cs₂₁, respectively.« less

Uranium hydrogeochemical and stream sediment reconnaissance of the Newcastle NTMS Quadrangle, Wyoming, including concentrations of forty-two additional elements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goff, S.J.; Sandoval, W.F.; Gallimore, D.L.

1980-06-01

Water and sediment samples were collected and each water sample was analyzed for U, and each sediment sample was analyzed for 43 elements, including U and Th. Uranium concentrations in water samples range from below the detection limit of 0.02 ppB to 702.26 ppB and have a median of 1.73 ppB and a mean of 11.76 ppB. Water samples containing high uranium concentrations generally are associated with known uranium mining activity or units known to be uranium bearing. About one-third of the water samples containing high uranium concentrations were collected from locations within the Pumpkin Buttes and Turnercrest-Ross Districts. Nearlymore » half of the water samples containing high uranium concentrations were collected from locations just west of the Monument Hill and Highland Flats-Box Creek Districts. Similar anomalous uranium concentrations in this region have been reported updip from Exxon's Highland uranium deposits. High uranium concentrations were also found associated with the Lance Creek-Old Woman Anticline District. Uranium concentrations in sediment samples range from 1.14 to 220.70 ppM and have a median of 3.37 ppM and a mean of 4.03 ppM. Throughout the major uranium mining districts of the Powder River Basin, sediment samples with high uranium concentrations were collected from dry streams located near wells producing water samples with high uranium concentrations. High uranium concentrations were also found associated with the Lance Creek oil field where uranium mineralization is known in the White River formation. High uranium concentrations were also found in sediment samples in areas where uranium mineralization is not known. These samples are from dry streams in areas underlain by the White River formation, the Niobrara formation, and the Pierre, Carlisle, Belle Fourche, and Mowry shales.« less

Influence of uranium hydride oxidation on uranium metal behaviour

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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, ifmore » 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)« less

Influence of acidic and alkaline waste solution properties on uranium migration in subsurface sediments.

PubMed

Szecsody, Jim E; Truex, Mike J; Qafoku, Nikolla P; Wellman, Dawn M; Resch, Tom; Zhong, Lirong

2013-08-01

This study shows that acidic and alkaline wastes co-disposed with uranium into subsurface sediments have significant impact on changes in uranium retardation, concentration, and mass during downward migration. For uranium co-disposal with acidic wastes, significant rapid (i.e., hours) carbonate and slow (i.e., 100 s of hours) clay dissolution resulted, releasing significant sediment-associated uranium, but the extent of uranium release and mobility change was controlled by the acid mass added relative to the sediment proton adsorption capacity. Mineral dissolution in acidic solutions (pH2) resulted in a rapid (<10 h) increase in aqueous carbonate (with Ca(2+), Mg(2+)) and phosphate and a slow (100 s of hours) increase in silica, Al(3+), and K(+), likely from 2:1 clay dissolution. Infiltration of uranium with a strong acid resulted in significant shallow uranium mineral dissolution and deeper uranium precipitation (likely as phosphates and carbonates) with downward uranium migration of three times greater mass at a faster velocity relative to uranium infiltration in pH neutral groundwater. In contrast, mineral dissolution in an alkaline environment (pH13) resulted in a rapid (<10h) increase in carbonate, followed by a slow (10 s to 100 s of hours) increase in silica concentration, likely from montmorillonite, muscovite, and kaolinite dissolution. Infiltration of uranium with a strong base resulted in not only uranium-silicate precipitation (presumed Na-boltwoodite) but also desorption of natural uranium on the sediment due to the high ionic strength solution, or 60% greater mass with greater retardation compared with groundwater. Overall, these results show that acidic or alkaline co-contaminant disposal with uranium can result in complex depth- and time-dependent changes in uranium dissolution/precipitation reactions and uranium sorption, which alter the uranium migration mass, concentration, and velocity. Copyright © 2013 Elsevier B.V. All rights reserved.

Uranium induces oxidative stress in lung epithelial cells

PubMed Central

Periyakaruppan, Adaikkappan; Kumar, Felix; Sarkar, Shubhashish; Sharma, Chidananda S.

2009-01-01

Uranium compounds are widely used in the nuclear fuel cycle, antitank weapons, tank armor, and also as a pigment to color ceramics and glass. Effective management of waste uranium compounds is necessary to prevent exposure to avoid adverse health effects on the population. Health risks associated with uranium exposure includes kidney disease and respiratory disorders. In addition, several published results have shown uranium or depleted uranium causes DNA damage, mutagenicity, cancer and neurological defects. In the current study, uranium toxicity was evaluated in rat lung epithelial cells. The study shows uranium induces significant oxidative stress in rat lung epithelial cells followed by concomitant decrease in the antioxidant potential of the cells. Treatment with uranium to rat lung epithelial cells also decreased cell proliferation after 72 h in culture. The decrease in cell proliferation was attributed to loss of total glutathione and superoxide dismutase in the presence of uranium. Thus the results indicate the ineffectiveness of antioxidant system’s response to the oxidative stress induced by uranium in the cells. PMID:17124605

Uranium ores and depleted uranium in the environment, with a reference to uranium in the biosphere from the Erzgebirge/Sachsen, Germany.

PubMed

Meinrath, A; Schneider, P; Meinrath, G

2003-01-01

The Erzgebirge ('Ore Mountains') area in the eastern part of Germany was a major source of uranium for Soviet nuclear programs between 1945 and 1989. During this time, the former German Democratic Republic became the third largest uranium producer in the world. The high abundance of uranium in the geological formations of the Erzgebirge are mirrored in the discovery of uranium by M. Klaproth close to Freiberg City in 1789 and the description of the so-called 'Schneeberg' disease, lung cancer caused in miners by the accumulation of the uranium decay product, radon, in the subsurfaces of shafts. Since 1991, remediation and mitigation of uranium at production facilities, rock piles and mill tailings has taken place. In parallel, efforts were initiated to assess the likely adverse effects of uranium mining to humans. The costs of these activities amount to about 6.5 10(9) Euro. A comparison with concentrations of depleted uranium at certain sites is given.

Structural parameterization and functional prediction of antigenic polypeptome sequences with biological activity through quantitative sequence-activity models (QSAM) by molecular electronegativity edge-distance vector (VMED).

PubMed

Li, ZhiLiang; Wu, ShiRong; Chen, ZeCong; Ye, Nancy; Yang, ShengXi; Liao, ChunYang; Zhang, MengJun; Yang, Li; Mei, Hu; Yang, Yan; Zhao, Na; Zhou, Yuan; Zhou, Ping; Xiong, Qing; Xu, Hong; Liu, ShuShen; Ling, ZiHua; Chen, Gang; Li, GenRong

2007-10-01

Only from the primary structures of peptides, a new set of descriptors called the molecular electronegativity edge-distance vector (VMED) was proposed and applied to describing and characterizing the molecular structures of oligopeptides and polypeptides, based on the electronegativity of each atom or electronic charge index (ECI) of atomic clusters and the bonding distance between atom-pairs. Here, the molecular structures of antigenic polypeptides were well expressed in order to propose the automated technique for the computerized identification of helper T lymphocyte (Th) epitopes. Furthermore, a modified MED vector was proposed from the primary structures of polypeptides, based on the ECI and the relative bonding distance of the fundamental skeleton groups. The side-chains of each amino acid were here treated as a pseudo-atom. The developed VMED was easy to calculate and able to work. Some quantitative model was established for 28 immunogenic or antigenic polypeptides (AGPP) with 14 (1-14) A(d) and 14 other restricted activities assigned as "1"(+) and "0"(-), respectively. The latter comprised 6 A(b)(15-20), 3 A(k)(21-23), 2 E(k)(24-26), 2 H-2(k)(27 and 28) restricted sequences. Good results were obtained with 90% correct classification (only 2 wrong ones for 20 training samples) and 100% correct prediction (none wrong for 8 testing samples); while contrastively 100% correct classification (none wrong for 20 training samples) and 88% correct classification (1 wrong for 8 testing samples). Both stochastic samplings and cross validations were performed to demonstrate good performance. The described method may also be suitable for estimation and prediction of classes I and II for major histocompatibility antigen (MHC) epitope of human. It will be useful in immune identification and recognition of proteins and genes and in the design and development of subunit vaccines. Several quantitative structure activity relationship (QSAR) models were developed for various oligopeptides and polypeptides including 58 dipeptides and 31 pentapeptides with angiotensin converting enzyme (ACE) inhibition by multiple linear regression (MLR) method. In order to explain the ability to characterize molecular structure of polypeptides, a molecular modeling investigation on QSAR was performed for functional prediction of polypeptide sequences with antigenic activity and heptapeptide sequences with tachykinin activity through quantitative sequence-activity models (QSAMs) by the molecular electronegativity edge-distance vector (VMED). The results showed that VMED exhibited both excellent structural selectivity and good activity prediction. Moreover, the results showed that VMED behaved quite well for both QSAR and QSAM of poly-and oligopeptides, which exhibited both good estimation ability and prediction power, equal to or better than those reported in the previous references. Finally, a preliminary conclusion was drawn: both classical and modified MED vectors were very useful structural descriptors. Some suggestions were proposed for further studies on QSAR/QSAM of proteins in various fields.

METHOD FOR RECOVERING URANIUM FROM OILS

DOEpatents

Gooch, L.H.

1959-07-14

A method is presented for recovering uranium from hydrocarbon oils, wherein the uranium is principally present as UF/sub 4/. According to the invention, substantially complete removal of the uranium from the hydrocarbon oil may be effected by intimately mixing one part of acetone to about 2 to 12 parts of the hydrocarbon oil containing uranium and separating the resulting cake of uranium from the resulting mixture. The uranium in the cake may be readily recovered by burning to the oxide.

High strength and density tungsten-uranium alloys

DOEpatents

Sheinberg, Haskell

1993-01-01

Alloys of tungsten and uranium and a method for making the alloys. The amount of tungsten present in the alloys is from about 55 vol % to about 85 vol %. A porous preform is made by sintering consolidated tungsten powder. The preform is impregnated with molten uranium such that (1) uranium fills the pores of the preform to form uranium in a tungsten matrix or (2) uranium dissolves portions of the preform to form a continuous uranium phase containing tungsten particles.

Influence of uncertainties of isotopic composition of the reprocessed uranium on effectiveness of its enrichment in gas centrifuge cascades

NASA Astrophysics Data System (ADS)

Smirnov, A. Yu; Mustafin, A. R.; Nevinitsa, V. A.; Sulaberidze, G. A.; Dudnikov, A. A.; Gusev, V. E.

2017-01-01

The effect of the uncertainties of the isotopic composition of the reprocessed uranium on its enrichment process in gas centrifuge cascades while diluting it by adding low-enriched uranium (LEU) and waste uranium. It is shown that changing the content of 232U and 236U isotopes in the initial reprocessed uranium within 15% (rel.) can significantly change natural uranium consumption and separative work (up to 2-3%). However, even in case of increase of these parameters is possible to find the ratio of diluents, where the cascade with three feed flows (depleted uranium, LEU and reprocessed uranium) will be more effective than ordinary separation cascade with one feed point for producing LEU from natural uranium.

METHOD OF RECOVERING URANIUM COMPOUNDS

DOEpatents

Poirier, R.H.

1957-10-29

S>The recovery of uranium compounds which have been adsorbed on anion exchange resins is discussed. The uranium and thorium-containing residues from monazite processed by alkali hydroxide are separated from solution, and leached with an alkali metal carbonate solution, whereby the uranium and thorium hydrorides are dissolved. The carbonate solution is then passed over an anion exchange resin causing the uranium to be adsorbed while the thorium remains in solution. The uranium may be recovered by contacting the uranium-holding resin with an aqueous ammonium carbonate solution whereby the uranium values are eluted from the resin and then heating the eluate whereby carbon dioxide and ammonia are given off, the pH value of the solution is lowered, and the uranium is precipitated.

Controlling intake of uranium in the workplace: Applications of biokinetic modeling and occupational monitoring data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leggett, Richard Wayne; Eckerman, Keith F; McGinn, Wilson

2012-01-01

This report provides methods for interpreting and applying occupational uranium monitoring data. The methods are based on current international radiation protection guidance, current information on the chemical toxicity of uranium, and best available biokinetic models for uranium. Emphasis is on air monitoring data and three types of bioassay data: the concentration of uranium in urine; the concentration of uranium in feces; and the externally measured content of uranium in the chest. Primary Reference guidance levels for prevention of chemical effects and limitation of radiation effects are selected based on a review of current scientific data and regulatory principles for settingmore » standards. Generic investigation levels and immediate action levels are then defined in terms of these primary guidance levels. The generic investigation and immediate actions levels are stated in terms of radiation dose and concentration of uranium in the kidneys. These are not directly measurable quantities, but models can be used to relate the generic levels to the concentration of uranium in air, urine, or feces, or the total uranium activity in the chest. Default investigation and immediate action levels for uranium in air, urine, feces, and chest are recommended for situations in which there is little information on the form of uranium taken into the body. Methods are prescribed also for deriving case-specific investigation and immediate action levels for uranium in air, urine, feces, and chest when there is sufficient information on the form of uranium to narrow the range of predictions of accumulation of uranium in the main target organs for uranium: kidneys for chemical effects and lungs for radiological effects. In addition, methods for using the information herein for alternative guidance levels, different from the ones selected for this report, are described.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gregoire, D.C.; Goltz, D.M.; Chakrabarti, C.L.

Graphite furnace atomic absorption spectrometry (GFAAS) is an insensitive technique for determination of uranium. Experiments were conducted using electrothermal vaporization inductively coupled plasma mass spectrometry to investigate the atomization and vaporization of atomic and molecular uranium species in the graphite furnace. ETV-ICP-MS signals for uranium were observed at temperatures well below the appearance temperature of uranium atoms suggesting the vaporization of molecular uranium oxide at temperatures below 2000{degrees}C. Examination of individual uranium ETV-ICP-MS signals reveals the vaporization of uranium carbide at temperatures above 2600{degrees}C. Chemical modifiers such as 0.2% HF and 0.1% CHF{sub 3} in the argon carrier gas, weremore » ineffective in preventing the formation of uranium carbide at 2700{degrees}C. Vaporization of uranium from a tungsten surface using tungsten foil inserted into the graphite tube prevented the formation of uranium carbide and eliminated the ETV-ICP-MS signal suppression caused by a sodium chloride matrix.« less

PRODUCTION OF PURIFIED URANIUM

DOEpatents

Burris, L. Jr.; Knighton, J.B.; Feder, H.M.

1960-01-26

A pyrometallurgical method for processing nuclear reactor fuel elements containing uranium and fission products and for reducing uranium compound; to metallic uranium is reported. If the material proccssed is essentially metallic uranium, it is dissolved in zinc, the sulution is cooled to crystallize UZn/sub 9/ , and the UZn/sub 9/ is distilled to obtain uranium free of fission products. If the material processed is a uranium compound, the sollvent is an alloy of zinc and magnesium and the remaining steps are the same.

METHOD OF SEPARATING URANIUM VALUES, PLUTONIUM VALUES AND FISSION PRODUCTS BY CHLORINATION

DOEpatents

Brown, H.S.; Seaborg, G.T.

1959-02-24

The separation of plutonium and uranium from each other and from other substances is described. In general, the method comprises the steps of contacting the uranium with chlorine in the presence of a holdback material selected from the group consisting of lanthanum oxide and thorium oxide to form a uranium chloride higher than uranium tetrachloride, and thereafter heating the uranium chloride thus formed to a temperature at which the uranium chloride is volatilized off but below the volatilizalion temperature of plutonium chloride.

SOLVENT EXTRACTION PROCESS FOR URANIUM RECOVERY

DOEpatents

Clark, H.M.; Duffey, D.

1958-06-17

A process is described for extracting uranium from uranium ore, wherein the uranium is substantially free from molybdenum contamination. In a solvent extraction process for recovering uranium, uranium and molybdenum ions are extracted from the ore with ether under high acidity conditions. The ether phase is then stripped with water at a lower controiled acidity, resaturated with salting materials such as sodium nitrate, and reextracted with the separation of the molybdenum from the uranium without interference from other metals that have been previously extracted.

78 FR 17450 - Notice of Issuance of Materials License Renewal, Operating License SUA-1341, Uranium One USA, Inc...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-21

... License Renewal, Operating License SUA-1341, Uranium One USA, Inc., Willow Creek Uranium In Situ Recovery.... SUA- 1341 to Uranium One USA, Inc. (Uranium One) for its Willow Creek Uranium In Situ Recovery (ISR) Project in Johnson and Campbell Counties, Wyoming. ADDRESSES: Please refer to Docket ID NRC-2009-0036 when...

Reactive transport modeling at uranium in situ recovery sites: uncertainties in uranium sorption on iron hydroxides

USGS Publications Warehouse

Johnson, Raymond H.; Tutu, Hlanganani; Brown, Adrian; Figueroa, Linda; Wolkersdorfer, Christian

2013-01-01

Geochemical changes that can occur down gradient from uranium in situ recovery (ISR) sites are important for various stakeholders to understand when evaluating potential effects on surrounding groundwater quality. If down gradient solid-phase material consists of sandstone with iron hydroxide coatings (no pyrite or organic carbon), sorption of uranium on iron hydroxides can control uranium mobility. Using one-dimensional reactive transport models with PHREEQC, two different geochemical databases, and various geochemical parameters, the uncertainties in uranium sorption on iron hydroxides are evaluated, because these oxidized zones create a greater risk for future uranium transport than fully reduced zones where uranium generally precipitates.

Method for the recovery of uranium values from uranium tetrafluoride

DOEpatents

Kreuzmann, Alvin B.

1983-01-01

The invention is a novel method for the recovery of uranium from dry, particulate uranium tetrafluoride. In one aspect, the invention comprises reacting particulate uranium tetrafluoride and calcium oxide in the presence of gaseous oxygen to effect formation of the corresponding alkaline earth metal uranate and alkaline earth metal fluoride. The product uranate is highly soluble in various acidic solutions wherein the product fluoride is virtually insoluble therein. The product mixture of uranate and alkaline earth metal fluoride is contacted with a suitable acid to provide a uranium-containing solution, from which the uranium is recovered. The invention can achieve quantitative recovery of uranium in highly pure form.

Method for the recovery of uranium values from uranium tetrafluoride

DOEpatents

Kreuzmann, A.B.

1982-10-27

The invention is a novel method for the recovery of uranium from dry, particulate uranium tetrafluoride. In one aspect, the invention comprises reacting particulate uranium tetrafluoride and calcium oxide in the presence of gaseous oxygen to effect formation of the corresponding alkaline earth metal uranate and alkaline earth metal fluoride. The product uranate is highly soluble in various acidic solutions whereas the product fluoride is virtually insoluble therein. The product mixture of uranate and alkaline earth metal fluoride is contacted with a suitable acid to provide a uranium-containing solution, from which the uranium is recovered. The invention can achieve quantitative recovery of uranium in highly pure form.

Fate of Uranium in Wetlands: Impact of Drought Followed by Re-flooding

NASA Astrophysics Data System (ADS)

Gilson, E.; Huang, S.; Koster van Groos, P. G.; Scheckel, K.; Peacock, A. D.; Kaplan, D. I.; Jaffe, P. R.

2014-12-01

Uranium contamination in groundwater can be mitigated in anoxic zones by iron-reducing bacteria that reduce soluble U(VI) to insoluble U(IV) and by uranium immobilization through complexation and sorption. Wetlands often link ground and surface-waters, making them strategic systems for potentially limiting migration of uranium contamination. Little is known about how drought periods that result in the drying of wetland soils, and consequent redox changes, affect uranium fate and transport in wetlands. In order to better understand the fate and stability of immobilized uranium in wetland soils, and how dry periods affect the uranium stability, we dosed saturated wetland mesocosms planted with Scirpus acutus with low levels of uranyl-acetate for 5 months before imposing a 9-day drying period followed by a 13-day rewetting period. Concentrations of uranium in mesocosm effluent increased after rewetting, but the cumulative amount of uranium released in the 13 days following the drying constituted less than 1% of the uranium immobilized in the soil during the 5 months prior to the drought. This low level of remobilization suggests that the uranium immobilized in these soils was not primarily bioreduced U(IV), which could have been oxidized to soluble U(VI) during the drought and released in the effluent during the subsequent flood. XANES analyses confirm that most of the uranium immobilized in the mesocosms was U(VI) sorbed to iron oxides. Compared to mesocosms that did not experience drying or rewetting, mesocosms that were sacrificed immediately after drying and after 13 days of rewetting had less uranium in soil near roots and more uranium on root surfaces. Metal-reducing bacteria only dominated the bacterial community after 13 days of rewetting and not immediately after drying, indicating that these bacteria are not responsible for this redistribution of uranium after the drying and rewetting. Results show that short periods of drought conditions in a wetland may impact uranium distribution, but these conditions may not cause large losses of immobilized uranium from the wetland.

The distribution of uranium and thorium in granitic rocks of the basin and range province, Western United States

USGS Publications Warehouse

McNeal, J.M.; Lee, D.E.; Millard, H.T.

1981-01-01

Some secondary uranium deposits are thought to have formed from uranium derived by the weathering of silicic igneous rocks such as granites, rhyolites, and tuffs. A regional geochemical survey was made to determine the distribution of uranium and thorium in granitic rocks of the Basin and Range province in order to evaluate the potential for secondary uranium occurrences in the area. The resulting geochemical maps of uranium, thorium, and the Th:U ratio may be useful in locating target areas for uranium exploration. The granites were sampled according to a five-level, nested, analysis-of-variance design, permitting estimates to be made of the variance due to differences between:(1) two-degree cells; (2) one-degree cells; (3) plutons; (4) samples; and (5) analyses. The cells are areas described in units of degrees of latitude and longitude. The results show that individual plutons tend to differ in uranium and thorium concentrations, but that each pluton tends to be relatively homogeneous. Only small amounts of variance occur at the two degree and the between-analyses levels. The three geochemical maps that were prepared are based on one-degree cell means. The reproducibility of the maps is U > Th ??? Th:U. These geochemical maps may be used in three methods of locating target areas for uranium exploration. The first method uses the concept that plutons containing the greatest amounts of uranium may supply the greatest amounts of uranium for the formation of secondary uranium occurrences. The second method is to examine areas with high thorium contents, because thorium and uranium are initially highly correlated but much uranium could be lost by weathering. The third method is to locate areas in which the plutons have particularly high Th:U ratios. Because uranium, but not thorium, is leached by chemical weathering, high Th:U ratios suggest a possible loss of uranium and possibly a greater potential for secondary uranium occurrences to be found in the area. ?? 1981.

Hydrologic and Temporal Influences of Evaporite Minerals on the Vertical Distribution, Storage, and Mobility of Uranium

NASA Astrophysics Data System (ADS)

Roycroft, S. J.; Noel, V.; Boye, K.; Besancon, C.; Weaver, K. L.; Johnson, R. H.; Dam, W. L.; Fendorf, S. E.; Bargar, J.

2016-12-01

Uranium contaminated groundwater in Riverton, Wyoming persists despite anticipated natural attenuation outside of a former uranium ore processing facility. The inability of natural flushing to dilute the uranium below the regulatory threshold indicates that sediments act as secondary sources likely (re)supplying uranium to groundwater. Throughout the contaminated floodplain, uranium rich-evaporites are readily abundant in the upper 2 m of sediments and are spatially coincident with the location of the plume, which suggests a likely link between evaporites and increased uranium levels. Knowledge of where and how uranium is stored within evaporite-associated sediments is required to understand processes controlling the mobility of uranium. We expect that flooding and seasonal changes in hydrologic conditions will affect U phase partitioning, and thus largely control U mobility. The primary questions we are addressing in this project are: What is the relative abundance of uranium incorporated in various mineral complexes throughout the evaporite sediments? How do the factors of depth, location, and seasonality influence the relative incorporation, mobility and speciation of uranium?We have systematically sampled from two soil columns over three dates in Riverton. The sampling dates span before and after a significant flooding event, providing insight into the flood's impact on local uranium mobility. Sequential chemical extractions are used to decipher the reactivity of uranium and approximate U operationally defined within reactants targeting carbonate, silicate, organic, and metal oxide bound or water and exchangeable phases. Extractions throughout the entirety of the sediment cores provide a high-resolution vertical profile of the distribution of uranium in various extracted phases. Throughout the profile, the majority (50-60%) of uranium is bound within carbonate-targeted extracts, a direct effect of the carbonate-rich evaporite sediments. The sum of our analyses provide a dynamic model of uranium incorporation within evaporite sediments holding implications for the fate of uranium throughout contaminated sites across the Colorado River Basin.

Inherently safe in situ uranium recovery

DOEpatents

Krumhansl, James L; Brady, Patrick V

2014-04-29

An in situ recovery of uranium operation involves circulating reactive fluids through an underground uranium deposit. These fluids contain chemicals that dissolve the uranium ore. Uranium is recovered from the fluids after they are pumped back to the surface. Chemicals used to accomplish this include complexing agents that are organic, readily degradable, and/or have a predictable lifetime in an aquifer. Efficiency is increased through development of organic agents targeted to complexing tetravalent uranium rather than hexavalent uranium. The operation provides for in situ immobilization of some oxy-anion pollutants under oxidizing conditions as well as reducing conditions. The operation also artificially reestablishes reducing conditions on the aquifer after uranium recovery is completed. With the ability to have the impacted aquifer reliably remediated, the uranium recovery operation can be considered inherently safe.

Uranium concentrations in groundwater, northeastern Washington

USGS Publications Warehouse

Kahle, Sue C.; Welch, Wendy B.; Tecca, Alison E.; Eliason, Devin M.

2018-04-18

A study of uranium in groundwater in northeastern Washington was conducted to make a preliminary assessment of naturally occurring uranium in groundwater relying on existing information and limited reconnaissance sampling. Naturally occurring uranium is associated with granitic and metasedimentary rocks, as well as younger sedimentary deposits, that occur in this region. The occurrence and distribution of uranium in groundwater is poorly understood. U.S. Environmental Protection Agency (EPA) regulates uranium in Group A community water systems at a maximum contaminant level (MCL) of 30 μg/L in order to reduce uranium exposure, protect from toxic kidney effects of uranium, and reduce the risk of cancer. However, most existing private wells in the study area, generally for single family use, have not been sampled for uranium. This document presents available uranium concentration data from throughout a multi-county region, identifies data gaps, and suggests further study aimed at understanding the occurrence of uranium in groundwater.The study encompasses about 13,000 square miles (mi2) in the northeastern part of Washington with a 2010 population of about 563,000. Other than the City of Spokane, most of the study area is rural with small towns interspersed throughout the region. The study area also includes three Indian Reservations with small towns and scattered population. The area has a history of uranium exploration and mining, with two inactive uranium mines on the Spokane Indian Reservation and one smaller inactive mine on the outskirts of Spokane. Historical (1977–2016) uranium in groundwater concentration data were used to describe and illustrate the general occurrence and distribution of uranium in groundwater, as well as to identify data deficiencies. Uranium concentrations were detected at greater than 1 microgram per liter (μg/L) in 60 percent of the 2,382 historical samples (from wells and springs). Uranium concentrations ranged from less than 1 to 88,600 μg/L, and the median concentration of uranium in groundwater for all sites was 1.4 μg/L.New (2017) uranium in groundwater concentration data were obtained by sampling 13 private domestic wells for uranium in areas without recent (2000s) water-quality data. Uranium was detected in all 13 wells sampled for this study; concentrations ranged from 1.03 to 1,180 μg/L with a median of 22 μg/L. Uranium concentrations of groundwater samples from 6 of the 13 wells exceeded the MCL for uranium. Uranium concentrations in water samples from two wells were 1,130 and 1,180 μg/L, respectively; nearly 40 times the MCL.Additional data collection and analysis are needed in rural areas where self-supplied groundwater withdrawals are the primary source of water for human consumption. Of the roughly 43,000 existing water wells in the study area, only 1,755 wells, as summarized in this document, have available uranium concentration data, and some of those data are decades old. Furthermore, analysis of area groundwater quality would benefit from a more extensive chemical-analysis suite including general chemistry in order to better understand local geochemical conditions that largely govern the mobility of uranium. Although the focus of the present study is uranium, it also is important to recognize that there are other radionuclides of concern that may be present in area groundwater.

Short-lived Rn-222 daughters in cryogenic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pelczar, Krzysztof; Frodyma, Nikodem; Wójcik, Marcin

In this paper a detection method of α emitters from {sup 222}Rn decay chain, present in cryogenic liquids, using bare Si-PIN diodes immersed in the liquids is presented. Properties of ionized {sup 222}Rn daughters deduced from conducted measurements are outlined. Life-time of positive ions was found to be of the order of 10 s, and nonzero content of electronegative ions was observed.

Assigning Oxidation States to Organic Compounds via Predictions from X-Ray Photoelectron Spectroscopy: A Discussion of Approaches and Recommended Improvements

ERIC Educational Resources Information Center

Gupta, Vipul; Ganegoda, Hasitha; Engelhard, Mark H.; Terry, Jeff; Linford, Matthew R.

2014-01-01

The traditional assignment of oxidation states to organic molecules is problematic. Accordingly, in 1999, Calzaferri proposed a simple and elegant solution that is based on the similar electronegativities of carbon and hydrogen: hydrogen would be assigned an oxidation state of zero when bonded to carbon. Here, we show that X-ray photoelectron…

Introducing a Simple Equation to Express Oxidation States as an Alternative to Using Rules Associated with Words Alone

ERIC Educational Resources Information Center

Minkiewicz, Piotr; Darewicz, Malgorzata; Iwaniak, Anna

2018-01-01

A simple equation to calculate the oxidation states (oxidation numbers) of individual atoms in molecules and ions may be introduced instead of rules associated with words alone. The equation includes two of three categories of bonds, classified as proposed by Goodstein: number of bonds with more electronegative atoms and number of bonds with less…

The Use of Optical Electronegativities to Assign Electronic Spectra of Semiquinone Complexes

DTIC Science & Technology

1990-08-03

Auburn, E.S. Dodsworth, M. Haga, W. Liu, M. Melnik and W.A. Nevin, J. Am. Chem. Soc. 110 (1988) 8076. 8. C. Benelli, A. Dei, D. Gatteschi and L. Pardi...Inorg. Chim. Acta 163 (1989) 99. 9. C. Benelli, A. Dei, D. Gatteschi and L. Pardi, Inorg. Chem. 28 (1989) 1476. 10. C. Benelli, A. Dei, D. Gatteschi , H.U

Charge conservation in electronegativity equalization and its implications for the electrostatic properties of fluctuating-charge models.

PubMed

Chen, Jiahao; Martínez, Todd J

2009-07-28

An analytical solution of fluctuating-charge models using Gaussian elimination allows us to isolate the contribution of charge conservation effects in determining the charge distribution. We use this analytical solution to calculate dipole moments and polarizabilities and show that charge conservation plays a critical role in maintaining the correct translational invariance of the electrostatic properties predicted by these models.

Single bubble of an electronegative gas in transformer oil in the presence of an electric field

NASA Astrophysics Data System (ADS)

Gadzhiev, M. Kh.; Tyuftyaev, A. S.; Il'ichev, M. V.

2017-10-01

The influence of the electric field on a single air bubble in transformer oil has been studied. It has been shown that, depending on its size, the bubble may initiate breakdown. The sizes of air and sulfur hexafluoride bubbles at which breakdown will not be observed have been estimated based on the condition for the avalanche-to-streamer transition.

A combined electronegativity equalization and electrostatic potential fit method for the determination of atomic point charges.

PubMed

Berente, Imre; Czinki, Eszter; Náray-Szabó, Gábor

2007-09-01

We report an approach for the determination of atomic monopoles of macromolecular systems using connectivity and geometry parameters alone. The method is appropriate also for the calculation of charge distributions based on the quantum mechanically determined wave function and does not suffer from the mathematical instability of other electrostatic potential fit methods. Copyright 2007 Wiley Periodicals, Inc.

Atomic and molecular analysis highlights the biophysics of unprotonated and protonated retinal in UV and scotopic vision.

PubMed

Kubli-Garfias, Carlos; Vázquez-Ramírez, Ricardo; Cabrera-Vivas, Blanca M; Gómez-Reyes, Baldomero; Ramírez, Juan Carlos

2015-09-26

During the photoreaction of rhodopsin, retinal isomerizes, rotating the C11[double bond, length as m-dash]C12 π-bond from cis to an all-trans configuration. Unprotonated (UR) or protonated (PR) retinal in the Schiff's base (SB) is related to UV and light vision. Because the UR and PR have important differences in their physicochemical reactivities, we compared the atomic and molecular properties of these molecules using DFT calculations. The C10-C11[double bond, length as m-dash]C12-C13 dihedral angle was rotated from 0° to 180° in 45° steps, giving five conformers, and the following were calculated from them: atomic orbital (AO) contributions to the HOMO and LUMO, atomic charges, bond length, bond order, HOMO, LUMO, hardness, electronegativity, polarizability, electrostatic potential, UV-vis spectra and dipole moment (DM). Similarly, the following were analyzed: the energy profile, hybridization, pyramidalization and the hydrogen-out-of-plane (HOOP) wagging from the H11-C11[double bond, length as m-dash]C12-H12 dihedral angle. In addition, retinal with a water H-bond (HR) in the SB was included for comparison. Interestingly, in the PR, C11 and C12 are totally the LUMO and the HOMO, respectively, and have a large electronegativity difference, which predicts an electron jump in these atoms during photoexcitation. At the same time, the PR showed a longer bond length and lower bond order, with a larger DM, lower HOMO-LUMO gap, lower hardness and higher electronegativity. In addition, the AOs of -45° and -90° conformers changed significantly, from pz to py, during the rotation concomitantly with marked hybridization, smooth pyramidalization and lower HOOP activity. Clearly, the atomic and molecular differences between the UR and PR are overwhelming, including the rotational energy profile and light absorption spectra, which indicates that light absorption of UR and PR is already determined by the retinal characteristics of the SB protonation. The HR-model compared with UR shows a lower energy barrier and a discreet bathochromic effect in the UV region.

QTAIM charge-charge flux-dipole flux interpretation of electronegativity and potential models of the fluorochloromethane mean dipole moment derivatives.

PubMed

Silva, Arnaldo F; da Silva, João V; Haiduke, R L A; Bruns, Roy E

2011-11-17

Infrared fundamental vibrational intensities and quantum theory atoms in molecules (QTAIM) charge-charge flux-dipole flux (CCFDF) contributions to the polar tensors of the fluorochloromethanes have been calculated at the QCISD/cc-pVTZ level. A root-mean-square error of 20.0 km mol(-1) has been found compared to an experimental error estimate of 14.4 and 21.1 km mol(-1) for MP2/6-311++G(3d,3p) results. The errors in the QCISD polar tensor elements and mean dipole moment derivatives are 0.059 e when compared with the experimental values. Both theoretical levels provide results showing that the dynamical charge and dipole fluxes provide significant contributions to the mean dipole moment derivatives and tend to be of opposite signs canceling one another. Although the experimental mean dipole moment derivative values suggest that all the fluorochloromethane molecules have electronic structures consistent with a simple electronegativity model with transferable atomic charges for their terminal atoms, the QTAIM/CCFDF models confirm this only for the fluoromethanes. Whereas the fluorine atom does not suffer a saturation effect in its capacity to drain electronic charge from carbon atoms that are attached to other fluorine and chlorine atoms, the zero flux electronic charge of the chlorine atom depends on the number and kind of the other substituent atoms. Both the QTAIM carbon charges (r = 0.990) and mean dipole moment derivatives (r = 0.996) are found to obey Siegbahn's potential model for carbon 1s electron ionization energies at the QCISD/cc-pVTZ level. The latter is a consequence of the carbon mean derivatives obeying the electronegativity model and not necessarily to their similarities with atomic charges. Atomic dipole contributions to the neighboring atom electrostatic potentials of the fluorochloromethanes are found to be of comparable size to the atomic charge contributions and increase the accuracy of Siegbahn's model for the QTAIM charge model results. Substitution effects of the hydrogen, fluorine, and chlorine atoms on the charge and dipole flux QTAIM contributions are found to be additive for the mean dipole derivatives of the fluorochloromethanes.

DYNAMIC PROPERTIES OF SHOCK LOADED THIN URANIUM FOILS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robbins, D. L.; Kelly, A. M.; Alexander, D. J.

A series of spall experiments has been completed with thin depleted uranium targets, nominally 0.1 mm thick. The first set of uranium spall targets was cut and ground to final thickness from electro-refined, high-purity, cast uranium. The second set was rolled to final thickness from low purity uranium. The impactors for these experiments were laser-launched 0.05-mm thick copper flyers, 3 mm in diameter. Laser energies were varied to yield a range of flyer impact velocities. This resulted in varying degrees of damage to the uranium spall targets, from deformation to complete spall or separation at the higher velocities. Dynamic measurementsmore » of the uranium target free surface velocities were obtained with dual velocity interferometers. Uranium targets were recovered and sectioned after testing. Free surface velocity profiles were similar for the two types of uranium, but spall strengths (estimated from the magnitude of the pull-back signal) are higher for the high-purity cast uranium. Velocity profiles and microstructural evidence of spall from the sectioned uranium targets are presented.« less

Aftermath of Uranium Ore Processing on Floodplains: Lasting Effects of Uranium on Soil and Microbes

NASA Astrophysics Data System (ADS)

Tang, H.; Boye, K.; Bargar, J.; Fendorf, S. E.

2016-12-01

A former uranium ore processing site located between the Wind River and the Little Wind River near the city of Riverton, Wyoming, has generated a uranium plume in the groundwater within the floodplain. Uranium is toxic and poses a threat to human health. Thus, controlling and containing the spread of uranium will benefit the human population. The primary source of uranium was removed from the processing site, but a uranium plume still exists in the groundwater. Uranium in its reduced form is relatively insoluble in water and therefore is retained in organic rich, anoxic layers in the subsurface. However, with the aid of microbes uranium becomes soluble in water which could expose people and the environment to this toxin, if it enters the groundwater and ultimately the river. In order to better understand the mechanisms controlling uranium behavior in the floodplains, we examined sediments from three sediment cores (soil surface to aquifer). We determined the soil elemental concentrations and measured microbial activity through the use of several instruments (e.g. Elemental Analyzer, X-ray Fluorescence, MicroResp System). Through the data collected, we aim to obtain a better understanding of how the interaction of geochemical factors and microbial metabolism affect uranium mobility. This knowledge will inform models used to predict uranium behavior in response to land use or climate change in floodplain environments.

New Technique for Speciation of Uranium in Sediments Following Acetate-Stimulated Bioremediation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

2011-06-22

Acetate-stimulated bioremediation is a promising new technique for sequestering toxic uranium contamination from groundwater. The speciation of uranium in sediments after such bioremediation attempts remains unknown as a result of low uranium concentration, and is important to analyzing the stability of sequestered uranium. A new technique was developed for investigating the oxidation state and local molecular structure of uranium from field site sediments using X-Ray Absorption Spectroscopy (XAS), and was implemented at the site of a former uranium mill in Rifle, CO. Glass columns filled with bioactive Rifle sediments were deployed in wells in the contaminated Rifle aquifer and amendedmore » with a hexavalent uranium (U(VI)) stock solution to increase uranium concentration while maintaining field conditions. This sediment was harvested and XAS was utilized to analyze the oxidation state and local molecular structure of the uranium in sediment samples. Extended X-Ray Absorption Fine Structure (EXAFS) data was collected and compared to known uranium spectra to determine the local molecular structure of the uranium in the sediment. Fitting was used to determine that the field site sediments did not contain uraninite (UO{sub 2}), indicating that models based on bioreduction using pure bacterial cultures are not accurate for bioremediation in the field. Stability tests on the monomeric tetravalent uranium (U(IV)) produced by bioremediation are needed in order to assess the efficacy of acetate-stimulation bioremediation.« less

Health effects of uranium: new research findings.

PubMed

Brugge, Doug; Buchner, Virginia

2011-01-01

Recent plans for a nuclear renaissance in both established and emerging economies have prompted increased interest in uranium mining. With the potential for more uranium mining worldwide and a growth in the literature on the toxicology and epidemiology of uranium and uranium mining, we found it timely to review the current state of knowledge. Here, we present a review of the health effects of uranium mining, with an emphasis on newer findings (2005-2011). Uranium mining can contaminate air, water, and soil. The chemical toxicity of the metal constitutes the primary environmental health hazard, with the radioactivity of uranium a secondary concern. The update of the toxicologic evidence on uranium adds to the established findings regarding nephrotoxicity, genotoxicity, and developmental defects. Additional novel toxicologic findings, including some at the molecular level, are now emerging that raise the biological plausibility of adverse effects on the brain, on reproduction, including estrogenic effects, on gene expression, and on uranium metabolism. Historically, most epidemiology on uranium mining has focused on mine workers and radon exposure. Although that situation is still overwhelmingly true, a smaller emerging literature has begun to form around environmental exposure in residential areas near uranium mining and processing facilities. We present and critique such studies. Clearly, more epidemiologic research is needed to contribute to causal inference. As much damage is irreversible, and possibly cumulative, present efforts must be vigorous to limit environmental uranium contamination and exposure.

METHOD OF APPLYING NICKEL COATINGS ON URANIUM

DOEpatents

Gray, A.G.

1959-07-14

A method is presented for protectively coating uranium which comprises etching the uranium in an aqueous etching solution containing chloride ions, electroplating a coating of nickel on the etched uranium and heating the nickel plated uranium by immersion thereof in a molten bath composed of a material selected from the group consisting of sodium chloride, potassium chloride, lithium chloride, and mixtures thereof, maintained at a temperature of between 700 and 800 deg C, for a time sufficient to alloy the nickel and uranium and form an integral protective coating of corrosion-resistant uranium-nickel alloy.

Uranium-bearing lignite in southwestern North Dakota

USGS Publications Warehouse

Moore, George W.; Melin, Robert E.; Kepferle, Roy C.

1954-01-01

Uranium-bearing lignite was mapped and sampled in the Bullion Butte, Sentinel Butte, HT Butte, and Chalky Buttes areas in southwestern North Dakota. The uraniferous lignite occurs at several stratigraphic positions in the Sentinel Butte member of the Fort Union formation of Paleocene age. A total of 261 samples were collected for uranium analysis from 85 localities, Lignite contained as much as 0.045 percent uranium, 10.0 percent ash, and 0.45 percent uranium in the ash was found although the average is lower. Inferred reserves for the four areas examined are estimated to be about 27 million tons of lignite in beds about 2 feet thick and containing more than 3000 tons of uranium. The lignite in beds about 2 feet thick and containing more than 3000 tons of uranium. The lignite averages more than 30 percent ash in the surface samples. The principal factor that seems to influence the uranium content of lignite beds is their stratigraphic position below the overlying rocks of the White River group of Oligocene age. All of the uranium-bearing beds closely underlie the base of the White River group. Although this relationship seems to be the controlling factor, the relative concentration of uranium may be modified by other conditions. Beds enclosed in permeable rocks are more uraniferous than beds in impermeable rocks, and thin beds have higher content of uranium than thick beds. In addition, thick lignite beds commonly have a top=preferential distribution of uranium. These and other factors suggest that the uranium is secondary and this it was introduced by ground water which had leached uranium from volcanic ash in the overlying rocks of the White River group. It is thought that the uranium is held in the lignite as part of a metallo-organic compound.

Potential uranium supply from phosphoric acid: A U.S. analysis comparing solvent extraction and Ion exchange recovery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Haeyeon; G. Eggert, Roderick; W. Carlsen, Brett

Phosphate rock contains significant amounts of uranium, although in low concentrations. Recovery of uranium as a by-product from phosphoric acid, an intermediate product produced during the recovery of phosphorus from phosphate rock, is not unprecedented. Phosphoric acid plants ceased to produce uranium as a by-product in the early 1990s with the fall of uranium prices. In the last decade, this topic has regained attention due to higher uranium prices and expected increase in demand for uranium. Our study revisits the topic and estimates how much uranium might be recoverable from current phosphoric acid production in the United States and whatmore » the associated costs might be considering two different recovery processes: solvent extraction and ion exchange. Based on U.S. phosphoric acid production in 2014, 5.5 million pounds of U 3O 8 could have been recovered, more than domestic U.S. mine production of uranium in the same year. Annualized costs for a hypothetical uranium recovery plant are US$48-66 per pound U 3O 8 for solvent extraction, the process used historically in the United States to recover uranium from phosphoric acid. For ion exchange, not yet proven at a commercial scale for uranium recovery, the estimated costs are US$33-54 per pound U 3O 8. Our results suggest that it is technically possible for the United States to recover significant quantities of uranium from current phosphoric acid production. And for this type of uranium production to be economically attractive on a large scale, either recovery costs must fall or uranium prices rise.« less

Potential uranium supply from phosphoric acid: A U.S. analysis comparing solvent extraction and Ion exchange recovery

DOE PAGES

Kim, Haeyeon; G. Eggert, Roderick; W. Carlsen, Brett; ...

2016-06-16

Phosphate rock contains significant amounts of uranium, although in low concentrations. Recovery of uranium as a by-product from phosphoric acid, an intermediate product produced during the recovery of phosphorus from phosphate rock, is not unprecedented. Phosphoric acid plants ceased to produce uranium as a by-product in the early 1990s with the fall of uranium prices. In the last decade, this topic has regained attention due to higher uranium prices and expected increase in demand for uranium. Our study revisits the topic and estimates how much uranium might be recoverable from current phosphoric acid production in the United States and whatmore » the associated costs might be considering two different recovery processes: solvent extraction and ion exchange. Based on U.S. phosphoric acid production in 2014, 5.5 million pounds of U 3O 8 could have been recovered, more than domestic U.S. mine production of uranium in the same year. Annualized costs for a hypothetical uranium recovery plant are US$48-66 per pound U 3O 8 for solvent extraction, the process used historically in the United States to recover uranium from phosphoric acid. For ion exchange, not yet proven at a commercial scale for uranium recovery, the estimated costs are US$33-54 per pound U 3O 8. Our results suggest that it is technically possible for the United States to recover significant quantities of uranium from current phosphoric acid production. And for this type of uranium production to be economically attractive on a large scale, either recovery costs must fall or uranium prices rise.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

B.R. Westphal; J.C. Price; R.D. Mariani

The pyroprocessing of used nuclear fuel via electrorefining requires the continued addition of uranium trichloride to sustain operations. Uranium trichloride is utilized as an oxidant in the system to allow separation of uranium metal from the minor actinides and fission products. The inventory of uranium trichloride had diminished to a point that production was necessary to continue electrorefiner operations. Following initial experimentation, cupric chloride was chosen as a reactant with uranium metal to synthesize uranium trichloride. Despite the variability in equipment and charge characteristics, uranium trichloride was produced in sufficient quantities to maintain operations in the electrorefiner. The results andmore » conclusions from several experiments are presented along with a set of optimized operating conditions for the synthesis of uranium trichloride.« less

PYROCHEMICAL DECONTAMINATION METHOD FOR REACTOR FUEL

DOEpatents

Buyers, A.G.

1959-06-30

A pyro-chemical method is presented for decontaminating neutron irradiated uranium and separating plutonium therefrom by contact in the molten state with a metal chloride salt. Uranium trichloride and uranium tetrachloride either alone or in admixture with alkaline metal and alkaline eanth metal fluorides under specified temperature and specified phase ratio conditions extract substantially all of the uranium from the irradiated uranium fuel together with certain fission products. The phases are then separated leaving purified uranium metal. The uranium and plutonium in the salt phase can be reduced to forin a highly decontaminated uraniumplutonium alloy. The present method possesses advantages for economically decontaminating irradiated nuclear fuel elements since irradiated fuel may be proccessed immediately after withdrawal from the reactor and the uranium need not be dissolved and later reduced to the metallic form. Accordingly, the uranium may be economically refabricated and reinserted into the reactor.

Carbon diffusion in molten uranium: an ab initio molecular dynamics study

NASA Astrophysics Data System (ADS)

Garrett, Kerry E.; Abrecht, David G.; Kessler, Sean H.; Henson, Neil J.; Devanathan, Ram; Schwantes, Jon M.; Reilly, Dallas D.

2018-04-01

In this work we used ab initio molecular dynamics within the framework of density functional theory and the projector-augmented wave method to study carbon diffusion in liquid uranium at temperatures above 1600 K. The electronic interactions of carbon and uranium were described using the local density approximation (LDA). The self-diffusion of uranium based on this approach is compared with literature computational and experimental results for liquid uranium. The temperature dependence of carbon and uranium diffusion in the melt was evaluated by fitting the resulting diffusion coefficients to an Arrhenius relationship. We found that the LDA calculated activation energy for carbon was nearly twice that of uranium: 0.55 ± 0.03 eV for carbon compared to 0.32 ± 0.04 eV for uranium. Structural analysis of the liquid uranium-carbon system is also discussed.

40 CFR 471.70 - Applicability; description of the uranium forming subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... uranium forming subcategory. 471.70 Section 471.70 Protection of Environment ENVIRONMENTAL PROTECTION... SOURCE CATEGORY Uranium Forming Subcategory § 471.70 Applicability; description of the uranium forming... introductions of pollutants into publicly owned treatment works from the process operations of the uranium...

40 CFR 471.70 - Applicability; description of the uranium forming subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... uranium forming subcategory. 471.70 Section 471.70 Protection of Environment ENVIRONMENTAL PROTECTION... SOURCE CATEGORY Uranium Forming Subcategory § 471.70 Applicability; description of the uranium forming... introductions of pollutants into publicly owned treatment works from the process operations of the uranium...

The Toxicity of Depleted Uranium

PubMed Central

Briner, Wayne

2010-01-01

Depleted uranium (DU) is an emerging environmental pollutant that is introduced into the environment primarily by military activity. While depleted uranium is less radioactive than natural uranium, it still retains all the chemical toxicity associated with the original element. In large doses the kidney is the target organ for the acute chemical toxicity of this metal, producing potentially lethal tubular necrosis. In contrast, chronic low dose exposure to depleted uranium may not produce a clear and defined set of symptoms. Chronic low-dose, or subacute, exposure to depleted uranium alters the appearance of milestones in developing organisms. Adult animals that were exposed to depleted uranium during development display persistent alterations in behavior, even after cessation of depleted uranium exposure. Adult animals exposed to depleted uranium demonstrate altered behaviors and a variety of alterations to brain chemistry. Despite its reduced level of radioactivity evidence continues to accumulate that depleted uranium, if ingested, may pose a radiologic hazard. The current state of knowledge concerning DU is discussed. PMID:20195447

Electrochemical method of producing eutectic uranium alloy and apparatus

DOEpatents

Horton, James A.; Hayden, H. Wayne

1995-01-01

An apparatus and method for continuous production of liquid uranium alloys through the electrolytic reduction of uranium chlorides. The apparatus includes an electrochemical cell formed from an anode shaped to form an electrolyte reservoir, a cathode comprising a metal, such as iron, capable of forming a eutectic uranium alloy having a melting point less than the melting point of pure uranium, and molten electrolyte in the reservoir comprising a chlorine or fluorine containing salt and uranium chloride. The method of the invention produces an eutectic uranium alloy by creating an electrolyte reservoir defined by a container comprising an anode, placing an electrolyte in the reservoir, the electrolyte comprising a chlorine or fluorine containing salt and uranium chloride in molten form, positioning a cathode in the reservoir where the cathode comprises a metal capable of forming an uranium alloy having a melting point less than the melting point of pure uranium, and applying a current between the cathode and the anode.

Geological and geochemical aspects of uranium deposits. A selected, annotated bibliography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garland, P.A.; Thomas, J.M.; Brock, M.L.

1980-06-01

A bibliography of 479 references encompassing the fields of uranium and thorium geochemistry and mineralogy, geology of uranium deposits, uranium mining, and uranium exploration techniques has been compiled by the Ecological Sciences Information Center of Oak Ridge National Laboratory. The bibliography was produced for the National Uranium Resource Evaluation Program, which is funded by the Grand Junction Office of the Department of Energy. The references contained in the bibliography have been divided into the following eight subject categories: (1) geology of deposits, (2) geochemistry, (3) genesis O deposits, (4) exploration, (5) mineralogy, (6) uranium industry, (7) reserves and resources, andmore » (8) geology of potential uranium-bearing areas. All categories specifically refer to uranium and thorium; the last category contains basic geologic information concerning areas which the Grand Junction Office feels are particularly favorable for uranium deposition. The references are indexed by author, geographic location, quadrangle name, geoformational feature, taxonomic name, and keyword.« less

Electrochemical method of producing eutectic uranium alloy and apparatus

DOEpatents

Horton, J.A.; Hayden, H.W.

1995-01-10

An apparatus and method are disclosed for continuous production of liquid uranium alloys through the electrolytic reduction of uranium chlorides. The apparatus includes an electrochemical cell formed from an anode shaped to form an electrolyte reservoir, a cathode comprising a metal, such as iron, capable of forming a eutectic uranium alloy having a melting point less than the melting point of pure uranium, and molten electrolyte in the reservoir comprising a chlorine or fluorine containing salt and uranium chloride. The method of the invention produces an eutectic uranium alloy by creating an electrolyte reservoir defined by a container comprising an anode, placing an electrolyte in the reservoir, the electrolyte comprising a chlorine or fluorine containing salt and uranium chloride in molten form, positioning a cathode in the reservoir where the cathode comprises a metal capable of forming an uranium alloy having a melting point less than the melting point of pure uranium, and applying a current between the cathode and the anode. 2 figures.

Conversion of depleted uranium hexafluoride to a solid uranium compound

DOEpatents

Rothman, Alan B.; Graczyk, Donald G.; Essling, Alice M.; Horwitz, E. Philip

2001-01-01

A process for converting UF.sub.6 to a solid uranium compound such as UO.sub.2 and CaF. The UF.sub.6 vapor form is contacted with an aqueous solution of NH.sub.4 OH at a pH greater than 7 to precipitate at least some solid uranium values as a solid leaving an aqueous solution containing NH.sub.4 OH and NH.sub.4 F and remaining uranium values. The solid uranium values are separated from the aqueous solution of NH.sub.4 OH and NH.sub.4 F and remaining uranium values which is then diluted with additional water precipitating more uranium values as a solid leaving trace quantities of uranium in a dilute aqueous solution. The dilute aqueous solution is contacted with an ion-exchange resin to remove substantially all the uranium values from the dilute aqueous solution. The dilute solution being contacted with Ca(OH).sub.2 to precipitate CaF.sub.2 leaving dilute NH.sub.4 OH.

The adsorption of methyl iodide on uranium and uranium dioxide: Surface characterization using X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES)

NASA Astrophysics Data System (ADS)

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

1984-09-01

The adsorption of methyl iodide on uranium and on uranium dioxide has been studied at 25 °C. Surfaces of the substrates were characterized before and after adsorption by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The XPS binding energy results indicate that CH 3I adsorption on uranium yields a carbide-type carbon, UC, and uranium iodide, UI 3. On uranium dioxide the carbon electron binding energy measurements are consistent with the formation of a hydrocarbon, —CH 3-type moiety. The interpretation of XPS and AES spectral features for CH 3I adsorption on uranium suggest that a complex dissociative adsorption reaction takes place. Adsorption of CH 3I on UO 2 occurs via a dissociative process. Saturation coverage occurs on uranium at approximately two langmuir (1 L = 10 -6 Torr s) exposure whereas saturation coverage on uranium dioxide is found at about five langmuir.

Maps showing the distribution of uranium-deposit clusters in the Colorado Plateau uranium province

USGS Publications Warehouse

Finch, Warren I.

1991-01-01

The Colorado Palteau Uranium Province (CPUP) is defined by the distribution of uranium deposits, chiefly the sandstone-type, in upper Paleozoic and Mesozoic sedimentary rocks within the Colorado Plateau physiographic province (Granger and others, 1986).  The uranium province is bordered by widely distributed and mostly minor uranium deposits in Precambrian and Tertiary rocks and by outcrops of Tertiary extrusive and intrusive igneous rocks.  

Uranium in bone: metabolic and autoradiographic studies in the rat.

PubMed

Priest, N D; Howells, G R; Green, D; Haines, J W

1982-03-01

The distribution and retention of intravenously injected hexavalent uranium-233 in the skeleton of the female rat has been investigated using a variety of autoradiographic and radiochemical techniques. These showed that approximately one third of the injected uranium is deposited in the skeleton where it is retained with an initial biological half-time of approximately 40 days. The studies also showed that: 1 Uranium is initially deposited onto all types of bone surface, but preferentially onto those that are accreting. 2 Uranium is deposited in the calcifying zones of skeletal cartilage. 3 Bone accretion results in the burial of surface deposits of uranium. 4 Bone resorption causes the removal of uranium from surfaces. 5 Resorbed uranium is not retained by osteoclasts and macrophages in the bone marrow. 6 Uranium removed from bone surfaces enters the bloodstream where most is either redeposited in bone or excreted via the kidneys. 7 The recycling of resorbed uranium within the skeleton tends to produce a uniform level of uranium contamination throughout mineralized bone. These results are taken to indicate that uranium deposition in bone shares characteristics in common with both the 'volume-seeking radionuclides' typified by the alkaline earth elements and with the 'bone surface-seeking radionuclides' typified by plutonium.

Process for producing enriched uranium having a .sup.235 U content of at least 4 wt. % via combination of a gaseous diffusion process and an atomic vapor laser isotope separation process to eliminate uranium hexafluoride tails storage

DOEpatents

Horton, James A.; Hayden, Jr., Howard W.

1995-01-01

An uranium enrichment process capable of producing an enriched uranium, having a .sup.235 U content greater than about 4 wt. %, is disclosed which will consume less energy and produce metallic uranium tails having a lower .sup.235 U content than the tails normally produced in a gaseous diffusion separation process and, therefore, eliminate UF.sub.6 tails storage and sharply reduce fluorine use. The uranium enrichment process comprises feeding metallic uranium into an atomic vapor laser isotope separation process to produce an enriched metallic uranium isotopic mixture having a .sup.235 U content of at least about 2 wt. % and a metallic uranium residue containing from about 0.1 wt. % to about 0.2 wt. % .sup.235 U; fluorinating this enriched metallic uranium isotopic mixture to form UF.sub.6 ; processing the resultant isotopic mixture of UF.sub.6 in a gaseous diffusion process to produce a final enriched uranium product having a .sup.235 U content of at least 4 wt. %, and up to 93.5 wt. % or higher, of the total uranium content of the product, and a low .sup.235 U content UF.sub.6 having a .sup.235 U content of about 0.71 wt. % of the total uranium content of the low .sup.235 U content UF.sub.6 ; and converting this low .sup.235 U content UF.sub.6 to metallic uranium for recycle to the atomic vapor laser isotope separation process.

Process for producing enriched uranium having a {sup 235}U content of at least 4 wt. % via combination of a gaseous diffusion process and an atomic vapor laser isotope separation process to eliminate uranium hexafluoride tails storage

DOEpatents

Horton, J.A.; Hayden, H.W. Jr.

1995-05-30

An uranium enrichment process capable of producing an enriched uranium, having a {sup 235}U content greater than about 4 wt. %, is disclosed which will consume less energy and produce metallic uranium tails having a lower {sup 235}U content than the tails normally produced in a gaseous diffusion separation process and, therefore, eliminate UF{sub 6} tails storage and sharply reduce fluorine use. The uranium enrichment process comprises feeding metallic uranium into an atomic vapor laser isotope separation process to produce an enriched metallic uranium isotopic mixture having a {sup 235} U content of at least about 2 wt. % and a metallic uranium residue containing from about 0.1 wt. % to about 0.2 wt. % {sup 235} U; fluorinating this enriched metallic uranium isotopic mixture to form UF{sub 6}; processing the resultant isotopic mixture of UF{sub 6} in a gaseous diffusion process to produce a final enriched uranium product having a {sup 235}U content of at least 4 wt. %, and up to 93.5 wt. % or higher, of the total uranium content of the product, and a low {sup 235}U content UF{sub 6} having a {sup 235}U content of about 0.71 wt. % of the total uranium content of the low {sup 235}U content UF{sub 6}; and converting this low {sup 235}U content UF{sub 6} to metallic uranium for recycle to the atomic vapor laser isotope separation process. 4 figs.

The importance of colloids and mires for the transport of uranium isotopes through the Kalix River watershed and Baltic Sea

DOE Office of Scientific and Technical Information (OSTI.GOV)

Porcelli, D.; Wasserburg, G.J.; Andersson, P.S.

The importance of colloids and organic deposits for the transport of uranium isotopes from continental source regions and through the estuarine environment was investigated in the mire-rich Kalix River drainage basin in northern Sweden and the Baltic Sea. Ultrafiltration techniques were used to separate uranium and other elements associated with colloids > 10 kD and >3 kD from {open_quotes}solute{close_quotes} uranium and provided consistent results and high recovery rates for uranium as well as for other elements from large volume samples. Uranium concentrations in 0.45 {mu}m-filtered Kalix River water samples increased by a factor of 3 from near the headwaters inmore » the Caledonides to the river mouth while major cation concentrations were relatively constant. {sup 234}U {sup 238}U ratios were high ({delta}{sup 234}U = 770-1500) throughout the basin, without showing any simple pattern, and required a supply of {sup 234}U-rich water. Throughout the Kalix River, a large fraction (30-90%) of the uranium is carried by >10 kD colloids, which is compatible with uranium complexation with humic acids. No isotopic differences were found between colloid-associated and solute uranium. Within the Baltic Sea, about half of the uranium is removed at low salinities. The proportion that is lost is equivalent to that of river-derived colloid-bound uranium, suggesting that while solute uranium behaves conservatively during estuarine mixing, colloid-bound uranium is lost due to rapid flocculation of colloidal material. The association of uranium with colloids therefore may be an important parameter in determining uranium estuarine behavior. Mire peats in the Kalix River highly concentrate uranium and are potentially a significant source of recoil {sup 234}U to the mirewaters and river waters. However, mirewater data clearly demonstrate that only small {sup 234}U/{sup 238}U shifts are generated relative to inflowing groundwater. 63 refs., 8 figs., 3 tabs.« less

Uranium hydrogeochemical and stream sediment reconnaissance of the Albuquerque NTMS Quadrangle, New Mexico, including concentrations of forty-three additional elements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maassen, L.W.; Bolivar, S.L.

1979-06-01

The Los Alamos Scientific Laboratory conducted a hydrogeochemical and stream sediment reconnaissance for uranium. Totals of 408 water and 1538 sediment samples were collected from 1802 locations over a 20 100-km/sup 2/ area at an average density of one location per 11 km/sup 2/. Water samples were collected from springs, wells, and streams; sediments samples were collected predominantly from streams, but also from springs. All water samples were analyzed for uranium and 12 other elements. Sediment samples were analyzed for uranium and 42 additional elements. The uranium concentrations in water samples range from below the detection limit of 0.02 ppBmore » to 194.06 ppB. The mean uranium concentration for all water types containing < 40 ppB uranium is 1.98 ppB. Six samples contained uranium concentrations > 40.00 ppB. Well waters have the highest mean uranium concentration; spring waters have the lowest. Clusters of water samples that contain anomalous uranium concentrations are delineated in nine areas. Sediments collected from the quadrangle have uranium concentrations that range between 0.63 ppM and 28.52 ppM, with a mean for all sediments of 3.53 ppM. Eight areas containing clusters of sediments with anomalous uranium concentrations are delineated. One cluster contains sample locations within the Ambrosia Lake uranium district. Five clusters of sediment samples with anomalous uranium concentrations were collected from streams that drain the Jemez volcanic field. Another cluster defines an area just northeast of Albuquerque where streams drain Precambrian rocks, predominantly granites, of the Sandia Mountains. The last cluster, consisting of spring sediments from Mesa Portales, was collected near the contact of the Tertiary Ojo Alamo sandstone with underlying Cretaceous sediments. Sediments from these springs exhibit some of the highest uranium values reported and are associated with high uranium/thorium ratios.« less

31 CFR 540.318 - Uranium Hexafluoride (UF6).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 31 Money and Finance:Treasury 3 2012-07-01 2012-07-01 false Uranium Hexafluoride (UF6). 540.318... OF FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.318 Uranium Hexafluoride (UF6). The term uranium...

49 CFR 173.426 - Excepted packages for articles containing natural uranium or thorium.

Code of Federal Regulations, 2013 CFR

2013-10-01

... uranium or thorium. 173.426 Section 173.426 Transportation Other Regulations Relating to Transportation....426 Excepted packages for articles containing natural uranium or thorium. A manufactured article in which the sole Class 7 (radioactive) material content is natural uranium, unirradiated depleted uranium...

31 CFR 540.318 - Uranium Hexafluoride (UF6).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 31 Money and Finance:Treasury 3 2011-07-01 2011-07-01 false Uranium Hexafluoride (UF6). 540.318... OF FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.318 Uranium Hexafluoride (UF6). The term uranium...

31 CFR 540.318 - Uranium Hexafluoride (UF6).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 31 Money and Finance:Treasury 3 2013-07-01 2013-07-01 false Uranium Hexafluoride (UF6). 540.318... OF FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.318 Uranium Hexafluoride (UF6). The term uranium...

31 CFR 540.316 - Uranium enrichment.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 31 Money and Finance:Treasury 3 2013-07-01 2013-07-01 false Uranium enrichment. 540.316 Section... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.316 Uranium enrichment. The term uranium enrichment means the process of...

31 CFR 540.318 - Uranium Hexafluoride (UF6).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 31 Money and Finance:Treasury 3 2014-07-01 2014-07-01 false Uranium Hexafluoride (UF6). 540.318... OF FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.318 Uranium Hexafluoride (UF6). The term uranium...

31 CFR 540.316 - Uranium enrichment.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 31 Money and Finance:Treasury 3 2014-07-01 2014-07-01 false Uranium enrichment. 540.316 Section... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.316 Uranium enrichment. The term uranium enrichment means the process of...

31 CFR 540.316 - Uranium enrichment.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 31 Money and Finance:Treasury 3 2011-07-01 2011-07-01 false Uranium enrichment. 540.316 Section... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.316 Uranium enrichment. The term uranium enrichment means the process of...

49 CFR 173.426 - Excepted packages for articles containing natural uranium or thorium.

Code of Federal Regulations, 2014 CFR

2014-10-01

... uranium or thorium. 173.426 Section 173.426 Transportation Other Regulations Relating to Transportation....426 Excepted packages for articles containing natural uranium or thorium. A manufactured article in which the sole Class 7 (radioactive) material content is natural uranium, unirradiated depleted uranium...

31 CFR 540.316 - Uranium enrichment.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 31 Money and Finance:Treasury 3 2012-07-01 2012-07-01 false Uranium enrichment. 540.316 Section... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.316 Uranium enrichment. The term uranium enrichment means the process of...

49 CFR 173.426 - Excepted packages for articles containing natural uranium or thorium.

Code of Federal Regulations, 2012 CFR

2012-10-01

... uranium or thorium. 173.426 Section 173.426 Transportation Other Regulations Relating to Transportation....426 Excepted packages for articles containing natural uranium or thorium. A manufactured article in which the sole Class 7 (radioactive) material content is natural uranium, unirradiated depleted uranium...

31 CFR 540.318 - Uranium Hexafluoride (UF6).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 31 Money and Finance: Treasury 3 2010-07-01 2010-07-01 false Uranium Hexafluoride (UF6). 540.318... OF FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.318 Uranium Hexafluoride (UF6). The term uranium...

31 CFR 540.309 - Natural uranium.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 31 Money and Finance:Treasury 3 2011-07-01 2011-07-01 false Natural uranium. 540.309 Section 540.309 Money and Finance: Treasury Regulations Relating to Money and Finance (Continued) OFFICE OF... REGULATIONS General Definitions § 540.309 Natural uranium. The term natural uranium means uranium found in...

31 CFR 540.309 - Natural uranium.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 31 Money and Finance: Treasury 3 2010-07-01 2010-07-01 false Natural uranium. 540.309 Section 540.309 Money and Finance: Treasury Regulations Relating to Money and Finance (Continued) OFFICE OF... REGULATIONS General Definitions § 540.309 Natural uranium. The term natural uranium means uranium found in...

THE RECOVERY OF URANIUM FROM GAS MIXTURE

DOEpatents

Jury, S.H.

1964-03-17

A method of separating uranium from a mixture of uranium hexafluoride and other gases is described that comprises bringing the mixture into contact with anhydrous calcium sulfate to preferentially absorb the uranium hexafluoride on the sulfate. The calcium sulfate is then leached with a selective solvent for the adsorbed uranium. (AEC)

PREPARATION OF URANIUM-ALUMINUM ALLOYS

DOEpatents

Moore, R.H.

1962-09-01

A process is given for preparing uranium--aluminum alloys from a solution of uranium halide in an about equimolar molten alkali metal halide-- aluminum halide mixture and excess aluminum. The uranium halide is reduced and the uranium is alloyed with the excess aluminum. The alloy and salt are separated from each other. (AEC)

Separation of uranium from (Th,U)O.sub.2 solid solutions

DOEpatents

Chiotti, Premo; Jha, Mahesh Chandra

1976-09-28

Uranium is separated from mixed oxides of thorium and uranium by a pyrometallurgical process in which the oxides are mixed with a molten chloride salt containing thorium tetrachloride and thorium metal which reduces the uranium oxide to uranium metal which can then be recovered from the molten salt. The process is particularly useful for the recovery of uranium from generally insoluble high-density sol-gel thoria-urania nuclear reactor fuel pellets.

PROCESS FOR SEGREGATING URANIUM FROM PLUTONIUM AND FISSION-PRODUCT CONTAMINATION

DOEpatents

Ellison, C.V.; Runion, T.C.

1961-06-27

An aqueous nitric acid solution containing uranium, plutonium, and fission product values is contacted with an organic extractant comprised of a trialkyl phosphate and an organic diluent. The relative amounts of trialkyl phosphate and uranium values are controlled to achieve a concentration of uranium values in the organic extractant of at least 0.35 moles uranium per mole of trialkyl phosphate, thereby preferentially extracting uranium values into the organic extractant.

URANIUM RECOVERY PROCESS

DOEpatents

Bailes, R.H.; Long, R.S.; Olson, R.S.; Kerlinger, H.O.

1959-02-10

A method is described for recovering uranium values from uranium bearing phosphate solutions such as are encountered in the manufacture of phosphate fertilizers. The solution is first treated with a reducing agent to obtain all the uranium in the tetravalent state. Following this reduction, the solution is treated to co-precipitate the rcduced uranium as a fluoride, together with other insoluble fluorides, thereby accomplishing a substantially complete recovery of even trace amounts of uranium from the phosphate solution. This precipitate usually takes the form of a complex fluoride precipitate, and after appropriate pre-treatment, the uranium fluorides are leached from this precipitate and rccovered from the leach solution.

Carbon diffusion in molten uranium: an ab initio molecular dynamics study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garrett, Kerry E.; Abrecht, David G.; Kessler, Sean H.

In this work we used ab initio molecular dynamics (AIMD) within the framework of density functional theory (DFT) and the projector-augmented wave (PAW) method to study carbon diffusion in liquid uranium at temperatures above 1600 K. The electronic interactions of carbon and uranium were described using the local density approximation (LDA). The self-diffusion of uranium based on this approach is compared with literature computational and experimental results for liquid uranium. The temperature dependence of carbon and uranium diffusion in the melt was evaluated by fitting the resulting diffusion coefficients to an Arrhenius relationship. We found that the LDA calculated activationmore » energy for carbon was nearly twice that of uranium: 0.55±0.03 eV for carbon compared to 0.32±0.04 eV for uranium. Structural analysis of the liquid uranium-carbon system is also discussed.« less

Absorption of Thermal Neutrons in Uranium

DOE R&D Accomplishments Database

Creutz, E. C.; Wilson, R. R.; Wigner, E. P.

1941-09-26

A knowledge of the absorption processes for neutrons in uranium is important for planning a chain reaction experiment. The absorption of thermal neutrons in uranium and uranium oxide has been studied. Neutrons from the cyclotron were slowed down by passage through a graphite block. A uranium or uranium oxide sphere was placed at various positions in the block. The neutron intensity at different points in the sphere and in the graphite was measured by observing the activity induced in detectors or uranium oxide or manganese. It was found that both the fission activity in the uranium oxide and the activity induced in manganese was affected by non-thermal neutrons. An experimental correction for such effects was made by making measurements with the detectors surrounded by cadmium. After such corrections the results from three methods of procedure with the uranium oxide detectors and from the manganese detectors were consistent to within a few per cent.

Process for producing an aggregate suitable for inclusion into a radiation shielding product

DOEpatents

Lessing, Paul A.; Kong, Peter C.

2000-01-01

The present invention is directed to methods for converting depleted uranium hexafluoride to a stable depleted uranium silicide in a one-step reaction. Uranium silicide provides a stable aggregate material that can be added to concrete to increase the density of the concrete and, consequently, shield gamma radiation. As used herein, the term "uranium silicide" is defined as a compound generically having the formula U.sub.x Si.sub.y, wherein the x represents the molecules of uranium and the y represent the molecules of silicon. In accordance with the present invention, uranium hexafluoride is converted to a uranium silicide by contacting the uranium hexafluoride with a silicon-containing material at a temperature in a range between about 1450.degree. C. and about 1750.degree. C. The stable depleted uranium silicide is included as an aggregate in a radiation shielding product, such as a concrete product.

Fermentation and Hydrogen Metabolism Affect Uranium Reduction by Clostridia

DOE PAGES

Gao, Weimin; Francis, Arokiasamy J.

2013-01-01

Previously, it has been shown that not only is uranium reduction under fermentation condition common among clostridia species, but also the strains differed in the extent of their capability and the pH of the culture significantly affected uranium(VI) reduction. In this study, using HPLC and GC techniques, metabolic properties of those clostridial strains active in uranium reduction under fermentation conditions have been characterized and their effects on capability variance of uranium reduction discussed. Then, the relationship between hydrogen metabolism and uranium reduction has been further explored and the important role played by hydrogenase in uranium(VI) and iron(III) reduction by clostridiamore » demonstrated. When hydrogen was provided as the headspace gas, uranium(VI) reduction occurred in the presence of whole cells of clostridia. This is in contrast to that of nitrogen as the headspace gas. Without clostridia cells, hydrogen alone could not result in uranium(VI) reduction. In alignment with this observation, it was also found that either copper(II) addition or iron depletion in the medium could compromise uranium reduction by clostridia. In the end, a comprehensive model was proposed to explain uranium reduction by clostridia and its relationship to the overall metabolism especially hydrogen (H 2 ) production.« less

Incorporation of Uranium: II. Distribution of Uranium Absorbed through the Lungs and the Skin

PubMed Central

Walinder, G.; Fries, B.; Billaudelle, U.

1967-01-01

In experiments on mice, rabbits, and piglets the distribution of uranium was studied at different times after exposure. Uranium was administered by inhalation (mice) and through the skin (rabbits and piglets). These investigations show that the uptakes of uranium in different organs of the three species are highly dependent on the amounts administered. There seems to be a saturation effect in the spleen and bone tissue whenever the uranium concentration in the blood exceeds a certain level. The effect in the kidney is completely different. If, in a series of animals, the quantity of uranium is continuously increased, the uptakes by the kidneys increase more rapidly than the quantities administered. This observation seems to be consistent with the toxic effects of uranium on the capillary system in the renal cortex. Polyphloretin phosphate, a compound which reduces permeability, was investigated with respect to its effect on the uptake of uranium deposited in skin wounds in rabbits and piglets. It significantly reduced the absorption of uranium, even from depots in deep wounds. The findings are discussed with reference to the routine screening of persons exposed to uranium at AB Atomenergi. Images PMID:6073090

Rapid Dissolution of Soluble Uranyl Phases in Arid, Mine-Impacted Catchments Near Church Rock, NM

DOE Office of Scientific and Technical Information (OSTI.GOV)

deLemos, J.L.; Bostick, B.C.; Quicksall, A.N.

2009-05-14

We tested the hypothesis that runoff of uranium-bearing particles from mining waste disposal areas was a significant mechanism for redistribution of uranium in the northeastern part of the Upper Puerco River watershed (New Mexico). However, our results were not consistent with this hypothesis. Analysis of >100 sediment and suspended sediment samples collected adjacent to and downstream from uranium source areas indicated that uranium levels in the majority of the samples were not elevated above background. Samples collected within 50 m of a known waste disposal site were subjected to detailed geochemical characterization. Uranium in these samples was found to bemore » highly soluble; treatment with synthetic pore water for 24 h caused dissolution of 10-50% of total uranium in the samples. Equilibrium uranium concentrations in pore water were >4.0 mg/L and were sustained in repeated wetting events, effectively depleting soluble uranium from the solid phase. The dissolution rate of uranium appeared to be controlled by solid-phase diffusion of uranium from within uranium-bearing mineral particles. X-ray adsorption spectroscopy indicated the presence of a soluble uranyl silicate, and possibly a uranyl phosphate. These phases were exhausted in transported sediment suggesting that uranium was readily mobilized from sediments in the Upper Puerco watershed and transported in the dissolved load. These results could have significance for uranium risk assessment as well as mining waste management and cleanup efforts.« less

Comparison of the Kinetic Rate Law Parameters for the Dissolution of Natural and Synthetic Autunite in the Presence of Aqueous Bicarbonate Ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gudavalli, Ravi; Katsenovich, Yelena; Wellman, Dawn M.

2013-08-02

Bicarbonate is one of the most significant components within the uranium geochemical cycle. In aqueous solutions, bicarbonate forms strong complexes with uranium. As such, aqueous bicarbonate may significantly increase the rate of uranium release from uranium minerals. Quantifying the relationship of aqueous bicarbonate concentration to the rate of uranium release during dissolution is critical to understanding the long-term fate of uranium within the environment. Single-pass flow-through (SPTF) experiments were conducted to estimate the rate of uranium release from Na meta-autunite as a function of bicarbonate (0.0005-0.003 M) under the pH range of 6-11 and a temperature range of 5-60oC. Consistentmore » with the results of previous investigation, the rate of uranium release exhibited minimal dependency on temperature; but were strongly dependent on pH. Increasing aqueous bicarbonate concentrations afforded comparable increases in the rate of release of uranium. Most notably under low pH conditions the aqueous bicarbonate resulted in up to 370 fold increases in the rate of uranium release in relative to the rate of uranium release in the absence of bicarbonate. However, the effect of aqueous bicarbonate on the release of uranium was significantly less under higher pH conditions. It is postulated that at high pH values, surface sites are saturated with carbonate, thus the addition of more bicarbonate would have less effect on uranium release.« less

Rapid Dissolution of Soluble Uranyl Phases in Arid, Mine-Impacted Catchments near Church Rock, NM

PubMed Central

DELEMOS, JAMIE L.; BOSTICK, BENJAMIN C.; QUICKSALL, ANDREW N.; LANDIS, JOSHUA D.; GEORGE, CHRISTINE C.; SLAGOWSKI, NAOMI L.; ROCK, TOMMY; BRUGGE, DOUG; LEWIS, JOHNNYE; DURANT, JOHN L.

2008-01-01

We tested the hypothesis that runoff of uranium-bearing particles from mining waste disposal areas was a significant mechanism for redistribution of uranium in the northeastern part of the Upper Puerco River watershed (New Mexico). However, our results were not consistent with this hypothesis. Analysis of >100 sediment and suspended sediment samples collected adjacent to and downstream from uranium source areas indicated that uranium levels in the majority of the samples were not elevated above background. Samples collected within 50 m of a known waste disposal site were subjected to detailed geochemical characterization. Uranium in these samples was found to be highly soluble; treatment with synthetic pore water for 24 h caused dissolution of 10–50% of total uranium in the samples. Equilibrium uranium concentrations in pore water were >4.0 mg/L and were sustained in repeated wetting events, effectively depleting soluble uranium from the solid phase. The dissolution rate of uranium appeared to be controlled by solid-phase diffusion of uranium from within uranium-bearing mineral particles. X-ray adsorption spectroscopy indicated the presence of a soluble uranyl silicate, and possibly a uranyl phosphate. These phases were exhausted in transported sediment suggesting that uranium was readily mobilized from sediments in the Upper Puerco watershed and transported in the dissolved load. These results could have significance for uranium risk assessment as well as mining waste management and cleanup efforts. PMID:18589950

Biosorption of uranium by Pseudomonas aeruginosa strain CSU: Characterization and comparison studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, M.Z.C.; Norman, J.M.; Faison, B.D.

1996-07-20

Pseudomonas aeruginosa strain CSU, a nongenetically engineered bacterial strain known to bind dissolved hexavalent uranium (as UO{sub 2}{sup 2+} and/or its cationic hydroxo complexes) was characterized with respect to its sorptive activity. The uranium biosorption equilibrium could be described by the Langmuir isotherm. The rate of uranium adsorption increased following permeabilization of the outer and/or cytoplasmic membrane by organic solvents such as acetone. P. aeruginosa CSU biomass was significantly more sorptive toward uranium than certain novel, patented biosorbents derived from algal or fungal biomass sources. P. aeruginosa CSU biomass was also competitive with commercial cation-exchange resins, particularly in the presencemore » of dissolved transition metals. Uranium binding by P. aeruginosa CSU was clearly pH dependent. Uranium loading capacity increased with increasing pH under acidic conditions, presumably as a function of uranium speciation and due to the H{sup +} competition at some binding sites. Nevertheless, preliminary evidence suggests that this microorganism is also capable of binding anionic hexavalent uranium complexes. Ferric iron was a strong inhibitor of uranium binding to P. aeruginosa CSU biomass, and the presence of uranium also decreased the Fe{sup 3+} loading when the biomass was not saturated with Fe{sup 3+}. Thus, a two-state process in which iron and uranium are removed in consecutive steps was proposed for efficient use of the biomass as a biosorbent in uranium removal from mine wastewater, especially acidic leachates.« less

Urinary excretion of uranium in adult inhabitants of the Czech Republic.

PubMed

Malátová, Irena; Bečková, Věra; Kotík, Lukáš

2016-02-01

The main aim of this study was to determine and evaluate urinary excretion of uranium in the general public of the Czech Republic. This value should serve as a baseline for distinguishing possible increase in uranium content in population living near legacy sites of mining and processing uranium ores and also to help to distinguish the proportion of the uranium content in urine among uranium miners resulting from inhaled dust. The geometric mean of the uranium concentration in urine of 74 inhabitants of the Czech Republic was 0.091 mBq/L (7.4 ng/L) with the 95% confidence interval 0.071-0.12 mBq/L (5.7-9.6 ng/L) respectively. The geometric mean of the daily excretion was 0.15 mBq/d (12.4 ng/d) with the 95% confidence interval 0.12-0.20 mBq/d (9.5-16.1 ng/d) respectively. Despite the legacy of uranium mines and plants processing uranium ore in the Czech Republic, the levels of uranium in urine and therefore, also human body content of uranium, is similar to other countries, esp. Germany, Slovenia and USA. Significant difference in the daily urinary excretion of uranium was found between individuals using public supply and private water wells as a source of drinking water. Age dependence of daily urinary excretion of uranium was not found. Mean values and their range are comparable to other countries, esp. Germany, Slovenia and USA. Copyright © 2015 Elsevier Ltd. All rights reserved.

Challenges dealing with depleted uranium in Germany - Reuse or disposal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moeller, Kai D.

2007-07-01

During enrichment large amounts of depleted Uranium are produced. In Germany every year 2.800 tons of depleted uranium are generated. In Germany depleted uranium is not classified as radioactive waste but a resource for further enrichment. Therefore since 1996 depleted Uranium is sent to ROSATOM in Russia. However it still has to be dealt with the second generation of depleted Uranium. To evaluate the alternative actions in case a solution has to be found in Germany, several studies have been initiated by the Federal Ministry of the Environment. The work that has been carried out evaluated various possibilities to dealmore » with depleted uranium. The international studies on this field and the situation in Germany have been analyzed. In case no further enrichment is planned the depleted uranium has to be stored. In the enrichment process UF{sub 6} is generated. It is an international consensus that for storage it should be converted to U{sub 3}O{sub 8}. The necessary technique is well established. If the depleted Uranium would have to be characterized as radioactive waste, a final disposal would become necessary. For the planned Konrad repository - a repository for non heat generating radioactive waste - the amount of Uranium is limited by the licensing authority. The existing license would not allow the final disposal of large amounts of depleted Uranium in the Konrad repository. The potential effect on the safety case has not been roughly analyzed. As a result it may be necessary to think about alternatives. Several possibilities for the use of depleted uranium in the industry have been identified. Studies indicate that the properties of Uranium would make it useful in some industrial fields. Nevertheless many practical and legal questions are open. One further option may be the use as shielding e.g. in casks for transport or disposal. Possible techniques for using depleted Uranium as shielding are the use of the metallic Uranium as well as the inclusion in concrete. Another possibility could be the use of depleted uranium for the blending of High enriched Uranium (HEU) or with Plutonium to MOX-elements. (authors)« less

Uranium mineralization and unconformities: how do they correlate? - A look beyond the classic unconformity-type deposit model?

NASA Astrophysics Data System (ADS)

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 varies from strata- to structure-bound and occurs above regional unconformities. The Proterozoic basins in the Mount Isa Inlier rest unconformably on Palaeoproterozoic basement accompanied by volcanic and igneous rocks, which were deformed and metamorphosed in the Mesoproterozoic. Uranium occurrences in the Western Succession of Mount Isa are either hosted in clastic metasediments or mafic volcanics that belong to the Palaeoproterozoic Eastern Creek Volcanics. Uranium and vanadium mineralization occur in metasomatised and hematite-magnetite-carbonate alteration zones, bounded by major faults and regional unconformities. The results of this study highlight the importance of unconformities in uranium minerals systems as possible fluid pathways and/or surfaces of physico-chemical contrast that could have facilitated the precipitation of uranium, not only in classical unconformity style uranium deposits but in several other styles of uranium mineralization as well. References Cuney, M., 2009. The extreme diversity of uranium deposits. Mineralium Deposita, 44, 3-9. Dahlkamp, F. J., 1993. Uranium ore deposits. Springer, Berlin, p 460. OECD / NEA Red Book & IAEA, 2000. Uranium 1999: Resources, Production and Demand. OECD Nuclear Energy Agency and International Atomic Energy Agency, Paris.

Natural uranium impairs the differentiation and the resorbing function of osteoclasts.

PubMed

Gritsaenko, Tatiana; Pierrefite-Carle, Valérie; Lorivel, Thomas; Breuil, Véronique; Carle, Georges F; Santucci-Darmanin, Sabine

2017-04-01

Uranium is a naturally occurring radionuclide ubiquitously present in the environment. The skeleton is the main site of uranium long-term accumulation. While it has been shown that natural uranium is able to perturb bone metabolism through its chemical toxicity, its impact on bone resorption by osteoclasts has been poorly explored. Here, we examined for the first time in vitro effects of natural uranium on osteoclasts. The effects of uranium on the RAW 264.7 monocyte/macrophage mouse cell line and primary murine osteoclastic cells were characterized by biochemical, molecular and functional analyses. We observed a cytotoxicity effect of uranium on osteoclast precursors. Uranium concentrations in the μM range are able to inhibit osteoclast formation, mature osteoclast survival and mineral resorption but don't affect the expression of the osteoclast gene markers Nfatc1, Dc-stamp, Ctsk, Acp5, Atp6v0a3 or Atp6v0d2 in RAW 274.7 cells. Instead, we observed that uranium induces a dose-dependent accumulation of SQSTM1/p62 during osteoclastogenesis. We show here that uranium impairs osteoclast formation and function in vitro. The decrease in available precursor cells, as well as the reduced viability of mature osteoclasts appears to account for these effects of uranium. The SQSTM1/p62 level increase observed in response to uranium exposure is of particular interest since this protein is a known regulator of osteoclast formation. A tempting hypothesis discussed herein is that SQSTM1/p62 dysregulation contributes to uranium effects on osteoclastogenesis. We describe cellular and molecular effects of uranium that potentially affect bone homeostasis. Copyright © 2017 Elsevier B.V. All rights reserved.

Bone as a Possible Target of Chemical Toxicity of Natural Uranium in Drinking Water

PubMed Central

Kurttio, Päivi; Komulainen, Hannu; Leino, Aila; Salonen, Laina; Auvinen, Anssi; Saha, Heikki

2005-01-01

Uranium accumulates in bone, affects bone metabolism in laboratory animals, and when ingested in drinking water increases urinary excretion of calcium and phosphate, important components in the bone structure. However, little is known about bone effects of ingested natural uranium in humans. We studied 146 men and 142 women 26–83 years of age who for an average of 13 years had used drinking water originating from wells drilled in bedrock, in areas with naturally high uranium content. Biochemical indicators of bone formation were serum osteocalcin and amino-terminal propeptide of type I procollagen, and a marker for bone resorption was serum type I collagen carboxy-terminal telopeptide (CTx). The primary measure of uranium exposure was uranium concentration in drinking water, with additional information on uranium intake and uranium concentration in urine. The data were analyzed separately for men and women with robust regression (which suppresses contributions of potential influential observations) models with adjustment for age, smoking, and estrogen use. The median uranium concentration in drinking water was 27 μg/L (interquartile range, 6–116 μg/L). The median of daily uranium intake was 36 μg (7–207 μg) and of cumulative intake 0.12 g (0.02–0.66 g). There was some suggestion that elevation of CTx (p = 0.05) as well as osteocalcin (p = 0.19) could be associated with increased uranium exposure (uranium in water and intakes) in men, but no similar relationship was found in women. Accordingly, bone may be a target of chemical toxicity of uranium in humans, and more detailed evaluation of bone effects of natural uranium is warranted. PMID:15626650

Integrated geophysical investigations for the delineation of source and subsurface structure associated with hydro-uranium anomaly: A case study from South Purulia Shear Zone (SPSZ), India

NASA Astrophysics Data System (ADS)

Sharma, S. P.; Biswas, A.

2012-12-01

South Purulia Shear Zone (SPSZ) is an important region for prospecting of uranium mineralization. Geological studies and hydro-uranium anomaly suggest the presence of Uranium deposit around Raghunathpur village which lies about 8 km north of SPSZ. However, detailed geophysical investigations have not been carried out in this region for investigation of uranium mineralization. Since surface signature of uranium mineralization is not depicted near the location, a deeper subsurface source is expected for hydro uranium anomaly. To delineate the subsurface structure and to investigate the origin of hydro-uranium anomaly present in the area, Vertical Electrical Sounding (VES) using Schlumberger array and Gradient Resistivity Profiling (GRP) were performed at different locations along a profile perpendicular to the South Purulia Shear Zone. Apparent resistivity computed from the measured sounding data at various locations shows a continuously increasing trend. As a result, conventional apparent resistivity data is not able to detect the possible source of hydro uranium anomaly. An innovative approach is applied which depicts the apparent conductivity in the subsurface revealed a possible connection from SPSZ to Raghunathpur. On the other hand resistivity profiling data suggests a low resistive zone which is also characterized by low Self-Potential (SP) anomaly zone. Since SPSZ is characterized by the source of uranium mineralization; hydro-uranium anomaly at Raghunathpur is connected with the SPSZ. The conducting zone has been delineated from SPSZ to Raghunathpur at deeper depths which could be uranium bearing. Since the location is also characterized by a low gravity and high magnetic anomaly zone, this conducting zone is likely to be mineralized zone. Keywords: Apparent resistivity; apparent conductivity; Self Potential; Uranium mineralization; shear zone; hydro-uranium anomaly.

Thermogravimetric Control of Intermediate Products in the Metallurgy of Uranium; CONTROL TERMOGRAVIMETRICO DE PRODUCTOS INTERMEDIOS DE LA METALURGIA DEL URANIO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanchez, L.G.; Cellini, R.F.

1959-01-01

The thermal decomposition of some intermediate compounds in the metallurgy of uranium such as uranium peroxide, ammonium uranate, ammonium uranium pentafluoride, uranium tetrafluoride, and UO/sub 2/, were studied using Chevenard's thermobalance. Some data on the pyrolysis of synthetic mixtures of intermediate compounds which may appear during the industrial processing are given. Thermogravimetric methods of control are suggested for use in uranium metallurgy. (tr-auth)

DECONTAMINATION OF URANIUM

DOEpatents

Feder, H.M.; Chellew, N.R.

1958-02-01

This patent deals with the separation of rare earth and other fission products from neutron bombarded uranium. This is accomplished by melting the uranium in contact with either thorium oxide, maguesium oxide, alumnum oxide, beryllium oxide, or uranium dioxide. The melting is preferably carried out at from 1150 deg to 1400 deg C in an inert atmosphere, such as argon or helium. During this treatment a scale of uranium dioxide forms on the uranium whtch contains most of the fission products.

Uranium(VI) interactions with mackinawite in the presence and absence of bicarbonate and oxygen.

PubMed

Gallegos, Tanya J; Fuller, Christopher C; Webb, Samuel M; Betterton, William

2013-07-02

Mackinawite, Fe(II)S, samples loaded with uranium (10(-5), 10(-4), and 10(-3) mol U/g FeS) at pH 5, 7, and 9, were characterized using X-ray absorption spectroscopy and X-ray diffraction to determine the effects of pH, bicarbonate, and oxidation on uptake. Under anoxic conditions, a 5 g/L suspension of mackinawite lowered 5 × 10(-5) M uranium(VI) to below 30 ppb (1.26 × 10(-7) M) U. Between 82 and 88% of the uranium removed from solution by mackinawite was U(IV) and was nearly completely reduced to U(IV) when 0.012 M bicarbonate was added. Near-neighbor coordination consisting of uranium-oxygen and uranium-uranium distances indicates the formation of uraninite in the presence and absence of bicarbonate, suggesting reductive precipitation as the dominant removal mechanism. Following equilibration in air, mackinawite was oxidized to mainly goethite and sulfur and about 76% of U(IV) was reoxidized to U(VI) with coordination of uranium to axial and equatorial oxygen, similar to uranyl. Additionally, uranium-iron distances, typical of coprecipitation of uranium with iron oxides, and uranium-sulfur distances indicating bidentate coordination of U(VI) to sulfate were evident. The affinity of mackinawite and its oxidation products for U(VI) provides impetus for further study of mackinawite as a potential reactive medium for remediation of uranium-contaminated water.

Hydrogeochemical and stream sediment reconnaissance basic data for Brownsville-McAllen NTMS Quadrangles, Texas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1980-09-30

Results of a reconnaissance geochemical survey of the Brownsville-McAllen Quadrangles, Texas are reported. Field and laboratory data are presented for 427 groundwater and 171 stream sediment samples. Statistical and areal distributions of uranium and possible uranium-related variables are displayed. Pertinent geologic factors which may be of significance in evaluating the potential for uranium mineralization are briefly discussed. Groundwater data indicate the most promising area for potential uranium mineralization occurs in the northwestern section of the quadrangles (Jim Hogg, Starr, and Zapata Counties), where waters are derived from the Catahoula Formation. These groundwaters have high concentrations of uranium, uranium associated elements,more » and low values for specific conductance. Another area with high uranium concentrations is in the southeastern portion of the survey area (Hidalgo, Cameron, and Willacy Counties). Shallow wells <10 m (30 ft) are numerous in this area and high specific conductance values may indicate contamination from extensive fertilization. Stream sediment data for the survey does not indicate an area favorable for uranium mineralization. Anomalous acid soluble uranium values in the southeastern area (Hidalgo, Cameron, and Willacy Counties) can be attributed to phosphate fertilizer contamination. Four samples in the western part of the area (western Starr County) have anomalously high total uranium values and low acid soluble uranium values, indicating the uranium may be contained in resistate minerals.« less

Uranium hydrogeochemical and stream sediment reconnaissance of the Newcastle NTMS quadrangle, Wyoming, including concentrations of forty-two additional elements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goff, S.J.; Sandoval, W.F.; Gallimore, D.L.

1980-06-01

During the summer and fall of 1977, 533 water and 1226 sediment samples were collected from 1740 locations within the 18,000 km/sup 2/ area of the Newcastle quadrangle, Wyoming. Water samples were collected from wells and springs; sediment samples were collected from stream channels and from springs. Each water sample was analyzed for uranium, and each sediment sample was analyzed for 43 elements, including uranium and thorium. Uranium concentrations in water samples range from below the detection limit of 0.02 ppB to 702.26 ppB and have a median of 1.73 ppB and a mean of 11.76 ppB. Water samples containingmore » high uranium concentrations (>20 ppB) generally are associated with known uranium mining activity or units known to be uranium bearing. About one-third of the water samples containing high uranium concentrations were collected from locations within the Pumpkin Buttes and Turnercrest-Ross Districts. Nearly half of the water samples containing high uranium concentrations were collected from locations just west of the Monument Hill and Highland Flats-Box Creek Districts. Similar anomalous uranium concentrations in this region have been reported updip from Exxon's Highland uranium deposits. High uranium concentrations were also found associated with the Lance Creek-Old Woman Anticline District.« less

Highly Efficient Interception and Precipitation of Uranium(VI) from Aqueous Solution by Iron-Electrocoagulation Combined with Cooperative Chelation by Organic Ligands.

PubMed

Li, Peng; Zhun, Bao; Wang, Xuegang; Liao, PingPing; Wang, Guanghui; Wang, Lizhang; Guo, Yadan; Zhang, Weimin

2017-12-19

A new strategy combining iron-electrocoagulation and organic ligands (OGLs) cooperative chelation was proposed to screen and precipitate low concentrations (0-18.52 μmol/L) of uranium contaminant in aqueous solution. We hypothesized that OGLs with amino, hydroxyl, and carboxyl groups hydrophobically/hydrophilically would realize precuring of uranyl ion at pH < 3.0, and the following iron-electrocoagulation would achieve faster and more efficient uranium precipitation. Experimentally, the strategy demonstrated highly efficient uranium(VI) precipitation efficiency, especially with hydrophilic macromolecular OGLs. The uranium removal efficiency at optimized experimental condition reached 99.65%. The decrease of zeta potential and the lattice enwrapping between U-OGLs chelates and flocculation precursor were ascribed to the enhanced uranium precipitation activity. Uranium was precipitated as oxides of U(VI) or higher valences that were easily captured in aggregated micelles under low operation current potential. The actual uranium tailing wastewater was treated, and a satisfied uranium removal efficiency of 99.02% was discovered. After elution of the precipitated flocs, a concentrated uranium solution (up to 106.52 μmol/L) with very few other metallic impurities was obtained. Therefore, the proposed strategy could remove uranium and concentrate it concurrently. This work could provide new insights into the purification and recovery of uranium from aqueous solutions in a cost-effective and environmentally friendly process.

31 CFR 540.315 - Uranium-235 (U235).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 31 Money and Finance:Treasury 3 2013-07-01 2013-07-01 false Uranium-235 (U235). 540.315 Section... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.315 Uranium-235 (U235). The term uranium-235 or U235 means the fissile...

31 CFR 540.315 - Uranium-235 (U235).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 31 Money and Finance:Treasury 3 2012-07-01 2012-07-01 false Uranium-235 (U235). 540.315 Section... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.315 Uranium-235 (U235). The term uranium-235 or U235 means the fissile...

49 CFR 173.434 - Activity-mass relationships for uranium and natural thorium.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 49 Transportation 2 2014-10-01 2014-10-01 false Activity-mass relationships for uranium and....434 Activity-mass relationships for uranium and natural thorium. The table of activity-mass relationships for uranium and natural thorium are as follows: Thorium and uranium enrichment 1(Wt% 235 U present...

49 CFR 173.434 - Activity-mass relationships for uranium and natural thorium.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 49 Transportation 2 2012-10-01 2012-10-01 false Activity-mass relationships for uranium and....434 Activity-mass relationships for uranium and natural thorium. The table of activity-mass relationships for uranium and natural thorium are as follows: Thorium and uranium enrichment 1(Wt% 235 U present...

49 CFR 173.434 - Activity-mass relationships for uranium and natural thorium.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 49 Transportation 2 2013-10-01 2013-10-01 false Activity-mass relationships for uranium and....434 Activity-mass relationships for uranium and natural thorium. The table of activity-mass relationships for uranium and natural thorium are as follows: Thorium and uranium enrichment 1(Wt% 235 U present...

31 CFR 540.315 - Uranium-235 (U235).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 31 Money and Finance:Treasury 3 2014-07-01 2014-07-01 false Uranium-235 (U235). 540.315 Section... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.315 Uranium-235 (U235). The term uranium-235 or U235 means the fissile...

31 CFR 540.315 - Uranium-235 (U235).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 31 Money and Finance:Treasury 3 2011-07-01 2011-07-01 false Uranium-235 (U235). 540.315 Section... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.315 Uranium-235 (U235). The term uranium-235 or U235 means the fissile...

SEPARATION OF URANIUM, PLUTONIUM AND FISSION PRODUCTS FROM NEUTRON- BOMBARDED URANIUM

DOEpatents

Martin, A.E.; Johnson, I.; Burris, L. Jr.; Winsch, I.O.; Feder, H.M.

1962-11-13

A process is given for removing plutonium and/or fission products from uranium fuel. The fuel is dissolved in molten zinc--magnesium (10 to 18% Mg) alloy, more magnesium is added to obtain eutectic composition whereby uranium precipitates, and the uranium are separated from the Plutoniumand fission-product- containing eutectic. (AEC)

31 CFR 540.315 - Uranium-235 (U235).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 31 Money and Finance: Treasury 3 2010-07-01 2010-07-01 false Uranium-235 (U235). 540.315 Section... FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.315 Uranium-235 (U235). The term uranium-235 or U235 means the fissile...

DISSOLUTION OF ZIRCONIUM-CONTAINING FUEL ELEMENTS

DOEpatents

Horn, F.L.

1961-12-12

Uranium is recovered from spent uranium fuel elements containing or clad with zirconium. These fuel elements are placed in an anhydrous solution of hydrogen fluoride and nitrogen dioxide. Within this system uranium forms a soluble complex and zirconium forms an insoluble complex. The uranium can then be separated, treated, and removed from solution as uranium hexafluoride. (AEC)

The role of uranium-arene bonding in H2O reduction catalysis

NASA Astrophysics Data System (ADS)

Halter, Dominik P.; Heinemann, Frank W.; Maron, Laurent; Meyer, Karsten

2018-03-01

The reactivity of uranium compounds towards small molecules typically occurs through stoichiometric rather than catalytic processes. Examples of uranium catalysts reacting with water are particularly scarce, because stable uranyl groups form that preclude the recovery of the uranium compound. Recently, however, an arene-anchored, electron-rich uranium complex has been shown to facilitate the electrocatalytic formation of H2 from H2O. Here, we present the precise role of uranium-arene δ bonding in intermediates of the catalytic cycle, as well as details of the atypical two-electron oxidative addition of H2O to the trivalent uranium catalyst. Both aspects were explored by synthesizing mid- and high-valent uranium-oxo intermediates and by performing comparative studies with a structurally related complex that cannot engage in δ bonding. The redox activity of the arene anchor and a covalent δ-bonding interaction with the uranium ion during H2 formation were supported by density functional theory analysis. Detailed insight into this catalytic system may inspire the design of ligands for new uranium catalysts.

Ramie (Boehmeria nivea)'s uranium bioconcentration and tolerance attributes.

PubMed

Wang, Wei-Hong; Luo, Xue-Gang; Liu, Lai; Zhang, Yan; Zhao, Hao-Zhou

2018-04-01

The authors sampled and analyzed 15 species of dominant wild plants in Huanan uranium tailings pond in China, whose tailings' uranium contents were 3.21-120.52 μg/g. Among the 15 species of wild plants, ramie (Boehmeria nivea) had the strongest uranium bioconcentration and transfer capacities. In order to study the uranium bioconcentration and tolerance attributes of ramie in detail, and provide a reference for the screening remediation plants to phytoremedy on a large scale in uranium tailings pond, a ramie cultivar Xiangzhu No. 7 pot experiment was carried out. We found that both wild ramie and Xiangzhu No. 7 could bioconcentrate uranium, but there were two differences. One was wild ramie's shoots bioconcentrated uranium up to 20 μg/g (which can be regarded as the critical content value of the shoot of uranium hyperaccumulator) even the soil uranium content was as low as 5.874 μg/g while Xiangzhu No. 7's shoots could reach 20 μg/g only when the uranium treatment concentrations were 275 μg/g or more; the other was that all the transfer factors of 3 wild samples were >1, and the transfer factors of 27 out of 28 pot experiment samples were <1. Probably wild ramie was a uranium hyperaccumulator. Xiangzhu No. 7 satisfied the needs of uranium hyperaccumulator on accumulation capability, tolerance capability, bioconcentration factor, but not transfer capability, so Xiangzhu No. 7 was not a uranium hyperaccumulator. We analyzed the possible reasons why there were differences in the uranium bioconcentration and transfer attributes between wild ramie and Xiangzhu No. 7., and proposed the direction for further research. In our opinion, both the plants which bioconcentrate contaminants in the shoots and roots can act as phytoextractors. Although Xiangzhu No. 7's biomass and accumulation of uranium were concentrated on the roots, the roots were small in volume and easy to harvest. And Xiangzhu No. 7's cultivating skills and protection measures had been developed very well. Xiangzhu No. 7's whole bioconcentration factors and the roots' bioconcentration factors, which were 1.200-1.834 and 1.460-2.341, respectively, increased with the increases of uranium contents of pot soil when the soil's uranium contents are 25-175 μg/g, so it can act as a potential phytoextractor when Huanan uranium tailings pond is phytoremediated. Copyright © 2018. Published by Elsevier Ltd.

Uranium contents in plants and mushrooms grown on a uranium-contaminated site near Ronneburg in Eastern Thuringia/Germany.

PubMed

Baumann, Nils; Arnold, Thuro; Haferburg, Götz

2014-01-01

Uranium concentrations in cultivated (sunflower, sunchoke, potato) and native plants, plant compartment specimens, and mushrooms, grown on a test site within a uranium-contaminated area in Eastern Thuringia, were analyzed and compared. This test site belongs to the Friedrich-Schiller University Jena and is situated on the ground of a former but now removed uranium mine waste leaching heap. For determination of the U concentrations in the biomaterials, the saps of the samples were squeezed out by using an ultracentrifuge, after that, the uranium concentrations in the saps and the remaining residue were measured, using ICP-MS. The study further showed that uranium concentrations observed in plant compartment and mushroom fruiting bodies sap samples were always higher than their associated solid residue sample. Also, it was found that the detected uranium concentration in the root samples were always higher than were observed in their associated above ground biomass, e.g., in shoots, leaves, blossoms etc. The highest uranium concentration was measured with almost 40 ppb U in a fruiting body of a mushroom and in roots of butterbur. However, the detected uranium concentrations in plants and mushrooms collected in this study were always lower than in the associated surface and soil water of the test site, indicating that under the encountered natural conditions, none of the studied plant and mushroom species turned out to be a hyperaccumulator for uranium, which could have extracted uranium in sufficient amounts out of the uranium-contaminated soil. In addition, it was found that the detected uranium concentrations in the sap samples, despite being above the sensitivity limit, proved to be too low-in combination with the presence of fluorescence quenching substances, e.g., iron and manganese ions, and/or organic quenchers-to extract a useful fluorescence signal, which could have helped to identify the uranium speciation in plants.

Uranium-Loaded Water Treatment Resins: 'Equivalent Feed' at NRC and Agreement State-Licensed Uranium Recovery Facilities - 12094

DOE Office of Scientific and Technical Information (OSTI.GOV)

Camper, Larry W.; Michalak, Paul; Cohen, Stephen

Community Water Systems (CWSs) are required to remove uranium from drinking water to meet EPA standards. Similarly, mining operations are required to remove uranium from their dewatering discharges to meet permitted surface water discharge limits. Ion exchange (IX) is the primary treatment strategy used by these operations, which loads uranium onto resin beads. Presently, uranium-loaded resin from CWSs and mining operations can be disposed as a waste product or processed by NRC- or Agreement State-licensed uranium recovery facilities if that licensed facility has applied for and received permission to process 'alternate feed'. The disposal of uranium-loaded resin is costly andmore » the cost to amend a uranium recovery license to accept alternate feed can be a strong disincentive to commercial uranium recovery facilities. In response to this issue, the NRC issued a Regulatory Issue Summary (RIS) to clarify the agency's policy that uranium-loaded resin from CWSs and mining operations can be processed by NRC- or Agreement State-licensed uranium recovery facilities without the need for an alternate feed license amendment when these resins are essentially the same, chemically and physically, to resins that licensed uranium recovery facilities currently use (i.e., equivalent feed). NRC staff is clarifying its current alternate feed policy to declare IX resins as equivalent feed. This clarification is necessary to alleviate a regulatory and financial burden on facilities that filter uranium using IX resin, such as CWSs and mine dewatering operations. Disposing of those resins in a licensed facility could be 40 to 50 percent of the total operations and maintenance (O and M) cost for a CWS. Allowing uranium recovery facilities to treat these resins without requiring a license amendment lowers O and M costs and captures a valuable natural resource. (authors)« less

As-cast uranium-molybdenum based metallic fuel candidates and the effects of carbon addition

NASA Astrophysics Data System (ADS)

Blackwood, Van Stephen

The objective of this research was to develop and recommend a metallic nuclear fuel candidate that lowered the onset temperature of gamma phase formation comparable or better than the uranium-10 wt. pct. molybdenum alloy, offered a solidus temperature as high or higher than uranium-10 wt. pct. zirconium (1250°C), and stabilized the fuel phase against interaction with iron and steel at least as much as uranium-10 wt. pct. zirconium stabilized the fuel phase. Two new as-cast alloy compositions were characterized to assess thermal equilibrium boundaries of the gamma phase field and the effect of carbon addition up to 0.22 wt. pct. The first system investigated was uranium- x wt. pct. M where x ranged between 5-20 wt. pct. M was held at a constant ratio of 50 wt. pct. molybdenum, 43 wt. pct. titanium, and 7 wt. pct. zirconium. The second system investigated was the uranium-molybdenum-tungsten system in the range 90 wt. pct. uranium - 10 wt. pct. molybdenum - 0 wt. pct. tungsten to 80 wt. pct. uranium - 10 wt. pct. molybdenum - 10 wt. pct. tungsten. The results showed that the solidus temperature increased with increased addition of M up to 12.5 wt. pct. for the uranium-M system. Alloy additions of titanium and zirconium were removed from uranium-molybdenum solid solution by carbide formation and segregation. The uranium-molybdenum-tungsten system solidus temperature increased to 1218°C at 2.5 wt. pct. with no significant change in temperature up to 5 wt. pct. tungsten suggesting the solubility limit of tungsten had been reached. Carbides were observed with surrounding areas enriched in both molybdenum and tungsten. The peak solidus temperatures for the alloy systems were roughly the same at 1226°C for the uranium-M system and 1218°C for the uranium-molybdenum-tungsten system. The uranium-molybdenum-tungsten system required less alloy addition to achieve similar solidus temperatures as the uranium-M system.

Low Temperature Fluorine Chemistry of Electronegative Elements.

DTIC Science & Technology

1980-07-15

mixtures were prepared in a stainless steel vacuum line well-passivated with chlorine trifluoride (Matheson 98%). In most cases gas mixtures were prepared...niversit% of Tennessee." Knoxville, Tennessee 37916 Matrix Reactions of Fluorine with Chlorine , Bromine, and Iodine. Infrared Detlection of the XF 2, X2F...stainless sieel vacuum line well-passivated with chlorine trifluoride in the formation of these new mixed halogen species. (Matheson. 98.0%). Research

Synthesis of Dual NIR Two-photon Absorptive [60]fullerenyl Multiadducts for Nonlinear Light-transmittance Reduction Application

DTIC Science & Technology

2014-11-01

INTRODUCTION Nonlinear optical characteristics of [60] fullerene -derived C60-(antenna)x nanostructure conjugates are based on excited singlet state...two-photon absorption (2PA) processes in the NIR region [3]. Fullerene cages exhibit high electronegativity and electron-accepting characteristics...photoenergy by the donor DPAF-Cn antenna was able to undergo efficient intramolecular electron- or energy-transfer to the fullerene acceptor moiety in

URANIUM IN ROCK MINERALS OF THE INTRUSION OF KYZL-OMPUL MOUNTAINS (NORTH KIRGISIA) (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leonova, L.L.; Pogiblova, L.S.

1961-01-01

The uranium distribution in rock minerals (syenites, granosyenites, and alaskite granites) of the Kyzyl-Ompul raassif is studied. Alaskite granites are characterized by the granite type of uranium distribution in minerals, about 50 percent of this element being connected with rockforming and about 50 percent with accessory uranium minerals. ln syenites uranium (about 70 percent) is bound to rockforming minerals. The same minerals from syenites and granites strongly differ by their uranium content and are constant in the ranges of each of those rock types. Granosyenites have aa intermediate (between syenites and granites) type of uranium distribution in minerals. (auth)

Removal of uranium from soil samples for ICP-OES analysis of RCRA metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wero, M.; Lederer-Cano, A.; Billy, C.

1995-12-01

Soil samples containing high levels of uranium present unique analytical problems when analyzed for toxic metals (Ag, As, Ba, Cd, Cr, Cu, Ni, Pb, Se and Tl) because of the spectral interference of uranium in the ICP-OES emission spectrometer. Methods to remove uranium from the digestates of soil samples, known to be high in uranium, have been developed that reduce the initial uranium concentration (1-3%) to less than 500 ppm. UTEVA ion exchange columns, used as an ICP-OES analytical pre-treatment, reduces uranium to acceptable levels, permitting good analytical results of the RCRA metals by ICP-OES.

The polar 2e/12c bond in phenalenyl-azaphenalenyl hetero-dimers: Stronger stacking interaction and fascinating interlayer charge transfer.

PubMed

Zhong, Rong-Lin; Xu, Hong-Liang; Li, Zhi-Ru

2016-08-07

An increasing number of chemists have focused on the two-electron/multicenter bond (2e/mc) that was first introduced to interpret the bonding mechanism of radical dimers. Herein, we report the polar two-electron/twelve center (2e/12c) bonding character in a series of phenalenyl-azaphenalenyl radical hetero-dimers. Interestingly, the bonding energy of weaker polar hetero-dimer (P-TAP) is dominated by the overlap of the two different singly occupied molecular orbital of radicals, while that of stronger polar hetero-dimer (P-HAP) is dominated by the electrostatic attraction. Results show that the difference between the electronegativity of the monomers plays a prominent role in the essential attribution of the polar 2e/12c bond. Correspondingly, a stronger stacking interaction in the hetero-dimer could be effectively achieved by increasing the difference of nitrogen atoms number between the monomers. It is worthy of note that an interesting interlayer charge transfer character is induced in the polar hetero-dimers, which is dependent on the difference between the electronegativity of the monomers. It is our expectation that the new knowledge about the bonding nature of radical hetero-dimers might provide important information for designing radical based functional materials with various applications.

Impurity effects on the grain boundary cohesion in copper

NASA Astrophysics Data System (ADS)

Li, Yunguo; Korzhavyi, Pavel A.; Sandström, Rolf; Lilja, Christina

2017-12-01

Segregated impurities at grain boundaries can dramatically change the mechanical behavior of metals, while the mechanism is still obscure in some cases. Here, we suggest a unified approach to investigate segregation and its effects on the mechanical properties of polycrystalline alloys using the example of 3 s p impurities (Mg, Al, Si, P, or S) at a special type Σ 5 (310 )[001 ] tilt grain boundary in Cu. We show that for these impurities segregating to the grain boundary, the strain contribution to the work of grain boundary decohesion is small and that the chemical contribution correlates with the electronegativity difference between Cu and the impurity. The strain contribution to the work of dislocation emission is calculated to be negative, while the chemical contribution is calculated to be always positive. Both the strain and chemical contributions to the work of dislocation emission generally become weaker with the increasing electronegativity from Mg to S. By combining these contributions together, we find, in agreement with experimental observations, that a strong segregation of S can reduce the work of grain boundary separation below the work of dislocation emission, thus embrittling Cu, while such an embrittlement cannot be produced by a P segregation because it lowers the energy barrier for dislocation emission relatively more than for work separation.

Proteomic analysis of electronegative low-density lipoprotein[S

PubMed Central

Bancells, Cristina; Canals, Francesc; Benítez, Sònia; Colomé, Nuria; Julve, Josep; Ordóñez-Llanos, Jordi; Sánchez-Quesada, José Luis

2010-01-01

Low density lipoprotein is a heterogeneous group of lipoproteins that differs in lipid and protein composition. One copy of apolipoprotein (apo)B accounts for over 95% of the LDL protein, but the presence of minor proteins could disturb its biological behavior. Our aim was to study the content of minor proteins in LDL subfractions separated by anion exchange chromatography. Electropositive LDL [LDL(+)] is the native form, whereas electronegative LDL [LDL(−)] is a minor atherogenic fraction present in blood. LC-ESI MS/MS analysis of both LDL fractions identified up to 28 different proteins. Of these, 13 proteins, including apoB, were detected in all the analyzed samples. LDL(−) showed a higher content of most minor proteins. Statistical analysis of proteomic data indicated that the content of apoE, apoA-I, apoC-III, apoA-II, apoD, apoF, and apoJ was higher in LDL(−) than in LDL(+). Immunoturbidimetry, ELISA, or Western blot analysis confirmed these differences. ApoJ and apoF presented the highest difference between LDL(+) and LDL(−) (>15-fold). In summary, the increased content of several apolipoproteins, and specifically of apoF and apoJ, could be related to the physicochemical characteristics of LDL(−), such as apoB misfolding, aggregation, and abnormal lipid composition. PMID:20699421

The polar 2e/12c bond in phenalenyl-azaphenalenyl hetero-dimers: Stronger stacking interaction and fascinating interlayer charge transfer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhong, Rong-Lin; Li, Zhi-Ru, E-mail: hlxu@nenu.edu.cn, E-mail: lzr@jlu.edu.cn; Xu, Hong-Liang, E-mail: hlxu@nenu.edu.cn, E-mail: lzr@jlu.edu.cn

An increasing number of chemists have focused on the two-electron/multicenter bond (2e/mc) that was first introduced to interpret the bonding mechanism of radical dimers. Herein, we report the polar two-electron/twelve center (2e/12c) bonding character in a series of phenalenyl-azaphenalenyl radical hetero-dimers. Interestingly, the bonding energy of weaker polar hetero-dimer (P-TAP) is dominated by the overlap of the two different singly occupied molecular orbital of radicals, while that of stronger polar hetero-dimer (P-HAP) is dominated by the electrostatic attraction. Results show that the difference between the electronegativity of the monomers plays a prominent role in the essential attribution of the polarmore » 2e/12c bond. Correspondingly, a stronger stacking interaction in the hetero-dimer could be effectively achieved by increasing the difference of nitrogen atoms number between the monomers. It is worthy of note that an interesting interlayer charge transfer character is induced in the polar hetero-dimers, which is dependent on the difference between the electronegativity of the monomers. It is our expectation that the new knowledge about the bonding nature of radical hetero-dimers might provide important information for designing radical based functional materials with various applications.« less

Assessment of isolated electronic effects on conformation. NMR analysis of nicotine and related compounds and ab initio studies of model compounds

NASA Astrophysics Data System (ADS)

Cox, Richard H.; Kao, James; Secor, Henry V.; Seeman, Jeffrey I.

1986-01-01

The influence of electronegative substituents on the N'-methyl group of nicotine upon the conformation of the pyrrolidine ring has been evaluated by the exact analysis of the high field 1H NMR spectra of nicotine ( 1), N'-ethylnornicotine ( 2), N'-(2,2-difluoroethyl)-nornicotine ( 3) and N'-(2,2,2-trifluoroethyl) nornicotine ( 4). The vicinal coupling constants for the pyrrolidine ring of 1-4 remain nearly constant, suggesting that as the electronegativity of the N'-methyl substituent increases, only very small changes are seen for the C 3'—C 4'—C 5'—N' and the C 2'—C 3'—C 4'—C 5' dihedral angles. Substitution on the N'-methyl group appears to have little effect on the orientation of the pyridyl ring with respect to the pyrrolidine ring. Ab initio calculations have been performed on the analogous 2-substituted diethylamines (diethylamine, N-ethyl-2-fluoroethylamine, N-ethyl-2,2-difluoroamine, and N-ehtyl-2,2,2-trifluoroethylamine) which constitute substructure models of 1-4. These calculations confirm the NMR results in that they both indicate little, if any, effects on the rotational barriers and conformational energy profiles as a function of number of fluorine atoms.

Estimation of Enthalpy of Formation of Liquid Transition Metal Alloys: A Modified Prescription Based on Macroscopic Atom Model of Cohesion

NASA Astrophysics Data System (ADS)

Raju, Subramanian; Saibaba, Saroja

2016-09-01

The enthalpy of formation Δo H f is an important thermodynamic quantity, which sheds significant light on fundamental cohesive and structural characteristics of an alloy. However, being a difficult one to determine accurately through experiments, simple estimation procedures are often desirable. In the present study, a modified prescription for estimating Δo H f L of liquid transition metal alloys is outlined, based on the Macroscopic Atom Model of cohesion. This prescription relies on self-consistent estimation of liquid-specific model parameters, namely electronegativity ( ϕ L) and bonding electron density ( n b L ). Such unique identification is made through the use of well-established relationships connecting surface tension, compressibility, and molar volume of a metallic liquid with bonding charge density. The electronegativity is obtained through a consistent linear scaling procedure. The preliminary set of values for ϕ L and n b L , together with other auxiliary model parameters, is subsequently optimized to obtain a good numerical agreement between calculated and experimental values of Δo H f L for sixty liquid transition metal alloys. It is found that, with few exceptions, the use of liquid-specific model parameters in Macroscopic Atom Model yields a physically consistent methodology for reliable estimation of mixing enthalpies of liquid alloys.

Structural and optical properties of (Ag,Cu)(In,Ga)Se{sub 2} polycrystalline thin film alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boyle, J. H.; Shafarman, W. N.; Birkmire, R. W.

2014-06-14

The structural and optical properties of pentenary alloy (Ag,Cu)(In,Ga)Se{sub 2} polycrystalline thin films were characterized over the entire compositional range at a fixed (Cu + Ag)/(In + Ga) ratio. Films deposited at 550 °C on bare and molybdenum coated soda-lime glass by elemental co-evaporation in a single-stage process with constant incident fluxes exhibit single phase chalcopyrite structure, corresponding to 122 spacegroup (I-42d) over the entire compositional space. Unit cell refinement of the diffraction patterns show that increasing Ag substitution for Cu, the refined a{sub o} lattice constant, (Ag,Cu)-Se bond length, and anion displacement increase in accordance with the theoretical model proposed by Jaffe, Wei, andmore » Zunger. However, the refined c{sub o} lattice constant and (In,Ga)-Se bond length deviated from theoretical expectations for films with mid-range Ag and Ga compositions and are attributed to influences from crystallographic bond chain ordering or cation electronegativity. The optical band gap, derived from transmission and reflection measurements, widened with increasing Ag and Ga content, due to influences from anion displacement and cation electronegativity, as expected from theoretical considerations for pseudo-binary chalcopyrite compounds.« less

Prediction of blood-brain partitioning: a model based on molecular electronegativity distance vector descriptors.

PubMed

Zhang, Yong-Hong; Xia, Zhi-Ning; Qin, Li-Tang; Liu, Shu-Shen

2010-09-01

The objective of this paper is to build a reliable model based on the molecular electronegativity distance vector (MEDV) descriptors for predicting the blood-brain barrier (BBB) permeability and to reveal the effects of the molecular structural segments on the BBB permeability. Using 70 structurally diverse compounds, the partial least squares regression (PLSR) models between the BBB permeability and the MEDV descriptors were developed and validated by the variable selection and modeling based on prediction (VSMP) technique. The estimation ability, stability, and predictive power of a model are evaluated by the estimated correlation coefficient (r), leave-one-out (LOO) cross-validation correlation coefficient (q), and predictive correlation coefficient (R(p)). It has been found that PLSR model has good quality, r=0.9202, q=0.7956, and R(p)=0.6649 for M1 model based on the training set of 57 samples. To search the most important structural factors affecting the BBB permeability of compounds, we performed the values of the variable importance in projection (VIP) analysis for MEDV descriptors. It was found that some structural fragments in compounds, such as -CH(3), -CH(2)-, =CH-, =C, triple bond C-, -CH<, =C<, =N-, -NH-, =O, and -OH, are the most important factors affecting the BBB permeability. (c) 2010. Published by Elsevier Inc.

Pauling Electronegativity On/Off Effects Assessed by 13 C and 29 Si NMR Spectroscopic Analysis.

PubMed

Benedetti, Michele; De Castro, Federica; Fanizzi, Francesco P

2017-11-27

In carbon and silicon tetrahalide compounds, the experimental 13 C and 29 Si NMR chemical-shift values are known to increase or decrease on increasing the overall sum of the ionic radii of the bonded halides Σ(r h ) (normal and inverse halogen dependence (NHD and IHD, respectively)). Herein, we extrapolate the main factors responsible for such NMR chemical shifts. Intriguingly, we found a characteristic value for the overall sum of the Pauling electronegativities of the bonded halides Σ(χ h ), which works as a triggering factor to determine the transition from the NHD to IHD. Below this Σ(χ h ) value, the chemical shift of the central atom was strictly related to only the Σ(r h ) value, thus producing a NHD trend. Conversely, above this value, the chemical shift of the central atom was dependent on both the Σ(r h ) and Σ(χ h ) values, thus producing a IHD trend. A simple model, in which the effect of the Σ(χ h ) value on 13 C and 29 Si NMR chemical shifts is related to an apparent increase in the Σ(r h ) value, is deduced. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Importance of electronegativity differences and surface structure in molecular dissociation reactions at transition metal surfaces.

PubMed

Crawford, Paul; Hu, P

2006-12-14

The dissociative adsorption of N2 has been studied at both monatomic steps and flat regions on the surfaces of the 4d transition metals from Zr to Pd. Using density functional theory (DFT) calculations, we have determined and analyzed the trends in both straight reactivity and structure sensitivity across the periodic table. With regards to reactivity, we find that the trend in activation energy (Ea) is determined mainly by a charge transfer from the surface metal atoms to the N atoms during transition state formation, namely, the degree of ionicity of the N-surface bond at the transition state. Indeed, we find that the strength of the metal-N bond at the transition state (and therefore the trend in Ea) can be predicted by the difference in Mulliken electronegativity between the metal and N. Structure sensitivity is analyzed in terms of geometric and electronic effects. We find that the lowering of Ea due to steps is more pronounced on the right-hand side of the periodic table. It is found that for the early transition metals the geometric and electronic effects work in opposition when going from terrace to step active site. In the case of the late 4d metals, however, these effects work in combination, producing a more marked reduction in Ea.

Study of lithium cation in water clusters: based on atom-bond electronegativity equalization method fused into molecular mechanics.

PubMed

Li, Xin; Yang, Zhong-Zhi

2005-05-12

We present a potential model for Li(+)-water clusters based on a combination of the atom-bond electronegativity equalization and molecular mechanics (ABEEM/MM) that is to take ABEEM charges of the cation and all atoms, bonds, and lone pairs of water molecules into the intermolecular electrostatic interaction term in molecular mechanics. The model allows point charges on cationic site and seven sites of an ABEEM-7P water molecule to fluctuate responding to the cluster geometry. The water molecules in the first sphere of Li(+) are strongly structured and there is obvious charge transfer between the cation and the water molecules; therefore, the charge constraint on the ionic cluster includes the charged constraint on the Li(+) and the first-shell water molecules and the charge neutrality constraint on each water molecule in the external hydration shells. The newly constructed potential model based on ABEEM/MM is first applied to ionic clusters and reproduces gas-phase state properties of Li(+)(H(2)O)(n) (n = 1-6 and 8) including optimized geometries, ABEEM charges, binding energies, frequencies, and so on, which are in fair agreement with those measured by available experiments and calculated by ab initio methods. Prospects and benefits introduced by this potential model are pointed out.

Electronegativity Equalization Method: Parameterization and Validation for Large Sets of Organic, Organohalogene and Organometal Molecule

PubMed Central

Vařeková, Radka Svobodová; Jiroušková, Zuzana; Vaněk, Jakub; Suchomel, Šimon; Koča, Jaroslav

2007-01-01

The Electronegativity Equalization Method (EEM) is a fast approach for charge calculation. A challenging part of the EEM is the parameterization, which is performed using ab initio charges obtained for a set of molecules. The goal of our work was to perform the EEM parameterization for selected sets of organic, organohalogen and organometal molecules. We have performed the most robust parameterization published so far. The EEM parameterization was based on 12 training sets selected from a database of predicted 3D structures (NCI DIS) and from a database of crystallographic structures (CSD). Each set contained from 2000 to 6000 molecules. We have shown that the number of molecules in the training set is very important for quality of the parameters. We have improved EEM parameters (STO-3G MPA charges) for elements that were already parameterized, specifically: C, O, N, H, S, F and Cl. The new parameters provide more accurate charges than those published previously. We have also developed new parameters for elements that were not parameterized yet, specifically for Br, I, Fe and Zn. We have also performed crossover validation of all obtained parameters using all training sets that included relevant elements and confirmed that calculated parameters provide accurate charges.

Molecular electronegativity distance vector model for the prediction of bioconcentration factors in fish.

PubMed

Liu, Shu-Shen; Qin, Li-Tang; Liu, Hai-Ling; Yin, Da-Qiang

2008-02-01

Molecular electronegativity distance vector (MEDV) derived directly from the molecular topological structures was used to describe the structures of 122 nonionic organic compounds (NOCs) and a quantitative relationship between the MEDV descriptors and the bioconcentration factors (BCF) of NOCs in fish was developed using the variable selection and modeling based on prediction (VSMP). It was found that some main structural factors influencing the BCFs of NOCs are the substructures expressed by four atomic types of nos. 2, 3, 5, and 13, i.e., atom groups -CH(2)- or =CH-, -CH< or =C<, -NH(2), and -Cl or -Br where the former two groups exist in the molecular skeleton of NOC and the latter three groups are related closely to the substituting groups on a benzene ring. The best 5-variable model, with the correlation coefficient (r(2)) of 0.9500 and the leave-one-out cross-validation correlation coefficient (q(2)) of 0.9428, was built by multiple linear regressions, which shows a good estimation ability and stability. A predictive power for the external samples was tested by the model from the training set of 80 NOCs and the predictive correlation coefficient (u(2)) for the 42 external samples in the test set was 0.9028.

Universal method to calculate the stability, electronegativity, and hardness of dianions.

PubMed

von Szentpály, László

2010-10-14

The electronic stability of gas-phase dianions of arbitrary size, X(2-), is determined by the first universal method to calculate second electron affinities, A(2). The model expresses A(2,calc) = A(1) - (7/6)η(0) by the first electron affinity, A(1), and chemical hardness, η(0), of the neutral "grandparent" species. A comparison with 37 reference data of atoms, molecules, superatoms, and clusters yields A(2,ref) = 1.004A(2,calc) - 0.023 eV, with a mean unsigned deviation of MUD = 0.095 eV and a correlation coefficient of R = 0.9987. Predictions of second electron affinities are given for a further 24 species. The universality of the model is apparent from the broad variety of compounds formed by 30 diverse elements. The electronegativity and hardness of dianions are determined for the first time as χ(X(2-)) = A(2) and η(X(2-)) = (7/12)η(0), respectively. Pearson and Parr's operational assumption regarding the hardness of anionic bases for the hard-soft acid-base (HSAB) principle is rationalized, and predictions for hard and soft dianionic bases are presented. For trianions, first criteria and predictions for electronic stability are given and require A(1) > (7/4)η(0).

Toward an Experimental Quantum Chemistry: Exploring a New Energy Partitioning.

PubMed

Rahm, Martin; Hoffmann, Roald

2015-08-19

Following the work of L. C. Allen, this work begins by relating the central chemical concept of electronegativity with the average binding energy of electrons in a system. The average electron binding energy, χ̅, is in principle accessible from experiment, through photoelectron and X-ray spectroscopy. It can also be estimated theoretically. χ̅ has a rigorous and understandable connection to the total energy. That connection defines a new kind of energy decomposition scheme. The changing total energy in a reaction has three primary contributions to it: the average electron binding energy, the nuclear-nuclear repulsion, and multielectron interactions. This partitioning allows one to gain insight into the predominant factors behind a particular energetic preference. We can conclude whether an energy change in a transformation is favored or resisted by collective changes to the binding energy of electrons, the movement of nuclei, or multielectron interactions. For example, in the classical formation of H2 from atoms, orbital interactions dominate nearly canceling nuclear-nuclear repulsion and two-electron interactions. While in electron attachment to an H atom, the multielectron interactions drive the reaction. Looking at the balance of average electron binding energy, multielectron, and nuclear-nuclear contributions one can judge when more traditional electronegativity arguments can be justifiably invoked in the rationalization of a particular chemical event.

Using machine learning to identify factors that govern amorphization of irradiated pyrochlores

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pilania, Ghanshyam; Whittle, Karl R.; Jiang, Chao

Structure–property relationships are a key materials science concept that enables the design of new materials. In the case of materials for application in radiation environments, correlating radiation tolerance with fundamental structural features of a material enables materials discovery. Here, we use a machine learning model to examine the factors that govern amorphization resistance in the complex oxide pyrochlore (A 2B 2O 7) in a regime in which amorphization occurs as a consequence of defect accumulation. We examine the fidelity of predictions based on cation radii and electronegativities, the oxygen positional parameter, and the energetics of disordering and amorphizing the material.more » No one factor alone adequately predicts amorphization resistance. We find that when multiple families of pyrochlores (with different B cations) are considered, radii and electronegativities provide the best prediction, but when the machine learning model is restricted to only the B = Ti pyrochlores, the energetics of disordering and amorphization are critical factors. We discuss how these static quantities provide insight into an inherently kinetic property such as amorphization resistance at finite temperature. Lastly, this work provides new insight into the factors that govern the amorphization susceptibility and highlights the ability of machine learning approaches to generate that insight.« less

Using machine learning to identify factors that govern amorphization of irradiated pyrochlores

DOE PAGES

Pilania, Ghanshyam; Whittle, Karl R.; Jiang, Chao; ...

2017-02-10

Structure–property relationships are a key materials science concept that enables the design of new materials. In the case of materials for application in radiation environments, correlating radiation tolerance with fundamental structural features of a material enables materials discovery. Here, we use a machine learning model to examine the factors that govern amorphization resistance in the complex oxide pyrochlore (A 2B 2O 7) in a regime in which amorphization occurs as a consequence of defect accumulation. We examine the fidelity of predictions based on cation radii and electronegativities, the oxygen positional parameter, and the energetics of disordering and amorphizing the material.more » No one factor alone adequately predicts amorphization resistance. We find that when multiple families of pyrochlores (with different B cations) are considered, radii and electronegativities provide the best prediction, but when the machine learning model is restricted to only the B = Ti pyrochlores, the energetics of disordering and amorphization are critical factors. We discuss how these static quantities provide insight into an inherently kinetic property such as amorphization resistance at finite temperature. Lastly, this work provides new insight into the factors that govern the amorphization susceptibility and highlights the ability of machine learning approaches to generate that insight.« less

Anion dependent self-assembly of 56-metal Cd-Ln nanoclusters with enhanced near-infrared luminescence properties

NASA Astrophysics Data System (ADS)

Yang, Xiaoping; Schipper, Desmond; Zhang, Lijie; Yang, Keqin; Huang, Shaoming; Jiang, Jijun; Su, Chengyong; Jones, Richard A.

2014-08-01

Two series of Cd-Ln clusters: nano-drum [Ln8Cd24L12(OAc)48] and nano-double-drum [Ln12Cd44L20Cl30(OAc)54] (Ln = Nd and Yb) were prepared using a flexible Schiff base ligand bearing two aryl-Br groups. Chloride (Cl-) ions, together with the interactions of Br with other electronegative atoms, play a key role in the formation of the nano-double-drums. The structures were studied by TEM and photophysical properties were determined.Two series of Cd-Ln clusters: nano-drum [Ln8Cd24L12(OAc)48] and nano-double-drum [Ln12Cd44L20Cl30(OAc)54] (Ln = Nd and Yb) were prepared using a flexible Schiff base ligand bearing two aryl-Br groups. Chloride (Cl-) ions, together with the interactions of Br with other electronegative atoms, play a key role in the formation of the nano-double-drums. The structures were studied by TEM and photophysical properties were determined. Electronic supplementary information (ESI) available: Full experimental and characterization details for 1-4. CCDC 972369-972372. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4nr03075c

PRODUCTION OF URANIUM

DOEpatents

Spedding, F.H.; Wilhelm, H.A.; Keller, W.H.

1958-04-15

The production of uranium metal by the reduction of uranium tetrafluoride is described. Massive uranium metal of high purily is produced by reacting uranium tetrafluoride with 2 to 20% stoichiometric excess of magnesium at a temperature sufficient to promote the reaction and then mantaining the reaction mass in a sealed vessel at temperature in the range of 1150 to 2000 d C, under a superatomospheric pressure of magnesium for a period of time sufficient 10 allow separation of liquid uranium and liquid magnesium fluoride into separate layers.

Depleted Uranium Program: Repository and Chemical Analysis of Biological Samples

DTIC Science & Technology

2010-11-01

Chemical Samples • Chemical Pathology and Analytical Assessment of U and DU in: • Tissues • Urine • Whole blood • Semen • Embedded fragments...preparation for determination of total uranium and isotopic uranium ratios  Semen – Total Uranium – dry ashed by concentrated nitric acid in muffle...Total uranium and DU measurements in blood 0.0 50.0 100.0 150.0 200.0 250.0 ng U in s am pl e Sample Number Semen Measured U Theortical U Uranium

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

DOEpatents

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.

Method for fabricating uranium foils and uranium alloy foils

DOEpatents

Hofman, Gerard L [Downers Grove, IL; Meyer, Mitchell K [Idaho Falls, ID; Knighton, Gaven C [Moore, ID; Clark, Curtis R [Idaho Falls, ID

2006-09-05

A method of producing thin foils of uranium or an alloy. The uranium or alloy is cast as a plate or sheet having a thickness less than about 5 mm and thereafter cold rolled in one or more passes at substantially ambient temperatures until the uranium or alloy thereof is in the shape of a foil having a thickness less than about 1.0 mm. The uranium alloy includes one or more of Zr, Nb, Mo, Cr, Fe, Si, Ni, Cu or Al.

RECOVERY OF URANIUM FROM ZIRCONIUM-URANIUM NUCLEAR FUELS

DOEpatents

Gens, T.A.

1962-07-10

An improvement was made in a process of recovering uranium from a uranium-zirconium composition which was hydrochlorinated with gsseous hydrogen chloride at a temperature of from 350 to 800 deg C resulting in volatilization of the zirconium, as zirconium tetrachloride, and the formation of a uranium containing nitric acid insoluble residue. The improvement consists of reacting the nitric acid insoluble hydrochlorination residue with gaseous carbon tetrachloride at a temperature in the range 550 to 600 deg C, and thereafter recovering the resulting uranium chloride vapors. (AEC)

Rhizofiltration using sunflower (Helianthus annuus L.) and bean (Phaseolus vulgaris L. var. vulgaris) to remediate uranium contaminated groundwater.

PubMed

Lee, Minhee; Yang, Minjune

2010-01-15

The uranium removal efficiencies of rhizofiltration in the remediation of groundwater were investigated in lab-scale experiments. Sunflower (Helianthus annuus L.) and bean (Phaseolus vulgaris L. var. vulgaris) were cultivated and an artificially uranium contaminated solution and three genuine groundwater samples were used in the experiments. More than 80% of the initial uranium in solution and genuine groundwater, respectively, was removed within 24h by using sunflower and the residual uranium concentration of the treated water was lower than 30 microg/L (USEPA drinking water limit). For bean, the uranium removal efficiency of the rhizofiltration was roughly 60-80%. The maximum uranium removal via rhizofiltration for the two plant cultivars occurred at pH 3-5 of solution and their uranium removal efficiencies exceeded 90%. The lab-scale continuous rhizofiltration clean-up system delivered over 99% uranium removal efficiency, and the results of SEM and EDS analyses indicated that most uranium accumulated in the roots of plants. The present results suggested that the uranium removal capacity of two plants evaluated in the clean-up system was about 25mg/kg of wet plant mass. Notably, the removal capacity of the root parts only was more than 500 mg/kg.

Organic geochemical analysis of sedimentary organic matter associated with uranium

USGS Publications Warehouse

Leventhal, J.S.; Daws, T.A.; Frye, J.S.

1986-01-01

Samples of sedimentary organic matter from several geologic environments and ages which are enriched in uranium (56 ppm to 12%) have been characterized. The three analytical techniqyes used to study the samples were Rock-Eval pyrolysis, pyrolysis-gas chromatography-mass spectrometry, and solid-state C-13 nuclear magnetic resonance (NMR) spectroscopy. In samples with low uranium content, the pyrolysis-gas chromatography products contain oxygenated functional groups (as hydroxyl) and molecules with both aliphatic and aromatic carbon atoms. These samples with low uranium content give measurable Rock-Eval hydrocarbon and organic-CO2 yields, and C-13 NMR values of > 30% aliphatic carbon. In contrast, uranium-rich samples have few hydrocarbon pyrolysis products, increased Rock-Eval organic-CO2 contents and > 70% aromatic carbon contents from C-13 NMR. The increase in aromaticity and decrease in hydrocarbon pyrolysis yield are related to the amount of uranium and the age of the uranium minerals, which correspond to the degree of radiation damage. The three analytical techniques give complementary results. Increase in Rock-Eval organic-CO2 yield correlates with uranium content for samples from the Grants uranium region. Calculations show that the amount of organic-CO2 corresponds to the quantity of uranium chemically reduced by the organic matter for the Grants uranium region samples. ?? 1986.

Large decadal-scale changes in uranium and bicarbonate in groundwater of the irrigated western U.S

USGS Publications Warehouse

Burow, Karen R.; Belitz, Kenneth; Dubrovsky, Neil M.; Jurgens, Bryant C.

2017-01-01

Samples collected about one decade apart from 1105 wells from across the U.S. were compiled to assess whether uranium concentrations in the arid climate are linked to changing bicarbonate concentrations in the irrigated western U.S. Uranium concentrations in groundwater were high in the arid climate in the western U.S, where uranium sources are abundant. Sixty-four wells (6%) were above the U.S. EPA MCL of 30 μg/L; all but one are in the arid west. Concentrations were low to non-detectable in the humid climate. Large uranium and bicarbonate increases (differences are greater than the uncertainty in concentrations) occur in 109 wells between decade 1 and decade 2. Similarly, large uranium and bicarbonate decreases occur in 76 wells between the two decades. Significantly more wells are concordant (uranium and bicarbonate are both going the same direction) than discordant (uranium and bicarbonate are going opposite directions) (p < 0.001; Chi-square test). The largest percent difference in uranium concentrations occur in wells where uranium is increasing and bicarbonate is also increasing. These large differences occur mostly in the arid climate. Results are consistent with the hypothesis that changing uranium concentrations are linked to changes in bicarbonate in irrigated areas of the western U.S.

Immobilization of uranium into magnetite from aqueous solution by electrodepositing approach.

PubMed

Lu, Bing-Qing; Li, Mi; Zhang, Xiao-Wen; Huang, Chun-Mei; Wu, Xiao-Yan; Fang, Qi

2018-02-05

Immobilization of uranium into magnetite (Fe 3 O 4 ), which was generated from metallic iron by electrochemical method, was proposed to rapidly remove uranium from aqueous solution. The effects of electrochemical parameters such as electrode materials, voltage, electrode gap, reaction time and pH value on the crystallization of Fe 3 O 4 and uranium removal efficiencies were investigated. More than 90% uranium in the solution was precipitated with Fe 3 O 4 under laboratory conditions when uranium concentration range from 0.5mg/L to 10mg/L. The Fe 3 O 4 crystallization mechanism and immobilization of uranium was proved by XPS, XRD, TEM, FTIR and VSM methods. The results indicated that the cationic (including Fe 2+ , Fe 3+ and U(VI)) migrate to cathode side under the electric field and the uranium was incorporated or adsorbed by Fe 3 O 4 which was generated at cathode while the pH ranges between 2-7. The uranium-containing precipitate of Fe 3 O 4 can exist stably at the acid concentration below 60g/L. Furthermore, the precipitate may be used as valuable resources for uranium or iron recycling, which resulted in no secondary pollution in the removal of uranium from aqueous solution. Copyright © 2017. Published by Elsevier B.V.

Uranium provinces of North America; their definition, distribution, and models

USGS Publications Warehouse

Finch, Warren Irvin

1996-01-01

Uranium resources in North America are principally in unconformity-related, quartz-pebble conglomerate, sandstone, volcanic, and phosphorite types of uranium deposits. Most are concentrated in separate, well-defined metallogenic provinces. Proterozoic quartz-pebble conglomerate and unconformity-related deposits are, respectively, in the Blind River–Elliot Lake (BRELUP) and the Athabasca Basin (ABUP) Uranium Provinces in Canada. Sandstone uranium deposits are of two principal subtypes, tabular and roll-front. Tabular sandstone uranium deposits are mainly in upper Paleozoic and Mesozoic rocks in the Colorado Plateau Uranium Province (CPUP). Roll-front sandstone uranium deposits are in Tertiary rocks of the Rocky Mountain and Intermontane Basins Uranium Province (RMIBUP), and in a narrow belt of Tertiary rocks that form the Gulf Coastal Uranium Province (GCUP) in south Texas and adjacent Mexico. Volcanic uranium deposits are concentrated in the Basin and Range Uranium Province (BRUP) stretching from the McDermitt caldera at the Oregon-Nevada border through the Marysvale district of Utah and Date Creek Basin in Arizona and south into the Sierra de Peña Blanca District, Chihuahua, Mexico. Uraniferous phosphorite occurs in Tertiary sediments in Florida, Georgia, and North and South Carolina and in the Lower Permian Phosphoria Formation in Idaho and adjacent States, but only in Florida has economic recovery been successful. The Florida Phosphorite Uranium Province (FPUP) has yielded large quantities of uranium as a byproduct of the production of phosphoric acid fertilizer. Economically recoverable quantities of copper, gold, molybdenum, nickel, silver, thorium, and vanadium occur with the uranium deposits in some provinces.Many major epochs of uranium mineralization occurred in North America. In the BRELUP, uranium minerals were concentrated in placers during the Early Proterozoic (2,500–2,250 Ma). In the ABUP, the unconformity-related deposits were most likely formed initially by hot saline formational water related to diagenesis (»1,400 to 1,330 Ma) and later reconcentrated by hydrothermal events at »1,280–»1,000, »575, and »225 Ma. Subsequently in North America, only minor uranium mineralization occurred until after continental collision in Permian time (255 Ma). Three principal epochs of uranium mineralization occurred in the CPUP: (1) » 210–200 Ma, shortly after Late Triassic sedimentation; (2) »155–150 Ma, in Late Jurassic time; and (3) » 135 Ma, after sedimentation of the Upper Jurassic Morrison Formation. The most likely source of the uranium was silicic volcaniclastics for the three epochs derived from a volcanic island arc at the west edge of the North American continent. Uranium mineralization occurred during Eocene, Miocene, and Pliocene times in the RMIBUP, GCUP, and BRUP. Volcanic activity took place near the west edge of the continent during and shortly after sedimentation of the host rocks in these three provinces. Some volcanic centers in the Sierra de Peña Blanca district within the BRUP may have provided uranium-rich ash to host rocks in the GCUP.Most of the uranium provinces in North America appear to have a common theme of close associations to volcanic activity related to the development of the western margin of the North American plate. The south and west margin of the Canadian Shield formed the leading edge of the progress of uranium source development and mineralization from the Proterozoic to the present. The development of favorable hosts and sources of uranium is related to various tectonic elements developed over time. Periods of major uranium mineralization in North America were Early Proterozoic, Middle Proterozoic, Late Triassic–Early Jurassic, Early Cretaceous, Oligocene, and Miocene. Tertiary mineralization was the most pervasive, covering most of Western and Southern North America. 

Behavior of uranium under conditions of interaction of rocks and ores with subsurface water

NASA Astrophysics Data System (ADS)

Omel'Yanenko, B. I.; Petrov, V. A.; Poluektov, V. V.

2007-10-01

The behavior of uranium during interaction of subsurface water with crystalline rocks and uranium ores is considered in connection with the problem of safe underground insulation of spent nuclear fuel (SNF). Since subsurface water interacts with crystalline rocks formed at a high temperature, the mineral composition of these rocks and uranium species therein are thermodynamically unstable. Therefore, reactions directed toward the establishment of equilibrium proceed in the water-rock system. At great depths that are characterized by hindered water exchange, where subsurface water acquires near-neutral and reducing properties, the interaction is extremely sluggish and is expressed in the formation of micro- and nanoparticles of secondary minerals. Under such conditions, the slow diffusion redistribution of uranium with enrichment in absorbed forms relative to all other uranium species is realized as well. The products of secondary alteration of Fe- and Ti-bearing minerals serve as the main sorbents of uranium. The rate of alteration of minerals and conversion of uranium species into absorbed forms is slow, and the results of these processes are insignificant, so that the rocks and uranium species therein may be regarded as unaltered. Under reducing conditions, subsurface water is always saturated with uranium. Whether water interacts with rock or uranium ore, the equilibrium uranium concentration in water is only ≤10-8 mol/l. Uraninite ore under such conditions always remains stable irrespective of its age. The stability conditions of uranium ore are quite suitable for safe insulation of SNF, which consists of 95% uraninite (UO2) and is a confinement matrix for all other radionuclides. The disposal of SNF in massifs of crystalline rocks at depths below 500 m, where reducing conditions are predominant, is a reliable guarantee of high SNF stability. Under oxidizing conditions of the upper hydrodynamic zone, the rate of interaction of rocks with subsurface water increases by orders of magnitude and subsurface water is commonly undersaturated with uranium. Uranium absorbed by secondary minerals, particularly by iron hydroxides and leucoxene, is its single stable species under oxidizing conditions. The impact of oxygen-bearing water leads to destruction of uranium ore. This process is realized simultaneously at different hypsometric levels even if the permeability of the medium is variable in both the lateral and vertical directions. As a result, intervals containing uranyl minerals and relics of primary uranium ore are combined in ore-bearing zones with intervals of completely dissolved uranium minerals. A wide halo of elevated uranium contents caused by sorption is always retained at the location of uranium ore entirely destroyed by weathering. Uranium ore commonly finds itself in the aeration zone due to technogenic subsidence of the groundwater table caused by open-pit mining or pumping out of water from underground mines. The capillary and film waters that interact with rocks and ores in this zone are supplemented by free water filtering along fractures when rain falls or snow is thawing. The interaction of uranium ore with capillary water results in oxidation of uraninite, accompanied by loosening of the mineral surface, formation of microfractures, and an increase in solubility with enrichment of capillary water in uranium up to 10-4 mol/l. Secondary U(VI) minerals, first of all, uranyl hydroxides and silicates, replace uraninite, and uranium undergoes local diffusion redistribution with its sorption by secondary minerals of host rocks. The influx of free water facilitates the complete dissolution of primary and secondary uranium minerals, the removal of uranium at the sites of groundwater discharge, and its redeposition under reducing conditions at a greater depth. It is evident that the conditions of the upper hydrodynamic zone and the aeration zone are unfit for long-term insulation of SNF and high-level wastes because, after the failure of containers, the leakage of radionuclides into the environment becomes inevitable.

Process for removing carbon from uranium

DOEpatents

Powell, George L.; Holcombe, Jr., Cressie E.

1976-01-01

Carbon contamination is removed from uranium and uranium alloys by heating in inert atmosphere to 700.degree.-1900.degree.C in effective contact with yttrium to cause carbon in the uranium to react with the yttrium. The yttrium is either in direct contact with the contaminated uranium or in indirect contact by means of an intermediate transport medium.

10 CFR 71.22 - General license: Fissile material.

Code of Federal Regulations, 2011 CFR

2011-01-01

... to obtain the value of X, then the values for the terms in the equation for uranium-233 and plutonium... if: (i) Uranium-233 is present in the package; (ii) The mass of plutonium exceeds 1 percent of the mass of uranium-235; (iii) The uranium is of unknown uranium-235 enrichment or greater than 24 weight...

10 CFR 71.22 - General license: Fissile material.

Code of Federal Regulations, 2012 CFR

2012-01-01

... to obtain the value of X, then the values for the terms in the equation for uranium-233 and plutonium... if: (i) Uranium-233 is present in the package; (ii) The mass of plutonium exceeds 1 percent of the mass of uranium-235; (iii) The uranium is of unknown uranium-235 enrichment or greater than 24 weight...

10 CFR 71.22 - General license: Fissile material.

Code of Federal Regulations, 2014 CFR

2014-01-01

... to obtain the value of X, then the values for the terms in the equation for uranium-233 and plutonium... if: (i) Uranium-233 is present in the package; (ii) The mass of plutonium exceeds 1 percent of the mass of uranium-235; (iii) The uranium is of unknown uranium-235 enrichment or greater than 24 weight...

10 CFR 71.22 - General license: Fissile material.

Code of Federal Regulations, 2010 CFR

2010-01-01

... to obtain the value of X, then the values for the terms in the equation for uranium-233 and plutonium... if: (i) Uranium-233 is present in the package; (ii) The mass of plutonium exceeds 1 percent of the mass of uranium-235; (iii) The uranium is of unknown uranium-235 enrichment or greater than 24 weight...

10 CFR 71.22 - General license: Fissile material.

Code of Federal Regulations, 2013 CFR

2013-01-01

... to obtain the value of X, then the values for the terms in the equation for uranium-233 and plutonium... if: (i) Uranium-233 is present in the package; (ii) The mass of plutonium exceeds 1 percent of the mass of uranium-235; (iii) The uranium is of unknown uranium-235 enrichment or greater than 24 weight...

PRODUCTION OF URANIUM TETRACHLORIDE

DOEpatents

Calkins, V.P.

1958-12-16

A process is descrlbed for the production of uranium tetrachloride by contacting uranlum values such as uranium hexafluoride, uranlum tetrafluoride, or uranium oxides with either aluminum chloride, boron chloride, or sodium alumlnum chloride under substantially anhydrous condltlons at such a temperature and pressure that the chlorldes are maintained in the molten form and until the uranium values are completely converted to uranlum tetrachloride.

PRODUCTION OF URANIUM MONOCARBIDE

DOEpatents

Powers, R.M.

1962-07-24

A method of making essentially stoichiometric uranium monocarbide by pelletizing a mixture of uranium tetrafluoride, silicon, and carbon and reacting the mixture at a temperature of approximately 1500 to 1700 deg C until the reaction goes to completion, forming uranium monocarbide powder and volatile silicon tetrafluoride, is described. The powder is then melted to produce uranium monocarbide in massive form. (AEC)

Nuclear reactor fuel structure containing uranium alloy wires embedded in a metallic matrix plate

DOEpatents

Travelli, A.

1985-10-25

A flat or curved plate structure, to be used as fuel in a nuclear reactor, comprises elongated fissionable wires or strips embedded in a metallic continuous non-fissionable matrix plate. The wires or strips are made predominantly of a malleable uranium alloy, such as uranium silicide, uranium gallide or uranium germanide. The matrix plate is made predominantly of aluminum or an aluminum alloy. The wires or strips are located in a single row at the midsurface of the plate, parallel with one another and with the length dimension of the plate. The wires or strips are separated from each other, and from the surface of the plate, by sufficient thicknesses of matrix material, to provide structural integrity and effective fission product retention, under neutron irradiation. This construction makes it safely feasible to provide a high uranium density, so that the uranium enrichment with uranium 235 may be reduced below about 20%, to deter the reprocessing of the uranium for use in nuclear weapons.

Nuclear reactor fuel structure containing uranium alloy wires embedded in a metallic matrix plate

DOEpatents

Travelli, Armando

1988-01-01

A flat or curved plate structure, to be used as fuel in a nuclear reactor, comprises elongated fissionable wires or strips embedded in a metallic continuous non-fissionable matrix plate. The wires or strips are made predominantly of a malleable uranium alloy, such as uranium silicide, uranium gallide or uranium germanide. The matrix plate is made predominantly of aluminum or an aluminum alloy. The wires or strips are located in a single row at the midsurface of the plate, parallel with one another and with the length dimension of the plate. The wires or strips are separated from each other, and from the surface of the plate, by sufficient thicknesses of matrix material, to provide structural integrity and effective fission product retention, under neutron irradiation. This construction makes it safely feasible to provide a high uranium density, so that the uranium enrichment with uranium 235 may be reduced below about 20%, to deter the reprocessing of the uranium for use in nuclear weapons.

High temperature UF6 RF plasma experiments applicable to uranium plasma core reactors

NASA Technical Reports Server (NTRS)

Roman, W. C.

1979-01-01

An investigation was conducted using a 1.2 MW RF induction heater facility to aid in developing the technology necessary for designing a self critical fissioning uranium plasma core reactor. Pure, high temperature uranium hexafluoride (UF6) was injected into an argon fluid mechanically confined, steady state, RF heated plasma while employing different exhaust systems and diagnostic techniques to simulate and investigate some potential characteristics of uranium plasma core nuclear reactors. The development of techniques and equipment for fluid mechanical confinement of RF heated uranium plasmas with a high density of uranium vapor within the plasma, while simultaneously minimizing deposition of uranium and uranium compounds on the test chamber peripheral wall, endwall surfaces, and primary exhaust ducts, is discussed. The material tests and handling techniques suitable for use with high temperature, high pressure, gaseous UF6 are described and the development of complementary diagnostic instrumentation and measurement techniques to characterize the uranium plasma, effluent exhaust gases, and residue deposited on the test chamber and exhaust system components is reported.

Preparation of carbon coated Fe3O4 nanoparticles for magnetic separation of uranium

NASA Astrophysics Data System (ADS)

Zhang, Xiaofei; Wang, Jun

2018-01-01

Uranium(VI) was removed from aqueous solutions using carbon coated Fe3O4 nanoparticles (Fe3O4@C). Batch experiments were conducted to study the effects of initial pH, shaking time and temperature on uranium sorption efficiency. It was found that the maximum adsorption capacity of the Fe3O4@C toward uranium(VI) was ∼120.20 mg g-1 when the initial uranium(VI) concentration was 100 mg L-1, displaying a high efficiency for the removal of uranium(VI) ions. Kinetics of the uranium(VI) removal is found to follow pseudo-second-order rate equation. In addition, the uranium(VI)-loaded Fe3O4@C nanoparticles can be recovered easily from aqueous solution by magnetic separation and regenerated by acid treatment. Present study suggested that magnetic Fe3O4@C composite particles can be used as an effective and recyclable adsorbent for the removal of uranium(VI) from aqueous solutions.

Can we predict uranium bioavailability based on soil parameters? Part 2: soil solution uranium concentration is not a good bioavailability index.

PubMed

Vandenhove, H; Van Hees, M; Wannijn, J; Wouters, K; Wang, L

2007-01-01

The present study aimed to quantify the influence of soil parameters on uranium uptake by ryegrass. Ryegrass was established on eighteen distinct soils, spiked with (238)U. Uranium soil-to-plant transfer factors (TF) ranged from 0.0003 to 0.0340kgkg(-1). There was no significant relation between the U soil-to-plant transfer (or total U uptake or flux) and the uranium concentration in the soil solution or any other soil factor measured, nor with the U recovered following selective soil extractions. Multiple linear regression analysis resulted in a significant though complex model explaining up to 99% of variation in TF. The influence of uranium speciation on uranium uptake observed was featured: UO(2)(+2), uranyl carbonate complexes and UO(2)PO(4)(-) seem the U species being preferentially taken up by the roots and transferred to the shoots. Improved correlations were obtained when relating the uranium TF with the summed soil solution concentrations of mentioned uranium species.

[Effect of the chelator BPCBG on the decorporation of uranium in vivo and uranium-induced damage of human renal tubular epithelial cells in vitro].

PubMed

Bao, Yi-zhong; Wang, Dan; Hu, Yu-xing; Xu, Ai-hong; Sun, Mei-zhen; Chen, Hong-hong

2011-11-01

This study is to assess the efficacy of BPCBG on the decorporation of uranium (VI) and protecting human renal proximal tubular epithelial cells (HK-2) against uranium-induced damage. BPCBG at different doses was injected intramuscularly to male SD rats immediately after a single intraperitoneal injection of UO2(CH3COO)2. Twenty-four hours later uranium contents in urine, kidneys and femurs were measured by ICP-MS. After HK-2 cells were exposed to UO2(CH3COO)2 immediately or for 24 h followed by BPCBG treatment at different doses for another 24 or 48 h, the uranium contents in HK-2 cells were measured by ICP-MS, the cell survival was assayed by cell counting kit-8 assay, formation of micronuclei was determined by the cytokinesis-block (CB) micronucleus assay and the production of intracellular reactive oxygen species (ROS) was detected by 2',7'-dichlorofluorescin diacetate (DCFH-DA) oxidation. DTPA-CaNa3 was used as control. It was found that BPCBG at dosages of 60, 120, and 600 micromol kg(-1) resulted in 37%-61% increase in 24 h-urinary uranium excretion, and significantly decreased the amount of uranium retention in kidney and bone to 41%-31% and 86%-42% of uranium-treated group, respectively. After HK-2 cells that had been pre-treated with UO2(CH3COO)2 for 24 h were treated with the chelators for another 24 h, 55%-60% of the intracellular uranium was removed by 10-250 micromol L(-1) of BPCBG. Treatment of uranium-treated HK-2 cells with BPCBG significantly enhanced the cell survival, decreased the formation of micronuclei and inhibited the production of intracellular ROS. Although DTPA-CaNa3 markedly reduced the uranium retention in kidney of rats and HK-2 cells, its efficacy of uranium removal from body was significantly lower than that of BPCBG and it could not protect uranium-induced cell damage. It can be concluded that BPCBG effectively decorporated the uranium from UO2(CH3COO)2-treated rats and HK-2 cells, which was better than DTPA-CaNa3. It could also scavenge the uranium-induced intracellular ROS and protect against the uranium-induced cell damage. BPCBG is worth further investigation.

[Uranium exposure and cancer risk: a review of epidemiological studies].

PubMed

Tirmarche, M; Baysson, H; Telle-Lamberton, M

2004-02-01

At the end of 2000, certain diseases including leukemia were reported among soldiers who participated in the Balkan and in the Gulf wars. Depleted uranium used during these conflicts was considered as a possible cause. Its radiotoxicity is close to that of natural uranium. This paper reviews the epidemiological knowledge of uranium, the means of exposure and the associated risk of cancer. The only available epidemiological data concerns nuclear workers exposed to uranium. A review of the international literature is proposed by distinguishing between uranium miners and other workers of the nuclear industry. French studies are described in details. In ionizing radiation epidemiology, contamination by uranium is often cited as a risk factor, but the dose-effect relationship is rarely studied. Retrospective assessment of individual exposure is generally insufficient. Moreover, it is difficult to distinguish between uranium radiotoxicity, its chemical toxicity and the radiotoxicity of its progeny. A causal relation between lung cancer and radon exposure, a gas derived from the decay of uranium, has been demonstrated in epidemiological studies of miners. Among other nuclear workers exposed to uranium, there is a mortality deficit from all causes (healthy worker effect). No cancer site appears systematically in excess compared to the national population; very few studies describe a dose-response relationship. Only studies with a precise reconstruction of doses and sufficient numbers of workers will allow a better assessment of risks associated with uranium exposure at levels encountered in industry or during conflicts using depleted uranium weapons.

Enhanced uranium immobilization and reduction by Geobacter sulfurreducens biofilms.

PubMed

Cologgi, Dena L; Speers, Allison M; Bullard, Blair A; Kelly, Shelly D; Reguera, Gemma

2014-11-01

Biofilms formed by dissimilatory metal reducers are of interest to develop permeable biobarriers for the immobilization of soluble contaminants such as uranium. Here we show that biofilms of the model uranium-reducing bacterium Geobacter sulfurreducens immobilized substantially more U(VI) than planktonic cells and did so for longer periods of time, reductively precipitating it to a mononuclear U(IV) phase involving carbon ligands. The biofilms also tolerated high and otherwise toxic concentrations (up to 5 mM) of uranium, consistent with a respiratory strategy that also protected the cells from uranium toxicity. The enhanced ability of the biofilms to immobilize uranium correlated only partially with the biofilm biomass and thickness and depended greatly on the area of the biofilm exposed to the soluble contaminant. In contrast, uranium reduction depended on the expression of Geobacter conductive pili and, to a lesser extent, on the presence of the c cytochrome OmcZ in the biofilm matrix. The results support a model in which the electroactive biofilm matrix immobilizes and reduces the uranium in the top stratum. This mechanism prevents the permeation and mineralization of uranium in the cell envelope, thereby preserving essential cellular functions and enhancing the catalytic capacity of Geobacter cells to reduce uranium. Hence, the biofilms provide cells with a physically and chemically protected environment for the sustained immobilization and reduction of uranium that is of interest for the development of improved strategies for the in situ bioremediation of environments impacted by uranium contamination. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Enhanced Uranium Immobilization and Reduction by Geobacter sulfurreducens Biofilms

PubMed Central

Cologgi, Dena L.; Speers, Allison M.; Bullard, Blair A.; Kelly, Shelly D.

2014-01-01

Biofilms formed by dissimilatory metal reducers are of interest to develop permeable biobarriers for the immobilization of soluble contaminants such as uranium. Here we show that biofilms of the model uranium-reducing bacterium Geobacter sulfurreducens immobilized substantially more U(VI) than planktonic cells and did so for longer periods of time, reductively precipitating it to a mononuclear U(IV) phase involving carbon ligands. The biofilms also tolerated high and otherwise toxic concentrations (up to 5 mM) of uranium, consistent with a respiratory strategy that also protected the cells from uranium toxicity. The enhanced ability of the biofilms to immobilize uranium correlated only partially with the biofilm biomass and thickness and depended greatly on the area of the biofilm exposed to the soluble contaminant. In contrast, uranium reduction depended on the expression of Geobacter conductive pili and, to a lesser extent, on the presence of the c cytochrome OmcZ in the biofilm matrix. The results support a model in which the electroactive biofilm matrix immobilizes and reduces the uranium in the top stratum. This mechanism prevents the permeation and mineralization of uranium in the cell envelope, thereby preserving essential cellular functions and enhancing the catalytic capacity of Geobacter cells to reduce uranium. Hence, the biofilms provide cells with a physically and chemically protected environment for the sustained immobilization and reduction of uranium that is of interest for the development of improved strategies for the in situ bioremediation of environments impacted by uranium contamination. PMID:25128347

Regularities of spatial association of major endogenous uranium deposits and kimberlitic dykes in the uranium ore regions of the Ukrainian Shield

NASA Astrophysics Data System (ADS)

Kalashnyk, Anna

2015-04-01

During exploration works we discovered the spatial association and proximity time formation of kimberlite dykes (ages are 1,815 and 1,900 Ga for phlogopite) and major industrial uranium deposits in carbonate-sodium metasomatites (age of the main uranium ore of an albititic formation is 1,85-1,70 Ga according to U-Pb method) in Kirovogradsky, Krivorozhsky and Alekseevsko-Lysogorskiy uranium ore regions of the Ukrainian Shield (UkrSh) [1]. In kimberlites of Kirovogradsky ore region uranium content reaches 18-20 g/t. Carbon dioxide is a major component in the formation of hydrothermal uranium deposits and the formation of the sodium in the process of generating the spectrum of alkaline ultrabasic magmas in the range from picritic to kimberlite and this is the connection between these disparate geochemical processes. For industrial uranium deposits in carbonate-sodium metasomatitics of the Kirovogradsky and Krivorozhsky uranium ore regions are characteristic of uranyl carbonate introduction of uranium, which causes correlation between CO2 content and U in range of "poor - ordinary - rich" uranium ore. In productive areas of uranium-ore fields of the Kirovogradsky ore region for phlogopite-carbonate veinlets of uranium ore albitites deep δ13C values (from -7.9 to -6.9o/oo) are characteristic. Isotope-geochemical investigation of albitites from Novokonstantynovskoe, Dokuchaevskoe, Partyzanskoe uranium deposits allowed obtaining direct evidence of the involvement of mantle material during formation of uranium albitites in Kirovogradsky ore region [2]. Petrological characteristics of kimberlites from uranium ore regions of the UkrSh (presence of nodules of dunite and harzburgite garnet in kimberlites, diamonds of peridotite paragenesis, chemical composition of indicator minerals of kimberlite, in particular Gruzskoy areas pyropes (Cr2O3 = 6,1-7,1%, MgO = 19,33-20,01%, CaO = 4,14-4,38 %, the content of knorringite component of most grains > 50mol%), chromites (Cr2O3 = 45,32-62,17%, MgO = 7,3-12,5%) allow us to estimate the depth of generation of kimberlite magmas more than 170-200 km. Ilmenites show two groups according to MgO, Cr2O3 and TiO2 content. Reconstructions of the mantle sections show also two intervals of pressures divided at 4.5 GPa, the upper part is highly metasomatized This high degree metasomatism is determined for almost all mantle columns. It is suggested that large-scale of uranium-bearing mantle fluids may be associated with the ancient degasation during the subduction which is highly enriched in U component . Analysis of the reasons for the marked association kimberlitic dykes and major industrial uranium deposits in carbonate-sodium metasomatic in the UkrSh led to the conclusion that hydrothermal uranium deposits are confined to the supply mantle fluid systems of mantle fault zones exercising brings sodium carbonate solutions enriched uranium from mantle sources. References: 1. Kalashnik A.A. New prognostic-evaluation criteria in technology prognosis of forming industrial endogenous uranium deposits of the Ukrainian Shield, 2014. Scientific proceedings of UkrSGRI, № 2, p. 27-54 (in Russian) 2. Stepanjuk L.M., Bondarenko S.V., Somka V.O. and other, 2012. Source of uranium and uranium-bearing sodium albitites for example of Dokuchaievskogo field of the Ingulsky megablock of the UkrSh: Abstracts of scientific conference "Theoretical issues and research practice metasomatic rocks and ores" (Kyiv, 14-16 March 2012), IGMOF, p.78-80. (in Ukrainian)

PROCESS OF PREPARING A FLUORIDE OF TETRAVLENT URANIUM

DOEpatents

Wheelwright, E.J.

1959-02-17

A method is described for producing a fluoride salt pf tetravalent uranium suitable for bomb reduction to metallic uranium. An aqueous solution of uranyl nitrate is treated with acetic acid and a nitrite-suppressor and then contacted with metallic lead whereby uranium is reduced from the hexavalent to the tetravalent state and soluble lead acetate is formed. Sulfate ions are then added to the solution to precipitate and remove the lead values. Hydrofluoric acid and alkali metal ions are then added causing the formation of an alkali metal uranium double-fluoride in which the uranium is in the tetravalent state. After recovery, this precipitate is suitable for using in the limited production of metallic uranium.

Chemical treatment of low-grade uranium ores. Extraction of uranium from tricalcium phosphate; TRAITEMENT CHIMIQUE DES MINERAIS PAUVRES D'URANIUM. EXTRACTION DE L'URANIUM DU PHOSPHATE TRICALCIQUE (in French)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mechelynck, Ph.

1958-07-15

After an examination of the different processes for the treatment of uranium minerals, it is concluded that the extraction of uranium by ion exchange is not applicable to hydrochloric acid solutions of phosphates. A sulfuric or phosphoric solution can be used. For solvent extraction of uranium, sulfuric or phosphoric solutions are the best, but hydrochloric solutions can be used. The cost of the solvents used would determine the cost of the operation. It is necessary, in the case of liquid-liquid extraction, to filter or decant the solution before extraction. (tr-auth)

PROCESS FOR PRODUCING URANIUM TETRAFLUORIDE

DOEpatents

Harvey, B.G.

1954-09-14

>This patent relates to improvements in the method for producing uranium tetrafluoride by treating an aqueous solutlon of a uranyl salt at an elevated temperature with a reducing agent effective in acld solutlon in the presence of hydrofluoric acid. Uranium tetrafluoride produced this way frequentiy contains impurities in the raw material serving as the source of uranium. Uranium tetrafluoride much less contaminated with impurities than when prepared by the above method can be prepared from materials containing such impurities by first adding a small proportion of reducing agent so as to cause a small fraction, for example 1 to 5% of the uranium tetrafluoride to be precipitated, rejecting such precipitate, and then precipitating and recovering the remainder of the uranium tetrafluoride.

Exposure assessment of natural uranium from drinking water.

PubMed

Jakhu, Rajan; Mehra, Rohit; Mittal, H M

2016-12-08

The uranium concentration in the drinking water of the residents of the Jaipur and Ajmer districts of Rajasthan has been measured for exposure assessment. The daily intake of uranium from the drinking water for the residents of the study area is found to vary from 0.4 to 123.9 μg per day. For the average uranium ingestion rate of 35.2 μg per day for a long term exposure period of 60 years, estimations have been made for the retention of uranium in different body organs and its excretion with time using ICRP's biokinetic model of uranium. Radioactive and chemical toxicity of uranium has been reported and discussed in detail in the present manuscript.

METHOD OF APPLYING COPPER COATINGS TO URANIUM

DOEpatents

Gray, A.G.

1959-07-14

A method is presented for protecting metallic uranium, which comprises anodic etching of the uranium in an aqueous phosphoric acid solution containing chloride ions, cleaning the etched uranium in aqueous nitric acid solution, promptly electro-plating the cleaned uranium in a copper electro-plating bath, and then electro-plating thereupon lead, tin, zinc, cadmium, chromium or nickel from an aqueous electro-plating bath.

Reconnaissance for uranium in asphalt-bearing rocks in the western states

USGS Publications Warehouse

Hail, William James

1955-01-01

Evaluation of field data indicates that naturally occurring asphalts with a relatively high uranium content probably originated in, or migrated through, rocks that contain more than average amounts of uranium. It is believed that some of the uranium was present as an original constituent of the oil but that some uranium may have been introduced during migration of the oil.

DISSOLUTION OF URANIUM FUELS BY MONOOR DIFLUOROPHOSPHORIC ACID

DOEpatents

Johnson, R.; Horn, F.L.; Strickland, G.

1963-05-01

A method of dissolving and separating uranium from a uranium matrix fuel element by dissolving the uraniumcontaining matrix in monofluorophosphoric acid and/or difluorophosphoric acid at temperatures ranging from 150 to 275 un. Concent 85% C, thereafter neutralizing the solution to precipitate uranium solids, and converting the solids to uranium hexafluoride by treatment with a halogen trifluoride is presented. (AEC)

Biogeochemical behaviour and bioremediation of uranium in waters of abandoned mines.

PubMed

Mkandawire, Martin

2013-11-01

The discharges of uranium and associated radionuclides as well as heavy metals and metalloids from waste and tailing dumps in abandoned uranium mining and processing sites pose contamination risks to surface and groundwater. Although many more are being planned for nuclear energy purposes, most of the abandoned uranium mines are a legacy of uranium production that fuelled arms race during the cold war of the last century. Since the end of cold war, there have been efforts to rehabilitate the mining sites, initially, using classical remediation techniques based on high chemical and civil engineering. Recently, bioremediation technology has been sought as alternatives to the classical approach due to reasons, which include: (a) high demand of sites requiring remediation; (b) the economic implication of running and maintaining the facilities due to high energy and work force demand; and (c) the pattern and characteristics of contaminant discharges in most of the former uranium mining and processing sites prevents the use of classical methods. This review discusses risks of uranium contamination from abandoned uranium mines from the biogeochemical point of view and the potential and limitation of uranium bioremediation technique as alternative to classical approach in abandoned uranium mining and processing sites.

Plant-uptake of uranium: Hydroponic and soil system studies

USGS Publications Warehouse

Ramaswami, A.; Carr, P.; Burkhardt, M.

2001-01-01

Limited information is available on screening and selection of terrestrial plants for uptake and translocation of uranium from soil. This article evaluates the removal of uranium from water and soil by selected plants, comparing plant performance in hydroponic systems with that in two soil systems (a sandy-loam soil and an organic-rich soil). Plants selected for this study were Sunflower (Helianthus giganteus), Spring Vetch (Vicia sativa), Hairy Vetch (Vicia villosa), Juniper (Juniperus monosperma), Indian Mustard (Brassica juncea), and Bush Bean (Phaseolus nanus). Plant performance was evaluated both in terms of the percent uranium extracted from the three systems, as well as the biological absorption coefficient (BAC) that normalized uranium uptake to plant biomass. Study results indicate that uranium extraction efficiency decreased sharply across hydroponic, sandy and organic soil systems, indicating that soil organic matter sequestered uranium, rendering it largely unavailable for plant uptake. These results indicate that site-specific soils must be used to screen plants for uranium extraction capability; plant behavior in hydroponic systems does not correlate well with that in soil systems. One plant species, Juniper, exhibited consistent uranium extraction efficiencies and BACs in both sandy and organic soils, suggesting unique uranium extraction capabilities.

Uranium removal from aqueous solution by coir pith: equilibrium and kinetic studies.

PubMed

Parab, Harshala; Joshi, Shreeram; Shenoy, Niyoti; Verma, Rakesh; Lali, Arvind; Sudersanan, M

2005-07-01

Basic aspects of uranium adsorption by coir pith have been investigated by batch equilibration. The influence of different experimental parameters such as final solution pH, adsorbent dosage, sorption time, temperature and various concentrations of uranium on uptake were evaluated. Maximum uranium adsorption was observed in the pH range 4.0-6.0. The Freundlich and Langmuir adsorption models were used for the mathematical description of the adsorption equilibrium. The equilibrium data fitted well to both the equilibrium models in the studied concentration range of uranium (200-800 mg/l) and temperatures (305-336 K). The coir pith exhibited the highest uptake capacity for uranium at 317 K, at the final solution pH value of 4.3 and at the initial uranium concentration of 800 mg/l. The kinetics of the adsorption process followed a second-order adsorption. The adsorbent used proved to be suitable for removal of uranium from aqueous solutions. 0.2 N HCl was effective in uranium desorption. The results indicated that the naturally abundant coir pith of otherwise nuisance value exhibited considerable potential for application in removal of uranium from aqueous solution.

Construction of the Syngonium podophyllum-Pseudomonas sp. XNN8 Symbiotic Purification System and Investigation of Its Capability of Remediating Uranium Wastewater.

PubMed

Deng, Qin-Wen; Wang, Yong-Dong; Ding, De-Xin; Hu, Nan; Sun, Jing; He, Jia-Dong; Xu, Fei

2017-02-01

The endophyte Pseudomonas sp. XNN8 was separated from Typha orientalis which can secrete indole-3-acetic acid and 1-aminocyclopropane-1-carboxylate deaminase and siderophores and has strong resistance to uranium it was then colonized in the Syngonium podophyllum; and the S. podophyllum-Pseudomonas sp. XNN8 symbiotic purification system (SPPSPS) for uranium-containing wastewater was constructed. Afterwards, the hydroponic experiments to remove uranium from uranium-containing wastewater by the SPPSPS were conducted. After 24 days of treatment, the uranium concentrations of the wastewater samples with uranium concentrations between 0.5 and 5.0 mg/L were lowered to below 0.05 mg/L. Furthermore, the uranium in the plants was assayed using Fourier transform infrared spectroscopy (FTIR) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The Pseudomonas sp. XNN8 was found to generate substantial organic groups in the roots of the Syngonium podophyllum, which could improve the complexing capability of S. podophyllum for uranium. The uranium in the roots of S. podophyllum was found to be the uranyl phosphate (47.4 %) and uranyl acetate (52.6 %).

In situ spectroscopy and spectroelectrochemistry of uranium in high-temperature alkali chloride molten salts.

PubMed

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 coordination environment in these melts.

Uraniferous opal, Virgin Valley, Nevada: conditions of formation and implications for uranium exploration

USGS Publications Warehouse

Zielinski, R.A.

1982-01-01

Uraniferous, fluorescent opal, which occurs in tuffaceous sedimentary rocks at Virgin Valley, Nevada, records the temperature and composition of uranium-rich solutions as well as the time of uranium-silica coprecipitation. Results are integrated with previous geologic and geochronologic data for the area to produce a model for uranium mobility that may be used to explore for uranium deposits in similar geologic settings. Uraniferous opal occurs as replacements of diatomite, or silicic air-fall ash layers in tuffaceous lakebeds of the Virgin Valley Formation (Miocene) of Merriam (1907). Fission-track radiography shows uranium to be homogeneously dispersed throughout the opal structure, suggesting coprecipitation of dissolved uranium and silica gel. Fluid inclusions preserved within opal replacements of diatomite have homogenization temperatures in the epithermal range and are of low salinity. Four samples of opal from one locality all have U-Pb apparent ages which suggest uraniferous opal precipitation in late Pliocene time. These ages correspond to a period of local, normal faulting, and highangle faults may have served as vertical conduits for transport of deep, thermalized ground water to shallower levels. Lateral migration of rising solutions occurred at intersections of faults with permeable strata. Silica and some uranium were dissolved from silica-rich host strata of 5-20 ppm original uranium content and reprecipitated as the solutions cooled. The model predicts that in similar geologic settings, ore-grade concentrations of uranium will occur in permeable strata that intersect high-angle faults and that contain uranium source rocks as well as efficient reductant traps for uranium. In the absence of sufficient quantities of reductant materials, uranium will be flushed from the system or will accumulate in low-grade disseminated hosts such as uraniferous opal. ?? 1982.

Visualizing different uranium oxidation states during the surface alteration of uraninite and uranium tetrachloride.

PubMed

Grossmann, Kay; Arnold, Thuro; Steudtner, Robin; Weiss, Stefan; Bernhard, Gert

2009-08-01

Low-temperature alteration reactions on uranium phases may lead to the mobilization of uranium and thereby poses a potential threat to humans living close to uranium-contaminated sites. In this study, the surface alteration of uraninite (UO(2)) and uranium tetrachloride (UCl(4)) in air atmosphere was studied by confocal laser scanning microscopy (CLSM) and laser-induced fluorescence spectroscopy using an excitation wavelength of 408 nm. It was found that within minutes the oxidation state on the surface of the uraninite and the uranium tetrachloride changed. During the surface alteration process U(IV) atoms on the uraninite and uranium tetrachloride surface became stepwise oxidized by a one-electron step at first to U(V) and then further to U(VI). These observed changes in the oxidation states of the uraninite surface were microscopically visualized and spectroscopically identified on the basis of their fluorescence emission signal. A fluorescence signal in the wavelength range of 415-475 nm was indicative for metastable uranium(V), and a fluorescence signal in the range of 480-560 nm was identified as uranium(VI). In addition, the oxidation process of tetravalent uranium in aqueous solution at pH 0.3 was visualized by CLSM and U(V) was fluorescence spectroscopically identified. The combination of microscopy and fluorescence spectroscopy provided a very convincing visualization of the brief presence of U(V) as a metastable reaction intermediate and of the simultaneous coexistence of the three states U(IV), U(V), and U(VI). These results have a significant importance for fundamental uranium redox chemistry and should contribute to a better understanding of the geochemical behavior of uranium in nature.

Uranium uptake history, open-system behaviour and uranium-series ages of fossil Tridacna gigas from Huon Peninsula, Papua New Guinea

NASA Astrophysics Data System (ADS)

Ayling, Bridget F.; Eggins, Stephen; McCulloch, Malcolm T.; Chappell, John; Grün, Rainer; Mortimer, Graham

2017-09-01

Molluscs incorporate negligible uranium into their skeleton while they are living, with any uranium uptake occurring post-mortem. As such, closed-system U-series dating of molluscs is unlikely to provide reliable age constraints for marine deposits. Even the application of open-system U-series modelling is challenging, because uranium uptake and loss histories can affect time-integrated uranium distributions and are difficult to constrain. We investigate the chemical and isotopic distribution of uranium in fossil Tridacna gigas (giant clams) from Marine Isotope Stage (MIS) 5e (128-116 ka) and MIS 11 (424-374 ka) reefs at Huon Peninsula in Papua New Guinea. The large size of the clams enables detailed chemical and isotopic mapping of uranium using LA-ICPMS and LA-MC-ICPMS techniques. Within each fossil Tridacna specimen, marked differences in uranium concentrations are observed across the three Tridacna growth zones (outer, inner, hinge), with the outer and hinge zones being relatively enriched. In MIS 5e and MIS 11 Tridacna, the outer and hinge zones contain approximately 1 ppm and 5 ppm uranium respectively. In addition to uptake of uranium, loss of uranium appears prevalent, especially in the MIS 11 specimens. The effect of uranium loss is to elevate measured [230Th/238U] values with little effect on [234U/238U] values. Closed-system age estimates are on average 50% too young for the MIS 5e Tridacna, and 25% too young for the MIS 11 Tridacna. A complex, multi-stage uptake and loss history is interpreted for the fossil Tridacna and we demonstrate that they cannot provide independent, reliable geochronological controls on the timing of past reef growth at Huon Peninsula.

Quantification of Kinetic Rate Law Parameters of Uranium Release from Sodium Autunite as a Function of Aqueous Bicarbonate Concentrations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gudavalli, Ravi; Katsenovich, Yelena; Wellman, Dawn M.

2013-09-05

ABSTRACT: Hydrogen carbonate is one of the most significant components within the uranium geochemical cycle. In aqueous solutions, hydrogen carbonate forms strong complexes with uranium. As such, aqueous bicarbonate may significantly increase the rate of uranium release from uranium minerals. Quantifying the relationship of aqueous hydrogen carbonate solutions to the rate of uranium release during dissolution is critical to understanding the long-term fate of uranium within the environment. Single-pass flow-through (SPTF) experiments were conducted to estimate the rate of uranium release from Na meta-autunite as a function of bicarbonate solutions (0.0005-0.003 M) under the pH range of 6-11 and temperaturesmore » of 5-60oC. Consistent with the results of previous investigation, the rate of uranium release from sodium autunite exhibited minimal dependency on temperature; but were strongly dependent on pH and increasing concentrations of bicarbonate solutions. Most notably at pH 7, the rate of uranium release exhibited 370 fold increases relative to the rate of uranium release in the absence of bicarbonate. However, the effect of increasing concentrations of bicarbonate solutions on the release of uranium was significantly less under higher pH conditions. It is postulated that at high pH values, surface sites are saturated with carbonate, thus the addition of more bicarbonate would have less effect on uranium release. Results indicate the activation energies were unaffected by temperature and bicarbonate concentration variations, but were strongly dependent on pH conditions. As pH increased from 6 to 11, activation energy values were observed to decrease from 29.94 kJ mol-1 to 13.07 kJ mol-1. The calculated activation energies suggest a surface controlled dissolution mechanism.« less

Inhibition of poly(ADP-ribose)polymerase-1 and DNA repair by uranium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooper, Karen L.; Dashner, Erica J.; Tsosie, Ranalda

Uranium has radiological and non-radiological effects within biological systems and there is increasing evidence for genotoxic and carcinogenic properties attributable to uranium through its heavy metal properties. In this study, we report that low concentrations of uranium (as uranyl acetate; < 10 μM) is not cytotoxic to human embryonic kidney cells or normal human keratinocytes; however, uranium exacerbates DNA damage and cytotoxicity induced by hydrogen peroxide, suggesting that uranium may inhibit DNA repair processes. Concentrations of uranyl acetate in the low micromolar range inhibited the zinc finger DNA repair protein poly(ADP-ribose) polymerase (PARP)-1 and caused zinc loss from PARP-1 protein.more » Uranyl acetate exposure also led to zinc loss from the zinc finger DNA repair proteins Xeroderma Pigmentosum, Complementation Group A (XPA) and aprataxin (APTX). In keeping with the observed inhibition of zinc finger function of DNA repair proteins, exposure to uranyl acetate enhanced retention of induced DNA damage. Co-incubation of uranyl acetate with zinc largely overcame the impact of uranium on PARP-1 activity and DNA damage. These findings present evidence that low concentrations of uranium can inhibit DNA repair through disruption of zinc finger domains of specific target DNA repair proteins. This may provide a mechanistic basis to account for the published observations that uranium exposure is associated with DNA repair deficiency in exposed human populations. - Highlights: • Low micromolar concentration of uranium inhibits polymerase-1 (PARP-1) activity. • Uranium causes zinc loss from multiple DNA repair proteins. • Uranium enhances retention of DNA damage caused by ultraviolet radiation. • Zinc reverses the effects of uranium on PARP activity and DNA damage repair.« less

PROCESS FOR REMOVING NOBLE METALS FROM URANIUM

DOEpatents

Knighton, J.B.

1961-01-31

A pyrometallurgical method is given for purifying uranium containing ruthenium and palladium. The uranium is disintegrated and oxidized by exposure to air and then the ruthenium and palladium are extracted from the uranium with molten zinc.

Method for producing uranium atomic beam source

DOEpatents

Krikorian, Oscar H.

1976-06-15

A method for producing a beam of neutral uranium atoms is obtained by vaporizing uranium from a compound UM.sub.x heated to produce U vapor from an M boat or from some other suitable refractory container such as a tungsten boat, where M is a metal whose vapor pressure is negligible compared to that of uranium at the vaporization temperature. The compound, for example, may be the uranium-rhenium compound, URe.sub.2. An evaporation rate in excess of about 10 times that of conventional uranium beam sources is produced.

Contribution of Uranium-Bearing Evaporites to Plume Persistence Issues at a Former Uranium Mill Site Riverton, Wyoming, USA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Raymond; Dam, William; Campbell, Sam

2016-08-01

• Evaporites occur in an unsaturated silt layer, which is underlain by a sand and gravel aquifer. • These evaporites are rich in chloride across the site. • Uranium concentrations are higher in the evaporites that overlie the uranium contaminant plume. • Flooding can solubilize the evaporites in the silt layer and release chloride, sulfate (not shown), and uranium into the underlyingsand and gravel aquifer. • The uranium-rich evaporites can delay natural flushing, creating plume persistence near the Little Wind River.

Rapid Method for Sodium Hydroxide Fusion of Concrete and ...

EPA Pesticide Factsheets

Technical Fact Sheet Analysis Purpose: Qualitative analysis Technique: Alpha spectrometry Method Developed for: Americium-241, plutonium-238, plutonium-239, radium-226, strontium-90, uranium-234, uranium-235 and uranium-238 in concrete and brick samples Method Selected for: SAM lists this method for qualitative analysis of americium-241, plutonium-238, plutonium-239, radium-226, strontium-90, uranium-234, uranium-235 and uranium-238 in concrete or brick building materials. Summary of subject analytical method which will be posted to the SAM website to allow access to the method.

URANIUM RECOVERY PROCESS

DOEpatents

Yeager, J.H.

1958-08-12

In the prior art processing of uranium ores, the ore is flrst digested with nitric acid and filtered, and the uranium values are then extracted tom the filtrate by contacting with an organic solvent. The insoluble residue has been processed separately in order to recover any uranium which it might contain. The improvement consists in contacting a slurry, composed of both solution and residue, with the organic solvent prior to filtration. Tbe result is that uranium values contained in the residue are extracted along with the uranium values contained th the solution in one step.

PROCESS FOR THE PRODUCTION OF AMMONIUM URANIUM FLUORIDE

DOEpatents

Ellis, A.S.; Mooney, R.B.

1953-08-25

This patent relates to the preparation of ammonium uranium fluoride. The process comprises adding a water soluble fluoride to an aqueous solution of a uranous compound containing an ammonium salt, and isolating the resulting precipitate. This patent relates to the manufacture of uranium tetnafluoride from ammonium uranium fluoride, NH/sub 4/UF/sub 5/. Uranium tetrafluoride is prepared by heating the ammonium uranium fluoride to a temperature at which dissociation occurs with liberation of ammonium fluoride. Preferably the process is carried out under reduced pressure, or in a current of an inert gas.

Process for alloying uranium and niobium

DOEpatents

Holcombe, Cressie E.; Northcutt, Jr., Walter G.; Masters, David R.; Chapman, Lloyd R.

1991-01-01

Alloys such as U-6Nb are prepared by forming a stacked sandwich array of uraniun sheets and niobium powder disposed in layers between the sheets, heating the array in a vacuum induction melting furnace to a temperature such as to melt the uranium, holding the resulting mixture at a temperature above the melting point of uranium until the niobium dissolves in the uranium, and casting the uranium-niobium solution. Compositional uniformity in the alloy product is enabled by use of the sandwich structure of uranium sheets and niobium powder.

METHOD OF OPERATING A CALUTRON

DOEpatents

Davidson, P.H.

1960-01-12

A method of operating an electromagnetic isotope separator of the calutron class is reported whereby uranium tetrachloride is produced at a controlled rate within the source rather than betng introduced therein as was formerly practiced. This is accomplished by placing a uranium-bearing material, such as uranium metal, uranium trichloride, or uranium carbide in the charge receptacle of the calutron, heating this material to about to produce uranium tetrachloride vapor at a rate controlled by the chlorine gas flow into the source. The vapor is subsequently ionized by an electric arc and mass separated by conventional calutron methods.

Uranium hexafluoride public risk

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fisher, D.R.; Hui, T.E.; Yurconic, M.

1994-08-01

The limiting value for uranium toxicity in a human being should be based on the concentration of uranium (U) in the kidneys. The threshold for nephrotoxicity appears to lie very near 3 {mu}g U per gram kidney tissue. There does not appear to be strong scientific support for any other improved estimate, either higher or lower than this, of the threshold for uranium nephrotoxicity in a human being. The value 3 {mu}g U per gram kidney is the concentration that results from a single intake of about 30 mg soluble uranium by inhalation (assuming the metabolism of a standard person).more » The concentration of uranium continues to increase in the kidneys after long-term, continuous (or chronic) exposure. After chronic intakes of soluble uranium by workers at the rate of 10 mg U per week, the concentration of uranium in the kidneys approaches and may even exceed the nephrotoxic limit of 3 {mu}g U per gram kidney tissue. Precise values of the kidney concentration depend on the biokinetic model and model parameters assumed for such a calculation. Since it is possible for the concentration of uranium in the kidneys to exceed 3 {mu}g per gram tissue at an intake rate of 10 mg U per week over long periods of time, we believe that the kidneys are protected from injury when intakes of soluble uranium at the rate of 10 mg U per week do not continue for more than two consecutive weeks. For long-term, continuous occupational exposure to low-level, soluble uranium, we recommend a reduced weekly intake limit of 5 mg uranium to prevent nephrotoxicity in workers. Our analysis shows that the nephrotoxic limit of 3 {mu}g U per gram kidney tissues is not exceeded after long-term, continuous uranium intake at the intake rate of 5 mg soluble uranium per week.« less

The discovery and character of Pleistocene calcrete uranium deposits in the Southern High Plains of west Texas, United States

USGS Publications Warehouse

Van Gosen, Bradley S.; Hall, Susan M.

2017-12-18

This report describes the discovery and geology of two near-surface uranium deposits within calcareous lacustrine strata of Pleistocene age in west Texas, United States. Calcrete uranium deposits have not been previously reported in the United States. The west Texas uranium deposits share characteristics with some calcrete uranium deposits in Western Australia—uranium-vanadium minerals hosted by nonpedogenic calcretes deposited in saline lacustrine environments.In the mid-1970s, Kerr-McGee Corporation conducted a regional uranium exploration program in the Southern High Plains province of the United States, which led to the discovery of two shallow uranium deposits (that were not publicly reported). With extensive drilling, Kerr-McGee delineated one deposit of about 2.1 million metric tons of ore with an average grade of 0.037 percent U3O8 and another deposit of about 0.93 million metric tons of ore averaging 0.047 percent U3O8.The west-Texas calcrete uranium-vanadium deposits occur in calcareous, fine-grained sediments interpreted to be deposited in saline lakes formed during dry interglacial periods of the Pleistocene. The lakes were associated with drainages upstream of a large Pleistocene lake. Age determinations of tephra in strata adjacent to one deposit indicate the host strata is middle Pleistocene in age.Examination of the uranium-vanadium mineralization by scanning-electron microscopy indicated at least two generations of uranium-vanadium deposition in the lacustrine strata identified as carnotite and a strontium-uranium-vanadium mineral. Preliminary uranium-series results indicate a two-component system in the host calcrete, with early lacustrine carbonate that was deposited (or recrystallized) about 190 kilo-annum, followed much later by carnotite-rich crusts and strontium-uranium-vanadium mineralization in the Holocene (about 5 kilo-annum). Differences in initial 234U/238U activity ratios indicate two separate, distinct fluid sources.

Uranium Associations with Kidney Outcomes Vary by Urine Concentration Adjustment Method

PubMed Central

Shelley, Rebecca; Kim, Nam-Soo; Parsons, Patrick J.; Lee, Byung-Kook; Agnew, Jacqueline; Jaar, Bernard G.; Steuerwald, Amy J.; Matanoski, Genevieve; Fadrowski, Jeffrey; Schwartz, Brian S.; Todd, Andrew C.; Simon, David; Weaver, Virginia M.

2017-01-01

Uranium is a ubiquitous metal that is nephrotoxic at high doses. Few epidemiologic studies have examined the kidney filtration impact of chronic environmental exposure. In 684 lead workers environmentally exposed to uranium, multiple linear regression was used to examine associations of uranium measured in a four-hour urine collection with measured creatinine clearance, serum creatinine- and cystatin-C-based estimated glomerular filtration rates, and N-acetyl-β-D-glucosaminidase (NAG). Three methods were utilized, in separate models, to adjust uranium levels for urine concentration - μg uranium/g creatinine; μg uranium/L and urine creatinine as separate covariates; and μg uranium/4 hr. Median urine uranium levels were 0.07 μg/g creatinine and 0.02 μg/4 hr and were highly correlated (rs =0.95). After adjustment, higher ln-urine uranium was associated with lower measured creatinine clearance and higher NAG in models that used urine creatinine to adjust for urine concentration but not in models that used total uranium excreted (μg/4 hr). These results suggest that, in some instances, associations between urine toxicants and kidney outcomes may be statistical, due to the use of urine creatinine in both exposure and outcome metrics, rather than nephrotoxic. These findings support consideration of non-creatinine-based methods of adjustment for urine concentration in nephrotoxicant research. PMID:23591699

Uptake of uranium by aquatic plants growing in fresh water ecosystem around uranium mill tailings pond at Jaduguda, India.

PubMed

Jha, V N; Tripathi, R M; Sethy, N K; Sahoo, S K

2016-01-01

Concentration of uranium was determined in aquatic plants and substrate (sediment or water) of fresh water ecosystem on and around uranium mill tailings pond at Jaduguda, India. Aquatic plant/substrate concentration ratios (CRs) of uranium were estimated for different sites on and around the uranium mill tailings disposal area. These sites include upstream and downstream side of surface water sources carrying the treated tailings effluent, a small pond inside tailings disposal area and residual water of this area. Three types of plant groups were investigated namely algae (filamentous and non-filamentous), other free floating & water submerged and sediment rooted plants. Wide variability in concentration ratio was observed for different groups of plants studied. The filamentous algae uranium concentration was significantly correlated with that of water (r=0.86, p<0.003). For sediment rooted plants significant correlation was found between uranium concentration in plant and the substrate (r=0.88, p<0.001). Both for other free floating species and sediment rooted plants, uranium concentration was significantly correlated with Mn, Fe, and Ni concentration of plants (p<0.01). Filamentous algae, Jussiaea and Pistia owing to their high bioproductivity, biomass, uranium accumulation and concentration ratio can be useful for prospecting phytoremediation of stream carrying treated or untreated uranium mill tailings effluent. Copyright © 2015 Elsevier B.V. All rights reserved.

Uranium(VI) interactions with mackinawite in the presence and absence of bicarbonate and oxygen

USGS Publications Warehouse

Gallegos, Tanya J.; Fuller, Christopher C.; Webb, Samuel M.; Betterton, William J.

2013-01-01

Mackinawite, Fe(II)S, samples loaded with uranium (10-5, 10-4, and 10-3 mol U/g FeS) at pH 5, 7, and 9, were characterized using X-ray absorption spectroscopy and X-ray diffraction to determine the effects of pH, bicarbonate, and oxidation on uptake. Under anoxic conditions, a 5 g/L suspension of mackinawite lowered 5 × 10-5 M uranium(VI) to below 30 ppb (1.26 × 10-7 M) U. Between 82 and 88% of the uranium removed from solution by mackinawite was U(IV) and was nearly completely reduced to U(IV) when 0.012 M bicarbonate was added. Near-neighbor coordination consisting of uranium–oxygen and uranium-uranium distances indicates the formation of uraninite in the presence and absence of bicarbonate, suggesting reductive precipitation as the dominant removal mechanism. Following equilibration in air, mackinawite was oxidized to mainly goethite and sulfur and about 76% of U(IV) was reoxidized to U(VI) with coordination of uranium to axial and equatorial oxygen, similar to uranyl. Additionally, uranium-iron distances, typical of coprecipitation of uranium with iron oxides, and uranium-sulfur distances indicating bidentate coordination of U(VI) to sulfate were evident. The affinity of mackinawite and its oxidation products for U(VI) provides impetus for further study of mackinawite as a potential reactive medium for remediation of uranium-contaminated water.

Investigating Freshwater Periphyton Community Response to Uranium with Phospholipid Fatty Acid and Denaturing Gradient Gel Electrophoresis Analyses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Small, Jack A.; Bunn, Amoret L.; McKinstry, Craig A.

2008-04-01

Periphyton communities can be used as monitors of ecosystem health and as indicators of contamination in lotic systems. Measures of biomass, community structure and genetic diversity were used to investigate impacts of uranium exposure on periphyton. Laboratory exposures of periphyton in river water amended with uranium were performed for 5 days, followed by 2 days of uranium depuration in unamended river water. Productivity as measured by biomass was not affected by concentrations up to 100 µg L-1 uranium. Phospholipid fatty acid (PLFA) profiles and denaturing gradient gel electrophoresis (DGGE) banding patterns found no changes in community or genetic structure relatedmore » to uranium exposure. We suggest that the periphyton community as a whole is not impacted by exposures of uranium up to a dose of 100 µg L-1. These findings have significance for the assessment and prediction of uranium impacts on aquatic ecosystems.« less

METHOD OF OPERATING NUCLEAR REACTORS

DOEpatents

Untermyer, S.

1958-10-14

A method is presented for obtaining enhanced utilization of natural uranium in heavy water moderated nuclear reactors by charging the reactor with an equal number of fuel elements formed of natural uranium and of fuel elements formed of uranium depleted in U/sup 235/ to the extent that the combination will just support a chain reaction. The reactor is operated until the rate of burnup of plutonium equals its rate of production, the fuel elements are processed to recover plutonium, the depleted uranium is discarded, and the remaining uranium is formed into fuel elements. These fuel elements are charged into a reactor along with an equal number of fuel elements formed of uranium depleted in U/sup 235/ to the extent that the combination will just support a chain reaction, and reuse of the uranium is continued as aforesaid until it wlll no longer support a chain reaction when combined with an equal quantity of natural uranium.

A graphene oxide/amidoxime hydrogel for enhanced uranium capture

PubMed Central

Wang, Feihong; Li, Hongpeng; Liu, Qi; Li, Zhanshuang; Li, Rumin; Zhang, Hongsen; Liu, Lianhe; Emelchenko, G. A.; Wang, Jun

2016-01-01

The efficient development of selective materials for the recovery of uranium from nuclear waste and seawater is necessary for their potential application in nuclear fuel and the mitigation of nuclear pollution. In this work, a graphene oxide/amidoxime hydrogel (AGH) exhibits a promising adsorption performance for uranium from various aqueous solutions, including simulated seawater. We show high adsorption capacities (Qm = 398.4 mg g−1) and high % removals at ppm or ppb levels in aqueous solutions for uranium species. In the presence of high concentrations of competitive ions such as Mg2+, Ca2+, Ba2+ and Sr2+, AGH displays an enhanced selectivity for uranium. For low uranium concentrations in simulated seawater, AGH binds uranium efficiently and selectively. The results presented here reveal that the AGH is a potential adsorbent for remediating nuclear industrial effluent and adsorbing uranium from seawater. PMID:26758649

Applied technology for mine waste water decontamination in the uranium ores extraction from Romania

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bejenaru, C.; Filip, G.; Vacariu, V.T.

1996-12-31

The exploitation of uranium ores in Romania is carried out in underground mines. In all exploited uranium deposits, mine waste waters results and will still result after the closure of uranium ore extraction activity. The mine waters are radioactively contaminated with uranium and its decay products being a hazard both for underground waters as for the environment. This paper present the results of research work carried out by authors for uranium elimination from waste waters as the problems involved during the exploitation process of the existent equipment as its maintenance in good experimental conditions. The main waste water characteristics aremore » discussed: solids as suspension, uranium, radium, mineral salts, pH, etc. The moist suitable way to eliminate uranium from mine waste waters is the ion exchange process based on ion exchangers in fluidized bed. A flowsheet is given with main advantages resulted.« less

Determination of uranium in clinical and environmental samples by FIAS-ICPMS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karpas, Z.; Lorber, A.; Halicz, L.

Uranium may enter the human body through ingestion or inhalation. Ingestion of uranium compounds through the diet, mainly drinking water, is a common occurrence, as these compounds are present in the biosphere. Inhalation of uranium-containing particles is mainly an occupational safety problem, but may also take place in areas where uranium compounds are abundant. The uranium concentration in urine samples may serve as an indication of the total uranium body content. A method based on flow injection and inductively coupled plasma mass spectrometry (FIAS-ICPMS) was found to be most suitable for determination of uranium in clinical samples (urine and serum),more » environmental samples (seawater, wells and carbonate rocks) and in liquids consumed by humans (drinking water and commercial beverages). Some examples of the application of the FIAS-ICPMS method are reviewed and presented here.« less

PREPARATION OF URANIUM HEXAFLUORIDE

DOEpatents

Lawroski, S.; Jonke, A.A.; Steunenberg, R.K.

1959-10-01

A process is described for preparing uranium hexafluoride from carbonate- leach uranium ore concentrate. The briquetted, crushed, and screened concentrate is reacted with hydrogen fluoride in a fluidized bed, and the uranium tetrafluoride formed is mixed with a solid diluent, such as calcium fluoride. This mixture is fluorinated with fluorine and an inert diluent gas, also in a fluidized bed, and the uranium hexafluoride obtained is finally purified by fractional distillation.

PROCESS FOR THE RECOVERY OF URANIUM

DOEpatents

Morris, G.O.

1955-06-21

This patent relates to a process for the recovery of uranium from impure uranium tetrafluoride. The process consists essentially of the steps of dissolving the impure uranium tetrafluoride in excess dilute sulfuric acid in the presence of excess hydrogen peroxide, precipitating ammonium uranate from the solution so formed by adding an excess of aqueous ammonia, dissolving the precipitate in sulfuric acid and adding hydrogen peroxide to precipitate uranium peroxdde.

10 CFR 40.28 - General license for custody and long-term care of uranium or thorium byproduct materials disposal...

Code of Federal Regulations, 2011 CFR

2011-01-01

... 10 Energy 1 2011-01-01 2011-01-01 false General license for custody and long-term care of uranium... long-term care of uranium or thorium byproduct materials disposal sites. (a) A general license is... in this part for uranium or thorium mill tailings sites closed under title II of the Uranium Mill...

10 CFR 40.28 - General license for custody and long-term care of uranium or thorium byproduct materials disposal...

Code of Federal Regulations, 2012 CFR

2012-01-01

... 10 Energy 1 2012-01-01 2012-01-01 false General license for custody and long-term care of uranium... long-term care of uranium or thorium byproduct materials disposal sites. (a) A general license is... in this part for uranium or thorium mill tailings sites closed under title II of the Uranium Mill...

10 CFR 40.28 - General license for custody and long-term care of uranium or thorium byproduct materials disposal...

Code of Federal Regulations, 2013 CFR

2013-01-01

... 10 Energy 1 2013-01-01 2013-01-01 false General license for custody and long-term care of uranium... long-term care of uranium or thorium byproduct materials disposal sites. (a) A general license is... in this part for uranium or thorium mill tailings sites closed under title II of the Uranium Mill...

10 CFR 40.28 - General license for custody and long-term care of uranium or thorium byproduct materials disposal...

Code of Federal Regulations, 2014 CFR

2014-01-01

... 10 Energy 1 2014-01-01 2014-01-01 false General license for custody and long-term care of uranium... long-term care of uranium or thorium byproduct materials disposal sites. (a) A general license is... in this part for uranium or thorium mill tailings sites closed under title II of the Uranium Mill...

Uranium speciation and stability after reductive immobilization in aquifer sediments

NASA Astrophysics Data System (ADS)

Sharp, Jonathan O.; Lezama-Pacheco, Juan S.; Schofield, Eleanor J.; Junier, Pilar; Ulrich, Kai-Uwe; Chinni, Satya; Veeramani, Harish; Margot-Roquier, Camille; Webb, Samuel M.; Tebo, Bradley M.; Giammar, Daniel E.; Bargar, John R.; Bernier-Latmani, Rizlan

2011-11-01

It has generally been assumed that the bioreduction of hexavalent uranium in groundwater systems will result in the precipitation of immobile uraninite (UO 2). In order to explore the form and stability of uranium immobilized under these conditions, we introduced lactate (15 mM for 3 months) into flow-through columns containing sediments derived from a former uranium-processing site at Old Rifle, CO. This resulted in metal-reducing conditions as evidenced by concurrent uranium uptake and iron release. Despite initial augmentation with Shewanella oneidensis, bacteria belonging to the phylum Firmicutes dominated the biostimulated columns. The immobilization of uranium (˜1 mmol U per kg sediment) enabled analysis by X-ray absorption spectroscopy (XAS). Tetravalent uranium associated with these sediments did not have spectroscopic signatures representative of U-U shells or crystalline UO 2. Analysis by microfocused XAS revealed concentrated micrometer regions of solid U(IV) that had spectroscopic signatures consistent with bulk analyses and a poor proximal correlation (μm scale resolution) between U and Fe. A plausible explanation, supported by biogeochemical conditions and spectral interpretations, is uranium association with phosphoryl moieties found in biomass; hence implicating direct enzymatic uranium reduction. After the immobilization phase, two months of in situ exposure to oxic influent did not result in substantial uranium remobilization. Ex situ flow-through experiments demonstrated more rapid uranium mobilization than observed in column oxidation studies and indicated that sediment-associated U(IV) is more mobile than biogenic UO 2. This work suggests that in situ uranium bioimmobilization studies and subsurface modeling parameters should be expanded to account for non-uraninite U(IV) species associated with biomass.

A survey of uranium levels in urine and hair of people living in a coal mining area in Yili, Xinjiang, China.

PubMed

Wufuer, Rehemanjiang; Song, Wenjuan; Zhang, Daoyong; Pan, Xiangliang; Gadd, Geoffrey Michael

2018-09-01

Recent reports have drawn attention to the uranium contamination arising from coal mining activities in the Yili region of Xinjiang, China due to the mixed distribution of uranium and coal mines, and some of the coal mines being associated with a high uranium content. In this study, we have collected water samples, solid samples such as soil, mud, coal, and coal ash, and hair and urine samples from local populations in order to evaluate the uranium level in this environment and its implications for humans in this high uranium coal mining area. Our results showed that uranium concentrations were 8.71-10.91 μg L -1 in underground water, whereas lower levels of uranium occurred in river water. Among the solid samples, coal ash contained fairly high concentrations of uranium (33.1 μg g -1 ) due to enrichment from coal burning. In addition, uranium levels in the other solid samples were around 2.8 μg g -1 (the Earth's average background value). Uranium concentrations in hair and urine samples were 22.2-634.5 ng g -1 (mean: 156.2 ng g -1 ) and 8.44-761.6 ng L -1 (mean: 202.6 ng L -1 ), respectively, which are significantly higher than reference values reported for unexposed subjects in other areas. Therefore, these results indicate that people living in this coal mining area have been subjected to uranium exposure for long periods of time. Copyright © 2018. Published by Elsevier Ltd.

Drinking Water with Uranium below the U.S. EPA Water Standard Causes Estrogen Receptor–Dependent Responses in Female Mice

PubMed Central

Raymond-Whish, Stefanie; Mayer, Loretta P.; O’Neal, Tamara; Martinez, Alisyn; Sellers, Marilee A.; Christian, Patricia J.; Marion, Samuel L.; Begay, Carlyle; Propper, Catherine R.; Hoyer, Patricia B.; Dyer, Cheryl A.

2007-01-01

Background The deleterious impact of uranium on human health has been linked to its radioactive and heavy metal–chemical properties. Decades of research has defined the causal relationship between uranium mining/milling and onset of kidney and respiratory diseases 25 years later. Objective We investigated the hypothesis that uranium, similar to other heavy metals such as cadmium, acts like estrogen. Methods In several experiments, we exposed intact, ovariectomized, or pregnant mice to depleted uranium in drinking water [ranging from 0.5 μg/L (0.001 μM) to 28 mg/L (120 μM). Results Mice that drank uranium-containing water exhibited estrogenic responses including selective reduction of primary follicles, increased uterine weight, greater uterine luminal epithelial cell height, accelerated vaginal opening, and persistent presence of cornified vaginal cells. Coincident treatment with the antiestrogen ICI 182,780 blocked these responses to uranium or the synthetic estrogen diethylstilbestrol. In addition, mouse dams that drank uranium-containing water delivered grossly normal pups, but they had significantly fewer primordial follicles than pups whose dams drank control tap water. Conclusions Because of the decades of uranium mining/milling in the Colorado plateau in the Four Corners region of the American Southwest, the uranium concentration and the route of exposure used in these studies are environmentally relevant. Our data support the conclusion that uranium is an endocrine-disrupting chemical and populations exposed to environmental uranium should be followed for increased risk of fertility problems and reproductive cancers. PMID:18087588

An artificially constructed Syngonium podophyllum-Aspergillus niger combinate system for removal of uranium from wastewater.

PubMed

He, Jia-dong; Wang, Yong-dong; Hu, Nan; Ding, Dexin; Sun, Jing; Deng, Qin-wen; Li, Chang-wu; Xu, Fei

2015-12-01

Aspergillus niger was inoculated to the roots of five plants, and the Syngonium podophyllum-A. niger combinate system (SPANCS) was found to be the most effective in removing uranium from hydroponic liquid with initial uranium concentration of 5 mg L(-1). Furthermore, the hydroponic experiments on the removal of uranium from the hydroponic liquids with initial uranium concentrations of 0.5, 1.0, and 3.0 mg L(-1) by the SPANCS were conducted, the inhibitory effect of A. niger on the growth of S. podophyllum in the SPANCS was studied, the accumulation characteristics of uranium by S. podophyllum in the SPANCS were analyzed, and the Fourier transform infrared (FT-IR) and extended X-ray absorption fine structure (EXAFS) spectra were measured. The results show that the removal of uranium by the SPANCS from the hydroponic liquids with initial uranium concentrations of 0.5, 1.0, and 3.0 mg L(-1) reached 98.20, 97.90, and 98.50%, respectively, after 37 days of accumulation of uranium; that the uranium concentrations in the hydroponic liquids decreased to 0.009, 0.021, and 0.045 mg L(-1), respectively, which are lower than the stipulated concentration for discharge of 0.050 mg L(-1) by the People's Republic of China; that A. niger helped to generate more groups in the root of S. podophyllum which can improve the complexing capability of S. podophyllum for uranium; and that the uranium accumulated in the root of S. podophyllum was in the form of phosphate uranyl and carboxylic uranyl.

Occurrences of uranium at Clinton, Hunterdon County, New Jersey

USGS Publications Warehouse

McKeown, F.A.; Klemic, H.; Choquette, P.W.

1954-01-01

An occurrence of uranium at Clinton, Hunterdon County, N. J. was first brought to the attention of the U.S. Geological Survey when Mr. Thomas L. Eak of Avenel, N. J. submitted to the Survey a sample containing 0.068 percent uranium. Subsequent examinations of the area around Clinton indicated that detailed mapping and study were warranted. The uranium occurrences at Clinton are in or associated with fault zones in the Kittatinny limestone of Cambro-Ordovician age. The limestone generally light gray, thick bedded, and dolomitic; chert is common but not abundant. Regionally and locally, faults are the most significant structural features. The local faults at Clinton are the loci for most of the uranium. The largest fault can be traced for about 700 feet and is radioactive everywhere it crops out. Samples from this fault contain as much as 0.038 percent uranium; the average content is about 0.010 percent uranium. Uranium also occurs disseminated in two 4-inch layers of black feldspathic dolomite and in several zones of residual soil derived from the Kittatinny limestone. The black layers contain as much as 0.046 percent uranium and can be traced only about 20 feet along strike. They are cut by a small fault that is also radioactive. The radioactive soil zones are roughly elongated parallel to bedding. Soil from them contains up to 0.008 percent uranium. The uranium occurrences are best explained by a supergene origin. The sampling, mapping, and radioactivity testing of uranium occurrences at Clinton indicate they are too low grade to be of current economic interest.

Uranium Bioreduction and Biomineralization.

PubMed

Wufuer, Rehemanjiang; Wei, Yongyang; Lin, Qinghua; Wang, Huawei; Song, Wenjuan; Liu, Wen; Zhang, Daoyong; Pan, Xiangliang; Gadd, Geoffrey Michael

2017-01-01

Following the development of nuclear science and technology, uranium contamination has been an ever increasing concern worldwide because of its potential for migration from the waste repositories and long-term contaminated environments. Physical and chemical techniques for uranium pollution are expensive and challenging. An alternative to these technologies is microbially mediated uranium bioremediation in contaminated water and soil environments due to its reduced cost and environmental friendliness. To date, four basic mechanisms of uranium bioremediation-uranium bioreduction, biosorption, biomineralization, and bioaccumulation-have been established, of which uranium bioreduction and biomineralization have been studied extensively. The objective of this review is to provide an understanding of recent developments in these two fields in relation to relevant microorganisms, mechanisms, influential factors, and obstacles. Copyright © 2017 Elsevier Inc. All rights reserved.

Study of the Dry Processing of Uranium Ores; ETUDE DES TRAITEMENTS DE MINERAIS D'URANIUM PAR VOIE SECHE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guillet, H.

1959-02-01

A description is given of direct fluorination of preconcentrated uranium ores in order to obtain the hexafluoride. After normal sulfuric acid treatment of the ore to eliminate silica, the uranium is precipitated by 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 productmore » in a diffusion plant. (auth)« less

METHOD AND FLUX COMPOSITION FOR TREATING URANIUM

DOEpatents

Foote, F.

1958-08-23

ABS>A flux composition is described fer use with molten uranium or uranium alloys. The flux consists of about 46 weight per cent calcium fiuoride, 46 weight per cent magnesium fluoride and about 8 weight per cent of uranium tetrafiuoride.

High Useful Yield and Isotopic Analysis of Uranium by Resonance Ionization Mass Spectrometry

DOE PAGES

Savina, Michael R.; Isselhardt, Brett H.; Kucher, Andrew; ...

2017-05-09

Useful yields from resonance ionization mass spectrometry can be extremely high compared to other mass spectrometry techniques, but uranium analysis shows strong matrix effects arising from the tendency of uranium to form strongly bound oxide molecules that do not dissociate appreciably on energetic ion bombardment. Here, we demonstrate a useful yield of 24% for metallic uranium. Modeling the laser ionization and ion transmission processes shows that the high useful yield is attributable to a high ion fraction achieved by resonance ionization. We quantify the reduction of uranium oxide surface layers by Ar + and Ga + sputtering. The useful yieldmore » for uranium atoms from a uranium dioxide matrix is 0.4% and rises to 2% when the surface is in sputter equilibrium with the ion beam. The lower useful yield from the oxide is almost entirely due to uranium oxide molecules reducing the neutral atom content of the sputtered flux. We also demonstrate rapid isotopic analysis of solid uranium oxide at a precision of <0.5% relative standard deviation using relatively broadband lasers to mitigate spectroscopic fractionation.« less

High Useful Yield and Isotopic Analysis of Uranium by Resonance Ionization Mass Spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Savina, Michael R.; Isselhardt, Brett H.; Kucher, Andrew

Useful yields from resonance ionization mass spectrometry can be extremely high compared to other mass spectrometry techniques, but uranium analysis shows strong matrix effects arising from the tendency of uranium to form strongly bound oxide molecules that do not dissociate appreciably on energetic ion bombardment. Here, we demonstrate a useful yield of 24% for metallic uranium. Modeling the laser ionization and ion transmission processes shows that the high useful yield is attributable to a high ion fraction achieved by resonance ionization. We quantify the reduction of uranium oxide surface layers by Ar + and Ga + sputtering. The useful yieldmore » for uranium atoms from a uranium dioxide matrix is 0.4% and rises to 2% when the surface is in sputter equilibrium with the ion beam. The lower useful yield from the oxide is almost entirely due to uranium oxide molecules reducing the neutral atom content of the sputtered flux. We also demonstrate rapid isotopic analysis of solid uranium oxide at a precision of <0.5% relative standard deviation using relatively broadband lasers to mitigate spectroscopic fractionation.« less

Isotopic Analysis of Uranium in NIST SRM Glass by Femtosecond Laser Ablation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duffin, Andrew M.; Hart, Garret L.; Hanlen, Richard C.

We employed femtosecond Laser Ablation Multicollector Inductively Coupled Mass Spectrometry for the 11 determination of uranium isotope ratios in a series of standard reference material glasses (NIST 610, 612, 614, and 12 616). This uranium concentration in this series of SRM glasses is a combination of isotopically natural uranium in 13 the materials used to make the glass matrix and isotopically depleted uranium added to increase the uranium 14 elemental concentration across the series. Results for NIST 610 are in excellent agreement with literature values. 15 However, other than atom percent 235U, little information is available for the remaining glasses.more » We present atom 16 percent and isotope ratios for 234U, 235U, 236U, and 238U for all four glasses. Our results show deviations from the 17 certificate values for the atom percent 235U, indicating the need for further examination of the uranium isotopes in 18 NIST 610-616. Our results are fully consistent with a two isotopic component mixing between the depleted 19 uranium spike and natural uranium in the bulk glass.« less

Reconnaissance for uranium in black shale, Northern Rocky Mountains and Great Plains, 1953

USGS Publications Warehouse

Mapel, W.J.

1954-01-01

Reconnaissance examinations for uranium in 22 formations containing black shale were conducted in parts of Montana, North Dakota, Utah, Idaho, and Oregon during 1953. About 150 samples from 80 outcrop localities and 5 oil and gas wells were submitted for uranium determinations. Most of the black shale deposits examined contain less than 0.003 percent uranium; however, thin beds of black shale at the base of the Mississippian system contain 0.005 percent uranium at 2 outcrop localities in southwestern Montana and as much as 0.007 percent uranium in a well in northeastern Montana. An eight-foot bed of phosphatic black shale at the base of the Brazer limestone of Late Mississippian age in Rich County, Utah, contains as much as 0.009 percent uranium. Commercial gamma ray logs of oil and gas wells drilled in Montana and adjacent parts of the Dakotas indicate that locally the Heath shale of Late Mississippian age contains as much as 0.01 percent equivalent uranium, and black shales of Late Cretaceous age contain as much as 0.008 percent equivalent uranium.

Inversion of chalcogen defect levels in silicon - An MNDO study. [modified neglect of diatomic overlap

NASA Technical Reports Server (NTRS)

Singh, R. K.; Sahu, S. N.; Singh, V. A.; Corbett, J. W.

1985-01-01

MNDO (modified neglect of diatomic overlap) calculations have been carried out for substitutional oxygen and sulfur impurities in silicon. The calculations of the gap levels reveal a reversal of trend with atomic ionization energies in agreement with self-consistent Green function results, and analysis of the MNDO charge distribution supports the view that the electronegativity difference between oxygen and sulfur gives rise to this shallower energy level.

Basic mechanisms study for MIS solar cell structures on GaAs

NASA Technical Reports Server (NTRS)

Fonash, S. J.

1978-01-01

The solar cell structure examined is the MIS configuration on (n) GaAs. The metal room temperature oxide/(n) GaAs materials system was studied. Metals with electronegativities varying from 2.4 (Au) to 1.5 (Al) were used as the upper electrode. The thinnest metallization that did not interfere with the measurement techniques (by introducing essentially transmission line series resistance problems across a device) was used. Photovoltaic response was not optimized.

Rapid Discovery of Tribological Materials with Improved Performance Using Materials Informatics

DTIC Science & Technology

2014-03-10

of New Solid State Lubricants The recursive portioning model illustrated in Fig. 3 has been applied to about 500 compounds from the FileMakerPro...neighboring cation. Based on this assumption, the large cationic charge of mineral compounds indicates the number of anions tends to be larger than the...The formation of bond types is highly dependent on the difference of electronegativity (EN) between the two elements in the compound . For instance

NUCLEAR REACTOR FUEL ELEMENTS AND METHOD OF PREPARATION

DOEpatents

Kingston, W.E.; Kopelman, B.; Hausner, H.H.

1963-07-01

A fuel element consisting of uranium nitride and uranium carbide in the form of discrete particles in a solid coherent matrix of a metal such as steel, beryllium, uranium, or zirconium and clad with a metal such as steel, aluminum, zirconium, or beryllium is described. The element is made by mixing powdered uranium nitride and uranium carbide with powdered matrix metal, then compacting and sintering the mixture. (AEC)

PROCESS OF PURIFYING URANIUM

DOEpatents

Seaborg, G.T.; Orlemann, E.F.; Jensen, L.H.

1958-12-23

A method of obtaining substantially pure uranium from a uranium composition contaminated with light element impurities such as sodium, magnesium, beryllium, and the like is described. An acidic aqueous solution containing tetravalent uranium is treated with a soluble molybdate to form insoluble uranous molybdate which is removed. This material after washing is dissolved in concentrated nitric acid to obtaln a uranyl nitrate solution from which highly purified uranium is obtained by extraction with ether.

SOLVENT EXTRACTION PROCESS FOR URANIUM FROM CHLORIDE SOLUTIONS

DOEpatents

Blake, C.A. Jr.; Brown, K.B.; Horner, D.E.

1960-05-24

An improvement was made in a uranium extraction process wherein the organic extractant is a phosphine oxide. An aqueous solution containing phosphate ions or sulfate ions together with uranium is provided with a source of chloride ions during the extraction step. The presence of the chloride ions enables a phosphine oxide to extract uranium in the presence of strong uranium- complexing ions such as phosphate or sulfate ions.

Process for recovering uranium from waste hydrocarbon oils containing the same. [Uranium contaminated lubricating oils from gaseous diffusion compressors

DOEpatents

Conrad, M.C.; Getz, P.A.; Hickman, J.E.; Payne, L.D.

1982-06-29

The invention is a process for the recovery of uranium from uranium-bearing hydrocarbon oils containing carboxylic acid as a degradation product. In one aspect, the invention comprises providing an emulsion of water and the oil, heating the same to a temperature effecting conversion of the emulsion to an organic phase and to an acidic aqueous phase containing uranium carboxylate, and recovering the uranium from the aqueous phase. The process is effective, simple and comparatively inexpensive. It avoids the use of toxic reagents and the formation of undesirable intermediates.

PROCESS OF RECOVERING URANIUM

DOEpatents

Carter, J.M.; Larson, C.E.

1958-10-01

A process is presented for recovering uranium values from calutron deposits. The process consists in treating such deposits to produce an oxidlzed acidic solution containing uranium together with the following imparities: Cu, Fe, Cr, Ni, Mn, Zn. The uranium is recovered from such an impurity-bearing solution by adjusting the pH of the solution to the range 1.5 to 3.0 and then treating the solution with hydrogen peroxide. This results in the precipitation of uranium peroxide which is substantially free of the metal impurities in the solution. The peroxide precipitate is then separated from the solution, washed, and calcined to produce uranium trioxide.

High loading uranium fuel plate

DOEpatents

Wiencek, Thomas C.; Domagala, Robert F.; Thresh, Henry R.

1990-01-01

Two embodiments of a high uranium fuel plate are disclosed which contain a meat comprising structured uranium compound confined between a pair of diffusion bonded ductile metal cladding plates uniformly covering the meat, the meat having a uniform high fuel loading comprising a content of uranium compound greater than about 45 Vol. % at a porosity not greater than about 10 Vol. %. In a first embodiment, the meat is a plurality of parallel wires of uranium compound. In a second embodiment, the meat is a dispersion compact containing uranium compound. The fuel plates are fabricated by a hot isostatic pressing process.

URANIUM SEPARATION PROCESS

DOEpatents

Hyde, E.K.; Katzin, L.I.; Wolf, M.J.

1959-07-14

The separation of uranium from a mixture of uranium and thorium by organic solvent extraction from an aqueous solution is described. The uranium is separrted from an aqueous mixture of uranium and thorium nitrates 3 N in nitric acid and containing salting out agents such as ammonium nitrate, so as to bring ihe total nitrate ion concentration to a maximum of about 8 N by contacting the mixture with an immiscible aliphatic oxygen containing organic solvent such as diethyl carbinol, hexone, n-amyl acetate and the like. The uranium values may be recovered from the organic phase by back extraction with water.

Safeguards on uranium ore concentrate? the impact of modern mining and milling process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Francis, Stephen

2013-07-01

Increased purity in uranium ore concentrate not only raises the question as to whether Safeguards should be applied to the entirety of uranium conversion facilities, but also as to whether some degree of coverage should be moved back to uranium ore concentrate production at uranium mining and milling facilities. This paper looks at uranium ore concentrate production across the globe and explores the extent to which increased purity is evident and the underlying reasons. Potential issues this increase in purity raises for IAEA's strategy on the Starting Point of Safeguards are also discussed.

Uranium transport in the Walker River Basin, California and Nevada

USGS Publications Warehouse

Benson, L.V.; Leach, D.L.

1979-01-01

During the summer of 1976 waters from tributaries, rivers, springs and wells were sampled in the Walker River Basin. Snow and sediments from selected sites were also sampled. All samples were analyzed for uranium and other elements. The resulting data provide an understanding of the transport of uranium within a closed hydrologic basin as well as providing a basis for the design of geochemical reconnaissance studies for the Basin and Range Province of the Western United States. Spring and tributary data are useful in locating areas containing anomalous concentrations of uranium. However, agricultural practices obscure the presence of known uranium deposits and render impossible the detection of other known deposits. Uranium is extremely mobile in stream waters and does not appear to sorb or precipitate. Uranium has a long residence time (2500 years) in the open waters of Walker Lake; however, once it crosses the sediment-water interface, it is reduced to the U(IV) state and is lost from solution. Over the past two million years the amount of uranium transported to the terminal point of the Walker River system may have been on the order of 4 ?? 108 kg. This suggests that closed basin termini are sites for significant uranium accumulations and are, therefore, potential sites of uranium ore deposits. ?? 1979.

Potential Aquifer Vulnerability in Regions Down-Gradient from ...

EPA Pesticide Factsheets

Sandstone-hosted roll-front uranium ore deposits originate when U(VI) dissolved in groundwater is reduced and precipitated as insoluble U(IV) minerals. Groundwater redox geochemistry, aqueous complexation, and solute migration are instrumental in leaching uranium from source rocks and transporting it in low concentrations to a chemical redox interface where it is deposited in an ore zone typically containing the uranium minerals uraninite, pitchblende, and/or coffinite; various iron sulfides; native selenium; clays; and calcite. In situ recovery (ISR) of these uranium ores is a process of contacting the uranium mineral deposit with leaching (lixiviant) fluids via injection of the lixiviant into wells drilled into the subsurface aquifer that hosts uranium ore, while other extraction wells pump the dissolved uranium after dissolution of the uranium minerals. Environmental concerns during and after ISR include water quality impacts from: 1) potential excursions of leaching solutions away from the injection zone into down-dip, underlying, or overlying aquifers; 2) potential migration of uranium and its decay products (e.g., Ra, Rn, Pb); and, 3) potential migration of redox-sensitive trace metals (e.g., Fe, Mn, Mo, Se, V), metalloids (e.g., As), and anions (e.g., sulfate). This review describes the geochemical processes that control roll-front uranium transport and fate in groundwater systems, identifies potential aquifer vulnerabilities to ISR operations, identifies

Uranium in groundwater--Fertilizers versus geogenic sources.

PubMed

Liesch, Tanja; Hinrichsen, Sören; Goldscheider, Nico

2015-12-01

Due to its radiological and toxicological properties even at low concentration levels, uranium is increasingly recognized as relevant contaminant in drinking water from aquifers. Uranium originates from different sources, including natural or geogenic, mining and industrial activities, and fertilizers in agriculture. The goal of this study was to obtain insights into the origin of uranium in groundwater while differentiating between geogenic sources and fertilizers. A literature review concerning the sources and geochemical processes affecting the occurrence and distribution of uranium in the lithosphere, pedosphere and hydrosphere provided the background for the evaluation of data on uranium in groundwater at regional scale. The state of Baden-Württemberg, Germany, was selected for this study, because of its hydrogeological and land-use diversity, and for reasons of data availability. Uranium and other parameters from N=1935 groundwater monitoring sites were analyzed statistically and geospatially. Results show that (i) 1.6% of all water samples exceed the German legal limit for drinking water (10 μg/L); (ii) The range and spatial distribution of uranium and occasional peak values seem to be related to geogenic sources; (iii) There is a clear relation between agricultural land-use and low-level uranium concentrations, indicating that fertilizers generate a measurable but low background of uranium in groundwater. Copyright © 2015 Elsevier B.V. All rights reserved.

Concerted Uranium Research in Europe (CURE): toward a collaborative project integrating dosimetry, epidemiology and radiobiology to study the effects of occupational uranium exposure.

PubMed

Laurent, Olivier; Gomolka, Maria; Haylock, Richard; Blanchardon, Eric; Giussani, Augusto; Atkinson, Will; Baatout, Sarah; Bingham, Derek; Cardis, Elisabeth; Hall, Janet; Tomasek, Ladislav; Ancelet, Sophie; Badie, Christophe; Bethel, Gary; Bertho, Jean-Marc; Bouet, Ségolène; Bull, Richard; Challeton-de Vathaire, Cécile; Cockerill, Rupert; Davesne, Estelle; Ebrahimian, Teni; Engels, Hilde; Gillies, Michael; Grellier, James; Grison, Stephane; Gueguen, Yann; Hornhardt, Sabine; Ibanez, Chrystelle; Kabacik, Sylwia; Kotik, Lukas; Kreuzer, Michaela; Lebacq, Anne Laure; Marsh, James; Nosske, Dietmar; O'Hagan, Jackie; Pernot, Eileen; Puncher, Matthew; Rage, Estelle; Riddell, Tony; Roy, Laurence; Samson, Eric; Souidi, Maamar; Turner, Michelle C; Zhivin, Sergey; Laurier, Dominique

2016-06-01

The potential health impacts of chronic exposures to uranium, as they occur in occupational settings, are not well characterized. Most epidemiological studies have been limited by small sample sizes, and a lack of harmonization of methods used to quantify radiation doses resulting from uranium exposure. Experimental studies have shown that uranium has biological effects, but their implications for human health are not clear. New studies that would combine the strengths of large, well-designed epidemiological datasets with those of state-of-the-art biological methods would help improve the characterization of the biological and health effects of occupational uranium exposure. The aim of the European Commission concerted action CURE (Concerted Uranium Research in Europe) was to develop protocols for such a future collaborative research project, in which dosimetry, epidemiology and biology would be integrated to better characterize the effects of occupational uranium exposure. These protocols were developed from existing European cohorts of workers exposed to uranium together with expertise in epidemiology, biology and dosimetry of CURE partner institutions. The preparatory work of CURE should allow a large scale collaborative project to be launched, in order to better characterize the effects of uranium exposure and more generally of alpha particles and low doses of ionizing radiation.

Experiments and Modeling of Uranium Adsorption in the Presence of Other Ions in Simulated Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ladshaw, Austin; Das, Sadananda; Liao, Wei-Po

2015-11-19

Seawater contains uranium at an average concentration of 3.3 ppb, as well as a variety of other ions at either overwhelmingly higher or similar concentrations, which complicate the recovery of uranium. This report describes an investigation of the effects of various factors such as uranium speciation and presence of salts including sodium, calcium, magnesium, and bicarbonate, as well as trace elements such as vanadium on uranium adsorption kinetics in laboratory experiments. Adsorption models are also developed to describe the experimental data of uranium extraction from seawater. Results show that the presence of calcium and magnesium significantly slows down the uraniummore » adsorption kinetics. Vanadium can replace uranium from amidoxime-based adsorbent in the presence of sodium in the solution. Results also show that bicarbonate in the solution strongly competes with amidoxime for binding uranium, and thus slows down the uranium adsorption kinetics. Developed on the basis of the experimental findings, the model is capable of describing the effects of pH, ionic strength, temperature, and concentration of various species. The results of this work are useful in the understanding of the important factors that control the adsorbent capacity and kinetics of uranium uptake by amidoxime-based adsorbents.« less

Uranium quantification in semen by inductively coupled plasma mass spectrometry

USGS Publications Warehouse

Todorov, Todor I.; Ejnik, John W.; Guandalini, Gustavo S.; Xu, Hanna; Hoover, Dennis; Anderson, Larry W.; Squibb, Katherine; McDiarmid, Melissa A.; Centeno, Jose A.

2013-01-01

In this study we report uranium analysis for human semen samples. Uranium quantification was performed by inductively coupled plasma mass spectrometry. No additives, such as chymotrypsin or bovine serum albumin, were used for semen liquefaction, as they showed significant uranium content. For method validation we spiked 2 g aliquots of pooled control semen at three different levels of uranium: low at 5 pg/g, medium at 50 pg/g, and high at 1000 pg/g. The detection limit was determined to be 0.8 pg/g uranium in human semen. The data reproduced within 1.4–7% RSD and spike recoveries were 97–100%. The uranium level of the unspiked, pooled control semen was 2.9 pg/g of semen (n = 10). In addition six semen samples from a cohort of Veterans exposed to depleted uranium (DU) in the 1991 Gulf War were analyzed with no knowledge of their exposure history. Uranium levels in the Veterans’ semen samples ranged from undetectable (<0.8 pg/g) to 3350 pg/g. This wide concentration range for uranium in semen is consistent with known differences in current DU body burdens in these individuals, some of whom have retained embedded DU fragments.

Caulobacter crescentus as a Whole-Cell Uranium Biosensor▿ †

PubMed Central

Hillson, Nathan J.; Hu, Ping; Andersen, Gary L.; Shapiro, Lucy

2007-01-01

We engineered a strain of the bacterium Caulobacter crescentus to fluoresce in the presence of micromolar levels of uranium at ambient temperatures when it is exposed to a hand-held UV lamp. Previous microarray experiments revealed that several Caulobacter genes are significantly upregulated in response to uranium but not in response to other heavy metals. We designated one of these genes urcA (for uranium response in caulobacter). We constructed a reporter that utilizes the urcA promoter to produce a UV-excitable green fluorescent protein in the presence of the uranyl cation, a soluble form of uranium. This reporter is specific for uranium and has little cross specificity for nitrate (<400 μM), lead (<150 μM), cadmium (<48 μM), or chromium (<41.6 μM). The uranium reporter construct was effective for discriminating contaminated groundwater samples (4.2 μM uranium) from uncontaminated groundwater samples (<0.1 μM uranium) collected at the Oak Ridge Field Research Center. In contrast to other uranium detection methodologies, the Caulobacter reporter strain can provide on-demand usability in the field; it requires minimal sample processing and no equipment other than a hand-held UV lamp, and it may be sprayed directly on soil, groundwater, or industrial surfaces. PMID:17905881

Depleted uranium analysis in blood by inductively coupled plasma mass spectrometry

USGS Publications Warehouse

Todorov, T.I.; Xu, H.; Ejnik, J.W.; Mullick, F.G.; Squibb, K.; McDiarmid, M.A.; Centeno, J.A.

2009-01-01

In this study we report depleted uranium (DU) analysis in whole blood samples. Internal exposure to DU causes increased uranium levels as well as change in the uranium isotopic composition in blood specimen. For identification of DU exposure we used the 235U/238U ratio in blood samples, which ranges from 0.00725 for natural uranium to 0.002 for depleted uranium. Uranium quantification and isotopic composition analysis were performed by inductively coupled plasma mass spectrometry. For method validation we used eight spiked blood samples with known uranium concentrations and isotopic composition. The detection limit for quantification was determined to be 4 ng L-1 uranium in whole blood. The data reproduced within 1-5% RSD and an accuracy of 1-4%. In order to achieve a 235U/238U ratio range of 0.00698-0.00752% with 99.7% confidence limit a minimum whole blood uranium concentration of 60 ng L??1 was required. An additional 10 samples from a cohort of veterans exposed to DU in Gulf War I were analyzed with no knowledge of their medical history. The measured 235U/ 238U ratios in the blood samples were used to identify the presence or absence of DU exposure within this patient group. ?? 2009 The Royal Society of Chemistry.

Removal and recovery of uranium(VI) by waste digested activated sludge in fed-batch stirred tank reactor.

PubMed

Jain, Rohan; Peräniemi, Sirpa; Jordan, Norbert; Vogel, Manja; Weiss, Stephan; Foerstendorf, Harald; Lakaniemi, Aino-Maija

2018-05-24

This study demonstrated the removal and recovery of uranium(VI) in a fed-batch stirred tank reactor (STR) using waste digested activated sludge (WDAS). The batch adsorption experiments showed that WDAS can adsorb 200 (±9.0) mg of uranium(VI) per g of WDAS. The maximum adsorption of uranium(VI) was achieved even at an acidic initial pH of 2.7 which increased to a pH of 4.0 in the equilibrium state. Desorption of uranium(VI) from WDAS was successfully demonstrated from the release of more than 95% of uranium(VI) using both acidic (0.5 M HCl) and alkaline (1.0 M Na 2 CO 3 ) eluents. Due to the fast kinetics of uranium(VI) adsorption onto WDAS, the fed-batch STR was successfully operated at a mixing time of 15 min. Twelve consecutive uranium(VI) adsorption steps with an average adsorption efficiency of 91.5% required only two desorption steps to elute more than 95% of uranium(VI) from WDAS. Uranium(VI) was shown to interact predominantly with the phosphoryl and carboxyl groups of the WDAS, as revealed by in situ infrared spectroscopy and time-resolved laser-induced fluorescence spectroscopy studies. This study provides a proof-of-concept of the use of fed-batch STR process based on WDAS for the removal and recovery of uranium(VI). Copyright © 2018 Elsevier Ltd. All rights reserved.

Potential aquifer vulnerability in regions down-gradient from uranium in situ recovery (ISR) sites.

PubMed

Saunders, James A; Pivetz, Bruce E; Voorhies, Nathan; Wilkin, Richard T

2016-12-01

Sandstone-hosted roll-front uranium ore deposits originate when U(VI) dissolved in groundwater is reduced and precipitated as insoluble U(IV) minerals. Groundwater redox geochemistry, aqueous complexation, and solute migration are important in leaching uranium from source rocks and transporting it in low concentrations to a chemical redox interface where it is deposited in an ore zone typically containing the uranium minerals uraninite, pitchblende, and/or coffinite; various iron sulfides; native selenium; clays; and calcite. In situ recovery (ISR) of uranium ores is a process of contacting the uranium mineral deposit with leaching and oxidizing (lixiviant) fluids via injection of the lixiviant into wells drilled into the subsurface aquifer that hosts uranium ore, while other extraction wells pump the dissolved uranium after dissolution of the uranium minerals. Environmental concerns during and after ISR include water quality degradation from: 1) potential excursions of leaching solutions away from the injection zone into down-gradient, underlying, or overlying aquifers; 2) potential migration of uranium and its decay products (e.g., Ra, Rn, Pb); and, 3) potential mobilization and migration of redox-sensitive trace metals (e.g., Fe, Mn, Mo, Se, V), metalloids (e.g., As), and anions (e.g., sulfate). This review describes the geochemical processes that control roll-front uranium transport and fate in groundwater systems, identifies potential aquifer vulnerabilities to ISR operations, identifies data gaps in mitigating these vulnerabilities, and discusses the hydrogeological characterization involved in developing a monitoring program. Published by Elsevier Ltd.

12. VIEW OF DEPLETED URANIUM INGOT AND MOLDS. DEPLETED URANIUM ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

12. VIEW OF DEPLETED URANIUM INGOT AND MOLDS. DEPLETED URANIUM CASTING OPERATIONS CEASED IN 1988. (11/14/57) - Rocky Flats Plant, Non-Nuclear Production Facility, South of Cottonwood Avenue, west of Seventh Avenue & east of Building 460, Golden, Jefferson County, CO

An Investigation on the Persistence of Uranium Hydride during Storage of Simulant Nuclear Waste Packages.

PubMed

Stitt, C A; Harker, N J; Hallam, K R; Paraskevoulakos, C; Banos, A; Rennie, S; Jowsey, J; Scott, T B

2015-01-01

Synchrotron X-rays have been used to study the oxidation of uranium and uranium hydride when encapsulated in grout and stored in de-ionised water for 10 months. Periodic synchrotron X-ray tomography and X-ray powder diffraction have allowed measurement and identification of the arising corrosion products and the rates of corrosion. The oxidation rates of the uranium metal and uranium hydride were slower than empirically derived rates previously reported for each reactant in an anoxic water system, but without encapsulation in grout. This was attributed to the grout acting as a physical barrier limiting the access of oxidising species to the uranium surface. Uranium hydride was observed to persist throughout the 10 month storage period and industrial consequences of this observed persistence are discussed.

URANIUM RECOVERY AND PURIFICATION PROCESS AND PRODUCTION OF HIGH PURITY URANIUM TETRAFLUORIDE

DOEpatents

Bailes, R.H.; Long, R.S.; Grinstead, R.R.

1957-09-17

A process is described wherein an anionic exchange technique is employed to separate uramium from a large variety of impurities. Very efficient and economical purification of contamimated uranium can be achieved by treatment of the contaminated uranium to produce a solution containing a high concentration of chloride. Under these conditions the uranium exists as an aniomic chloride complex. Then the uranium chloride complex is adsorbed from the solution on an aniomic exchange resin, whereby a portion of the impurities remain in the solution and others are retained with the uramium by the resin. The adsorbed impurities are then removed by washing the resin with pure concentrated hydrochloric acid, after which operation the uranium is eluted with pure water yielding an acidic uranyl chloride solution of high purity.

Electrorefining process and apparatus for recovery of uranium and a mixture of uranium and plutonium from spent fuels

DOEpatents

Ackerman, John P.; Miller, William E.

1989-01-01

An electrorefining process and apparatus for the recovery of uranium and a mixture of uranium and plutonium from spent fuel using an electrolytic cell having a lower molten cadmium pool containing spent nuclear fuel, an intermediate electrolyte pool, an anode basket containing spent fuel, and two cathodes, the first cathode composed of either a solid alloy or molten cadmium and the second cathode composed of molten cadmium. Using this cell, additional amounts of uranium and plutonium from the anode basket are dissolved in the lower molten cadmium pool, and then substantially pure uranium is electrolytically transported and deposited on the first alloy or molten cadmium cathode. Subsequently, a mixture of uranium and plutonium is electrotransported and deposited on the second molten cadmium cathode.

Electrorefining process and apparatus for recovery of uranium and a mixture of uranium and plutonium from spent fuels

DOEpatents

Ackerman, J.P.; Miller, W.E.

1987-11-05

An electrorefining process and apparatus for the recovery of uranium and a mixture of uranium and plutonium from spent fuels is disclosed using an electrolytic cell having a lower molten cadmium pool containing spent nuclear fuel, an intermediate electrolyte pool, an anode basket containing spent fuels, two cathodes and electrical power means connected to the anode basket, cathodes and lower molten cadmium pool for providing electrical power to the cell. Using this cell, additional amounts of uranium and plutonium from the anode basket are dissolved in the lower molten cadmium pool, and then purified uranium is electrolytically transported and deposited on a first molten cadmium cathode. Subsequently, a mixture of uranium and plutonium is electrotransported and deposited on a second cathode. 3 figs.

Characterization of low concentration uranium glass working materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eppich, G. R.; Wimpenny, J. B.; Leever, M. E.

A series of uranium-doped silicate glasses were created at (Lawrence Livermore National Laboratory) LLNL, to be used as working reference material analogs for low uranium concentration research. Specifically, the aim of this effort was the generation of well-characterized glasses spanning a range of concentrations and compositions, and of sufficient homogeneity in uranium concentration and isotopic composition, for instrumentation research and development purposes. While the glasses produced here are not intended to replace or become standard materials for uranium concentration or uranium isotopic composition, it is hoped that they will help fill a current gap, providing low-level uranium glasses sufficient formore » methods development and method comparisons within the limitations of the produced glass suite. Glasses are available for research use by request.« less