Alkali Metal Variation and Twisting of the FeNNFe Core in Bridging Diiron Dinitrogen Complexes.

Science.gov (United States)

McWilliams, Sean F; Rodgers, Kenton R; Lukat-Rodgers, Gudrun; Mercado, Brandon Q; Grubel, Katarzyna; Holland, Patrick L

2016-03-21

Alkali metal cations can interact with Fe-N2 complexes, potentially enhancing back-bonding or influencing the geometry of the iron atom. These influences are relevant to large-scale N2 reduction by iron, such as in the FeMoco of nitrogenase and the alkali-promoted Haber-Bosch process. However, to our knowledge there have been no systematic studies of a large range of alkali metals regarding their influence on transition metal-dinitrogen complexes. In this work, we varied the alkali metal in [alkali cation]2[LFeNNFeL] complexes (L = bulky β-diketiminate ligand) through the size range from Na(+) to K(+), Rb(+), and Cs(+). The FeNNFe cores have similar Fe-N and N-N distances and N-N stretching frequencies despite the drastic change in alkali metal cation size. The two diketiminates twist relative to one another, with larger dihedral angles accommodating the larger cations. In order to explain why the twisting has so little influence on the core, we performed density functional theory calculations on a simplified LFeNNFeL model, which show that the two metals surprisingly do not compete for back-bonding to the same π* orbital of N2, even when the ligand planes are parallel. This diiron system can tolerate distortion of the ligand planes through compensating orbital energy changes, and thus, a range of ligand orientations can give very similar energies.

Thorium valency in molten alkali halides in equilibrium with metallic thorium

International Nuclear Information System (INIS)

Smirnov, M.V.; Kudyakov, V.Ya.

1983-01-01

Metallic thorium is shown to corrode in molten alkali halides even in the absence of external oxidizing agents, alkali cations acting as oxidizing agents. Its corrosion rate grows in the series of alkali chlorides from LiCl to CsCl at constant temperature. Substituting halide anions for one another exerts a smaller influence, the rate rising slightly in going from chlorides to bromides and iodides, having the same alkali cations. Thorium valency is determined coulometrically, the metal being dissolved anodically in molten alkali halides and their mixtures. In fluoride melts it is equal to 4 but in chloride, bromide and iodide ones, as a rule, it has non-integral values between 4 and 2 which diminish as the temperature is raised, as the thorium concentration is lowered, as the radii of alkali cations decrease and those of halide anions increase. The emf of cells Th/N ThHlsub(n) + (1-N) MHl/MHl/C, Hlsub(2(g)) where Hl is Cl, Br or I, M is Li, Na, K, Cs or Na + K, and N < 0.05, is measured as a function of concentration at several temperatures. Expressions are obtained for its concentration dependence. The emf grows in the series of alkali chlorides from LiCl to CsCl, other conditions being equal. (author)

Synthesis and adsorption investigations of zeolites MCM-22 and MCM-49 modified by alkali metal cations

Czech Academy of Sciences Publication Activity Database

Pawlesa, Justyna; Zukal, Arnošt; Čejka, Jiří

2007-01-01

Roč. 13, 3-4 (2007), s. 257-265 ISSN 0929-5607 Grant - others:DeSSANS(XE) SES6-CT-2005-020133; INDENS(XE) MRTN-CT-2004-005503 Institutional research plan: CEZ:AV0Z40400503 Source of funding: R - rámcový projekt EK ; R - rámcový projekt EK Keywords : MCM-22 zeolite * MCM-49 zeolite * alkali metal cation exchange * N2 and CO2 adsorption Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.880, year: 2007

Correction: A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

Science.gov (United States)

Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

2016-12-22

Correction for 'A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide' by Chee Koon Ng et al., Chem. Commun., 2016, 52, 11842-11845.

Effects of alkali metal cations on phospho-enzyme levels and [3H] ouabain binding to (Na+ + K+)-ATPase.

Science.gov (United States)

Han, C S; Tobin, T; Akera, T; Brody, T M

1976-05-13

The effects of several alkali metal cations on the relationship between steady state phospho-enzyme levels and initial velocity and equilibrium levels of [3H]-ouabain binding to (Na+ + K+)-ATPase (ATP phosphohydrolase EC 3.6.1.3.) were examined. Only Na+ increased both phospho-enzyme and [3H] ouabain binding levels above those observed in the presence of Mg2+ alone. While Na+ stimulated phosphorylation with an apparent Km of about 1 mM, its stimulation of [3H] ouabain binding was biphasic, the lower Km for stimulation corresponding to the Km for formation of phospho-enzyme. Among the other alkali metal cations, potassium, rubidium and lithium were at least eight times more effect in reducing phospho-enzyme levels than in reducing [3H] ouabain binding. This discrepancy is not due to the stability of the enzyme-ouabain complex, nor to any action on the rates of formation or dissociation of the enzyme-ouabain complex. The data thus suggest that [3H] ouabain interacts with the K+, Rb+ or Li+ -enzyme complexes. For Li+, this hypothesis is further supported by the observation that Li+ can cirectly increase the equilibrium level of [3H] ouabain binding to this enzyme under certain conditions.

Cobalt(2) and nickel(2) tris-acetylacetonates with alkali metal cations in outer sphere

International Nuclear Information System (INIS)

Steblyanko, A.Yu.; Grigor'ev, A.N.; Martynenko, L.I.

1996-01-01

Anhydrous tris-acetylacetonates of Co(2) and Ni(2) with alkali metal cations in outer sphere were synthesized and investigated by different physicochemical methods. Chemical analysis and IR-spectroscopy show, that complex composition corresponds to the formula Eh[MA 3 ] (where Eh + - Li + , Na + , K + , Rb + , Cs + ; M - Co(2), Ni(2); A - - acetyacetonate-ion). Eh[MA 3 ] heating in vacuum leads to transition of volatile Co(2) and Ni(2) acetylacetonates to gaseous phase. The data of photoelectron spectroscopy and vacuum sublimation show, that Li[MA 3 ] is transformed to gaseous phase congruently and only partially dissociates to EhA and MA 2 . Li[MA 3 ] and Cs[MA 3 ] are characterized by the lowest thermal stability at atmospheric pressure. Low stability of Li[MA 3 ] is related with detachment of one of A - radical from [MA 3 ] complex anion by Li + cation under conditions, when LiA and Li[MA 3 ] are volatile. 11 refs.; 2 figs.; 3 tabs

Discriminating Properties of Alkali Metal Ions Towards the Constituents of Proteins and Nucleic Acids. Conclusions from Gas-Phase and Theoretical Studies.

Science.gov (United States)

Rodgers, Mary T; Armentrout, Peter B

2016-01-01

Quantitative insight into the structures and thermodynamics of alkali metal cations interacting with biological molecules can be obtained from studies in the gas phase combined with theoretical work. In this chapter, the fundamentals of the experimental and theoretical techniques are first summarized and results for such work on complexes of alkali metal cations with amino acids, small peptides, and nucleobases are reviewed. Periodic trends in how these interactions vary as the alkali metal cations get heavier are highlighted.

Influence of alkali metal hydroxides on corrosion of Zr-base alloys

International Nuclear Information System (INIS)

Jeong, Yong Hwan

1996-01-01

The influence of group-1 alkali hydroxides on different Zr-based alloys have been carried out in static autoclaves at 350 deg C in pressurized water, conditioned in low(0.32 mmol), medium(4.3 mmol) and high(31.5 mmol) equimolar concentration of Li-, Na-, K-, Rb- and Cs-hydroxide. Two types of alloys have been investigated: Zr-Sn-(TRM, Transition metal) and Zr-Sn-Nb-(TRM, Transition metal). From the experiments the cation could be identified as the responsible species for corrosion of Zr alloy in alkalized water. The radius of the cation governs the accelerated corrosion in the pre-transition region of Zr alloy. Incorporation of alkali cation into the zirconium oxide lattice is probably the mechanism which allows the corrosion enhancement for Li and Na and the significant lower effect for the other bases. Nb containing alloys showed lower corrosion resistance than Zr-Sn-TRM alloys in all alkali solutions. Both types of alloys were corroded significantly more in LiOH and NaOH than in the other alkali environments. Lowest corrosive aggressiveness has been found for CsOH followed by KOH. Concluding from the corrosion behavior in the different alkali environments and taking into account the tendency to accelerate the corrosion of Zr alloys, CsOH and KOH are possible alternate alkali for PWR (Pressurized Water Reactor) application. (author)

Potential-modulated intercalation of alkali cations into metal hexacyanoferrate coated electrodes. 1998 annual progress report

International Nuclear Information System (INIS)

Schwartz, D.T.

1998-01-01

'This program is studying potential-driven cation intercalation and deintercalation in metal hexacyanoferrate compounds, with the eventual goal of creating materials with high selectivity for cesium separations and long cycle lifetimes. The separation of radiocesium from other benign cations has important implications for the cost of processing a variety of cesium contaminated DOE wasteforms. This report summarizes results after nine months of work. Much of the initial efforts have been directed towards quantitatively characterizing the selectivity of nickel hexacyanoferrate derivatized electrodes for intercalating cesium preferentially over other alkali metal cations. Using energy dispersive xray spectroscopy (ex-situ, but non-destructive) and ICP analysis (ex-situ and destructive), the authors have demonstrated that the nickel hexacyanoferrate lattice has a strong preference for intercalated cesium over sodium. For example, when ions are reversibly loaded into a nickel hexacyanoferrate thin film from a solution containing 0.9999 M Na + and 0.0001 M Cs + , the film intercalates 40% as much Cs + as when loaded from pure 1 M Cs + containing electrolyte (all electrolytes use nitrates as the common anion). The authors have also shown that, contrary to the common assumptions found in the literature, a significant fraction of the thin film is not active initially. A new near infrared laser has been purchased and is being added to the Raman spectroscopy facilities to allow in-situ studies of the intercalation processes.'

Process to separate alkali metal salts from alkali metal reacted hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Gordon, John Howard; Alvare, Javier; Larsen, Dennis; Killpack, Jeff

2017-06-27

A process to facilitate gravimetric separation of alkali metal salts, such as alkali metal sulfides and polysulfides, from alkali metal reacted hydrocarbons. The disclosed process is part of a method of upgrading a hydrocarbon feedstock by removing heteroatoms and/or one or more heavy metals from the hydrocarbon feedstock composition. This method reacts the oil feedstock with an alkali metal and an upgradant hydrocarbon. The alkali metal reacts with a portion of the heteroatoms and/or one or more heavy metals to form an inorganic phase containing alkali metal salts and reduced heavy metals, and an upgraded hydrocarbon feedstock. The inorganic phase may be gravimetrically separated from the upgraded hydrocarbon feedstock after mixing at a temperature between about 350.degree. C. to 400.degree. C. for a time period between about 15 minutes and 2 hours.

Ionic conductivity of polymer gels deriving from alkali metal ionic liquids and negatively charged polyelectrolytes

International Nuclear Information System (INIS)

Ogihara, Wataru; Sun Jiazeng; Forsyth, Maria; MacFarlane, Douglas R.; Yoshizawa, Masahiro; Ohno, Hiroyuki

2004-01-01

We have prepared polymer gel electrolytes with alkali metal ionic liquids (AMILs) that inherently contain alkali metal ions. The AMIL consisted of sulfate anion, imidazolium cation, and alkali metal cation. AMILs were mixed directly with poly(3-sulfopropyl acrylate) lithium salt or poly(2-acrylamido-2-methylpropanesulfonic acid) lithium salt to form polymer gels. The ionic conductivity of these gels decreased with increasing polymer fraction, as in general ionic liquid/polymer mixed systems. At low polymer concentrations, these gels displayed excellent ionic conductivity of 10 -4 to 10 -3 S cm -1 at room temperature. Gelation was found to cause little change in the 7 Li diffusion coefficient of the ionic liquid, as measured by pulse-field-gradient NMR. These data strongly suggest that the lithium cation migrates in successive pathways provided by the ionic liquids

Rice Na+/H+- antiporter Nhx1 partially complements the alkali-metal-cation sensitivity of yeast strains lacking three sodium transporters

Czech Academy of Sciences Publication Activity Database

Kinclová-Zimmermannová, Olga; Flegelová, Hana; Sychrová, Hana

2004-01-01

Roč. 49, č. 5 (2004), s. 519-525 ISSN 0015-5632 R&D Projects: GA ČR GA204/02/1240; GA AV ČR IAA5011407 Grant - others:EU(XE) QLK3-CT-2001-00533 Institutional research plan: CEZ:AV0Z5011922 Keywords : alkali metal cations * Na/H antiporter * yeast Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 1.034, year: 2004

(abstract) Experimental and Modeling Studies of the Exchange Current at the Alkali Beta'-Alumina/Porous Electrode/Alkali Metal Vapor Three Phase Boundary

Science.gov (United States)

Williams, R. M.; Jeffries-Nakamura, B.; Ryan, M. A.; Underwood, M. L.; O'Connor, D.; Kikkert, S.

1993-01-01

The microscopic mechanism of the alkali ion-electron recombination reaction at the three phase boundary zone formed by a porous metal electrode in the alkali vapor on the surface of an alkali beta'-alumina solid electrolyte (BASE) ceramic has been studied by comparison of the expected rates for the three simplest reaction mechanisms with known temperature dependent rate data; and the physical parameters of typical porous metal electrode/BASE/alkali metal vapor reaction zones. The three simplest reactions are tunneling of electrons from the alkali coated electrode to a surface bound alkali metal ion; emission of an electron from the electrode with subsequent capture by a surface bound alkali metal ion; and thermal emission of an alkali cation from the BASE and its capture on the porous metal electrode surface where it may recombine with an electron. Only the first reaction adequately accounts for both the high observed rate and its temperature dependence. New results include crude modeling of simple, one step, three phase, solid/solid/gas electrochemical reaction.

Influence of alkali metal hydroxides on corrosion of Zr-based alloys

International Nuclear Information System (INIS)

Jeong, Y.H.; Ruhmann, H.; Garzarolli, F.

1997-01-01

In this study the influence of group-1 alkali hydroxides on different zirconium based alloys has been evaluated. The experiments have been carried out in small stainless steel autoclaves at 350 deg. C in pressurized 17 MPa water, with in low (0.32 mmol), medium (4.3 mmol) and high (31.5 mmol) equimolar concentrations of Li-, Na-, K-, Rb- and Cs-Hydroxides. Two types of alloys have been investigated: Zr-Sn-(Transition metal) and Zr-Sn-Nb-(Transition metal). The corrosion behaviour was evaluated from weight gain measurements. From the experiments the cation could be identified as the responsible species for zirconium alloy corrosion in alkalized water. The radius of the cation governs the corrosion behaviour in the pre accelerated region of zircaloy corrosion. Incorporating of alkali cations into the zirconium oxide lattice is probably the mechanism which allows the corrosion enhancement for Li and Na and the significantly lower effect for the other bases. Nb containing alloys show lower corrosion resistance than alloys from the Zr-Sn-TRM system in all alkali solutions. Both types of alloys corrode significantly more in LiOH and NaOH than in the other alkali environments. Lowest corrosive aggressiveness has been found for CsOH followed by KOH. Concluding from the corrosion behaviour in the different alkali environments and taking into account the tendency to promote accelerate corrosion, CsOH and KOH are possible alternate alkalis for PWR application. (author). 17 refs, 15 figs, 5 tabs

Influence of alkali metal hydroxides on corrosion of Zr-based alloys

Energy Technology Data Exchange (ETDEWEB)

Jeong, Y H [Korea Atomic Energy Research Inst., Dae Jun (Korea, Republic of); Ruhmann, H; Garzarolli, F [Siemens-KWU, Power Generation Group, Erlangen (Germany)

1997-02-01

In this study the influence of group-1 alkali hydroxides on different zirconium based alloys has been evaluated. The experiments have been carried out in small stainless steel autoclaves at 350 deg. C in pressurized 17 MPa water, with in low (0.32 mmol), medium (4.3 mmol) and high (31.5 mmol) equimolar concentrations of Li-, Na-, K-, Rb- and Cs-Hydroxides. Two types of alloys have been investigated: Zr-Sn-(Transition metal) and Zr-Sn-Nb-(Transition metal). The corrosion behaviour was evaluated from weight gain measurements. From the experiments the cation could be identified as the responsible species for zirconium alloy corrosion in alkalized water. The radius of the cation governs the corrosion behaviour in the pre accelerated region of zircaloy corrosion. Incorporating of alkali cations into the zirconium oxide lattice is probably the mechanism which allows the corrosion enhancement for Li and Na and the significantly lower effect for the other bases. Nb containing alloys show lower corrosion resistance than alloys from the Zr-Sn-TRM system in all alkali solutions. Both types of alloys corrode significantly more in LiOH and NaOH than in the other alkali environments. Lowest corrosive aggressiveness has been found for CsOH followed by KOH. Concluding from the corrosion behaviour in the different alkali environments and taking into account the tendency to promote accelerate corrosion, CsOH and KOH are possible alternate alkalis for PWR application. (author). 17 refs, 15 figs, 5 tabs.

Selectivity in stripping of alkali-metal cations from crown ether carboxylate complexes

International Nuclear Information System (INIS)

Bartsch, R.A.; Walkowiak, W.; Robison, T.W.

1992-01-01

To probe the effect of structural variations within the ionophore upon the efficiency and selectivity of solvent extraction, a variety of crown ether carboxylic acids and phosphonic acid monoesters have been synthesized. In other studies the influence of the organic diluent upon extraction efficiency and selectivity has been probed for such proton-ionizable crown ethers. In the present investigation, attention is focused upon selectivity in the stripping step. Although the efficiency of metal ion stripping is often examined in solvent extraction studies, the selectivity of competitive metal ion release under different conditions is much less frequently considered. In this study, competitive stripping of metal ions from chloroform solutions of five-alkali-metal crown ether carboxylates by varying concentrations of aqueous hydrochloric acid is examined. Alkali metals used were Li, Na, K, Rb, and Cs

A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

Science.gov (United States)

Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

2016-09-27

Binary catalyst systems comprising a cationic Ru-CNC pincer complex and an alkali metal salt were developed for selective hydroboration of CO 2 utilizing pinacolborane at r.t. and 1 atm CO 2 , with the combination of [Ru(CNC Bn )(CO) 2 (H)][PF 6 ] and KOCO 2 t Bu producing formoxyborane in 76% yield. A bicyclic catalytic mechanism was proposed and discussed.

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

International Nuclear Information System (INIS)

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

2011-01-01

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, 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 polyatomic nature of NH4.

Alkali metal and alkali earth metal gadolinium halide scintillators

Science.gov (United States)

Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

2016-08-02

The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

Methods of recovering alkali metals

Science.gov (United States)

Krumhansl, James L; Rigali, Mark J

2014-03-04

Approaches for alkali metal extraction, sequestration and recovery are described. For example, a method of recovering alkali metals includes providing a CST or CST-like (e.g., small pore zeolite) material. The alkali metal species is scavenged from the liquid mixture by the CST or CST-like material. The alkali metal species is extracted from the CST or CST-like material.

Alkali metal ion battery with bimetallic electrode

Science.gov (United States)

Boysen, Dane A; Bradwell, David J; Jiang, Kai; Kim, Hojong; Ortiz, Luis A; Sadoway, Donald R; Tomaszowska, Alina A; Wei, Weifeng; Wang, Kangli

2015-04-07

Electrochemical cells having molten electrodes having an alkali metal provide receipt and delivery of power by transporting atoms of the alkali metal between electrode environments of disparate chemical potentials through an electrochemical pathway comprising a salt of the alkali metal. The chemical potential of the alkali metal is decreased when combined with one or more non-alkali metals, thus producing a voltage between an electrode comprising the molten the alkali metal and the electrode comprising the combined alkali/non-alkali metals.

Carbon nitride nanotube as a sensor for alkali and alkaline earth cations

Energy Technology Data Exchange (ETDEWEB)

Beheshtian, Javad [Department of Chemistry, Shahid Rajaee Teacher Training University, P.O. Box: 16875-163, Tehran (Iran, Islamic Republic of); Baei, Mohammad T. [Department of Chemistry, Azadshahr Branch, Islamic Azad University, Azadshahr, Golestan (Iran, Islamic Republic of); Bagheri, Zargham [Physics Group, Science Department, Islamic Azad University, Islamshahr Branch, P.O. Box: 33135-369, Islamshahr, Tehran (Iran, Islamic Republic of); Peyghan, Ali Ahmadi, E-mail: ahmadi.iau@gmail.com [Young Researchers Club, Islamic Azad University, Islamshahr Branch, Tehran (Iran, Islamic Republic of)

2013-01-01

Highlights: Black-Right-Pointing-Pointer Adsorption of alkali and alkaline earth cations on a CN nanotube studied by DFT. Black-Right-Pointing-Pointer The alkaline cation adsorption may raise potential barrier of the electron emission. Black-Right-Pointing-Pointer The tube may act as a sensor in the presence of alkali and alkaline cations. - Abstract: Adsorption of several alkali (Li{sup +}, Na{sup +}, and K{sup +}) and alkaline earth (Be{sup 2+}, Mg{sup 2+}, and Ca{sup 2+}) cations on the surface of a zigzag (9, 0) carbon nitride nanotube has been investigated using density functional theory. It has been found that almost all of the cations prefer to be strongly chemisorbed at the center of porous site of the tube surface. The adsorption of alkaline cations much more influences the electronic properties of the tube, in comparison with the alkali ones, so that it is transformed from an intrinsic semiconductor with HOMO/LUMO energy gap of 4.02 eV to extrinsic p-type one with the gap of 0.54-1.94 eV. The alkaline cation adsorption may significantly raise potential barrier of the electron emission from the tube surface, hence impeding the field emission. It has been also concluded that the electrical sensitivity of the tube toward the cations may be in the order: Be{sup 2+} Much-Greater-Than Mg{sup 2+} Much-Greater-Than Ca{sup 2+} Much-Greater-Than Li{sup +} {approx} Na{sup +} {approx} K{sup +}.

Alkali metal for ultraviolet band-pass filter

Science.gov (United States)

Mardesich, Nick (Inventor); Fraschetti, George A. (Inventor); Mccann, Timothy A. (Inventor); Mayall, Sherwood D. (Inventor); Dunn, Donald E. (Inventor); Trauger, John T. (Inventor)

1993-01-01

An alkali metal filter having a layer of metallic bismuth deposited onto the alkali metal is provided. The metallic bismuth acts to stabilize the surface of the alkali metal to prevent substantial surface migration from occurring on the alkali metal, which may degrade optical characteristics of the filter. To this end, a layer of metallic bismuth is deposited by vapor deposition over the alkali metal to a depth of approximately 5 to 10 A. A complete alkali metal filter is described along with a method for fabricating the alkali metal filter.

IR spectroscopy of cationized aliphatic amino acids: Stability of charge-solvated structure increases with metal cation size

NARCIS (Netherlands)

Drayss, M. K.; Armentrout, P. B.; Oomens, J.; Schaefer, M.

2010-01-01

Gas-phase structures of alkali metal cationized (Li+, Na+,K+, Rb+, and Cs+) proline (Pro) and N-methyl alanine have been investigated using infrared multiple photon dissociation (IRMPD) spectroscopy utilizing light generated by a free electron laser and computational modeling. Measured IRMPD spectra

IR spectroscopy of cationized aliphatic amino acids: Stability of charge-solvated structure increases with metal cation size

NARCIS (Netherlands)

Drayß, M.K.; Armentrout, P.B.; Oomens, J.; Schäfer, M.

2010-01-01

Gas-phase structures of alkali metal cationized (Li+, Na+, K+, Rb+, and Cs+) proline (Pro) and N-methyl alanine have been investigated using infrared multiple photon dissociation (IRMPD) spectroscopy utilizing light generated by a free electron laser and computational modeling. Measured IRMPD

Purification of alkali metal nitrates

Science.gov (United States)

Fiorucci, Louis C.; Gregory, Kevin M.

1985-05-14

A process is disclosed for removing heavy metal contaminants from impure alkali metal nitrates containing them. The process comprises mixing the impure nitrates with sufficient water to form a concentrated aqueous solution of the impure nitrates, adjusting the pH of the resulting solution to within the range of between about 2 and about 7, adding sufficient reducing agent to react with heavy metal contaminants within said solution, adjusting the pH of the solution containing reducing agent to effect precipitation of heavy metal impurities and separating the solid impurities from the resulting purified aqueous solution of alkali metal nitrates. The resulting purified solution of alkali metal nitrates may be heated to evaporate water therefrom to produce purified molten alkali metal nitrate suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of alkali metal nitrates.

Quantum-chemistry based calibration of the alkali metal cation series (Li(+)-Cs(+)) for large-scale polarizable molecular mechanics/dynamics simulations.

Science.gov (United States)

Dudev, Todor; Devereux, Mike; Meuwly, Markus; Lim, Carmay; Piquemal, Jean-Philip; Gresh, Nohad

2015-02-15

The alkali metal cations in the series Li(+)-Cs(+) act as major partners in a diversity of biological processes and in bioinorganic chemistry. In this article, we present the results of their calibration in the context of the SIBFA polarizable molecular mechanics/dynamics procedure. It relies on quantum-chemistry (QC) energy-decomposition analyses of their monoligated complexes with representative O-, N-, S-, and Se- ligands, performed with the aug-cc-pVTZ(-f) basis set at the Hartree-Fock level. Close agreement with QC is obtained for each individual contribution, even though the calibration involves only a limited set of cation-specific parameters. This agreement is preserved in tests on polyligated complexes with four and six O- ligands, water and formamide, indicating the transferability of the procedure. Preliminary extensions to density functional theory calculations are reported. © 2014 Wiley Periodicals, Inc.

A study on optical properties of poly (ethylene oxide) based polymer electrolyte with different alkali metal iodides

Science.gov (United States)

Rao, B. Narasimha; Suvarna, R. Padma

2016-05-01

Polymer electrolytes were prepared by adding poly (ethylene glycol) dimethyl ether (PEGDME), TiO2 (nano filler), different alkali metal iodide salts RI (R+=Li+, Na+, K+, Rb+, Cs+) and I2 into Acetonitrile gelated with Poly (ethylene oxide) (PEO). Optical properties of poly (ethylene oxide) based polymer electrolytes were studied by FTIR, UV-Vis spectroscopic techniques. FTIR spectrum reveals that the alkali metal cations were coordinated to ether oxygen of PEO. The optical absorption studies were made in the wavelength range 200-800 nm. It is observed that the optical absorption increases with increase in the radius of alkali metal cation. The optical band gap for allowed direct transitions was evaluated using Urbach-edges method. The optical properties such as optical band gap, refractive index and extinction coefficient were determined. The studied polymer materials are useful for solar cells, super capacitors, fuel cells, gas sensors etc.

Alkali metal hydride formation

International Nuclear Information System (INIS)

1976-01-01

The present invention relates to a method of producing alkali metal hydrides by absorbing hydrogen gas under pressure into a mixture of lower alkyl mono amines and alkali metal alkyl amides selected from sodium and potassium amides formed from said amines. The present invention also includes purification of a mixture of the amines and amides which contain impurities, such as is used as a catalytic exchange liquid in the enrichment of deuterium, involving the formation of the alkali metal hydride

Process for the disposal of alkali metals

International Nuclear Information System (INIS)

Lewis, L.C.

1979-01-01

The invention describes a method of disposing of alkali metals by forming a solid waste for storage. The method comprises preparing an aqueous disposal solution of at least 55 weight percent alkali metal hydroxide, heating the alkali metal to melting temperature to form a feed solution, and spraying the molten feed solution into the disposal solution. The alkali metal reacts with the water in the disposal solution in a controlled reaction which produces alkali metal hydroxide, hydrogen and heat and thereby forms a solution of alkali metal hydroxides. Water is added to the solution in amounts sufficient to maintain the concentration of alkali metal hydroxides in the solution at 70 to 90 weight percent, and to maintain the temperature of the solution at about the boiling point. Removing and cooling the alkali metal hydroxide solution thereby forms a solid waste for storage. The method is particularly applicable to radioactive alkali metal reactor coolant. (auth)

The chemistry of the liquid alkali metals

International Nuclear Information System (INIS)

Addison, C.C.

1984-01-01

A study of liquid alkali metals. It encourages comparison with molecular solvents in chapter covering the nature and reactivity of dissolved species, solvation, solubility and electrical conductivity of solutions. It demonstrates lab techniques unique to liquid alkali metals. It discusses large-scale applications from storage batteries to sodium-cooled reactors and future fusion reactors, and associated technological problems. Contents: Some Basic Physical and Chemical Properties; Manipulation of the Liquids; The Chemistry of Purification Methods; Species Formed by Dissolved Elements; Solubilities and Analytical Methods; Alkali Metal Mixtures; Solvation in Liquid Metal; Reactions Between Liquid Alkali Metals and Water; Reactions of Nitrogen with Lithium and the Group II Metals in Liquid Sodium; The Formation, Dissociation and Stability of Heteronuclear Polyatomic Anions; Reactions of the Liquid Alkali Metals and Their Alloys with Simple Alipatic Hydrocarbons; Reactions of the Liquid Alkali Metals with Some Halogen Compounds; Hydrogen, Oxygen and Carbon Meters; Surface Chemistry and Wetting; Corrosion of Transition Metals by the Liquid Alkali Metals; Modern Applications of the Liquid Alkali Metals

On-chip fabrication of alkali-metal vapor cells utilizing an alkali-metal source tablet

International Nuclear Information System (INIS)

Tsujimoto, K; Hirai, Y; Sugano, K; Tsuchiya, T; Tabata, O; Ban, K; Mizutani, N

2013-01-01

We describe a novel on-chip microfabrication technique for the alkali-metal vapor cell of an optically pumped atomic magnetometer (OPAM), utilizing an alkali-metal source tablet (AMST). The newly proposed AMST is a millimeter-sized piece of porous alumina whose considerable surface area holds deposited alkali-metal chloride (KCl) and barium azide (BaN 6 ), source materials that effectively produce alkali-metal vapor at less than 400 °C. Our experiments indicated that the most effective pore size of the AMST is between 60 and 170 µm. The thickness of an insulating glass spacer holding the AMST was designed to confine generated alkali metal to the interior of the vapor cell during its production, and an integrated silicon heater was designed to seal the device using a glass frit, melted at an optimum temperature range of 460–490 °C that was determined by finite element method thermal simulation. The proposed design and AMST were used to successfully fabricate a K cell that was then operated as an OPAM with a measured sensitivity of 50 pT. These results demonstrate that the proposed concept for on-chip microfabrication of alkali-metal vapor cells may lead to effective replacement of conventional glassworking approaches. (paper)

Alkali metals and group IIA metals

International Nuclear Information System (INIS)

Fenton, D.E.

1987-01-01

This chapter on the coordination complexes of the alkali metals of group IIA starts with a historical perspective of their chemistry, from simple monodentate ligands, metal-β-diketonates to the macrocyclic polyethers which act as ligands to the alkali and akaline earth metals. Other macrocyclic ligands include quarterenes, calixarenes, porphyrins, phthalocyanines and chlorophylls. A section on the naturally occurring ionophores and carboxylic ionophores is included. (UK)

Saturated vapor pressure over molten mixtures of GaCl3 and alkali metal chlorides

International Nuclear Information System (INIS)

Salyulev, A.B.; Smolenskij, V.V.; Moskalenko, N.I.

2004-01-01

Volatilities of GaCl 3 and alkali metal chlorides over diluted (up to 3 mol %) solutions of GaCl 3 in LiCl, NaCl, KCl, RbCl, and CsCl were measured at 1100 K by dynamic and indirect static methods. Chemical composition of saturated vapor over the mixed melts was determined. Partial pressures of the components were calculated. Their values depend essentially on specific alkali metal cation and on concentration of GaCl 3 ; their variation permits altering parameters of GaCl 3 distillation from the salt melt in a wide range [ru

Coordination chemistry insights into the role of alkali metal promoters in dinitrogen reduction.

Science.gov (United States)

Connor, Gannon P; Holland, Patrick L

2017-05-15

The Haber-Bosch process is a major contributor to fixed nitrogen that supports the world's nutritional needs and is one of the largest-scale industrial processes known. It has also served as a testing ground for chemists' understanding of surface chemistry. Thus, it is significant that the most thoroughly developed catalysts for N 2 reduction use potassium as an electronic promoter. In this review, we discuss the literature on alkali metal cations as promoters for N 2 reduction, in the context of the growing knowledge about cooperative interactions between N 2 , transition metals, and alkali metals in coordination compounds. Because the structures and properties are easier to characterize in these compounds, they give useful information on alkali metal interactions with N 2 . Here, we review a variety of interactions, with emphasis on recent work on iron complexes by the authors. Finally, we draw conclusions about the nature of these interactions and areas for future research.

Alkali metal hafnium oxide scintillators

Science.gov (United States)

Bourret-Courchesne, Edith; Derenzo, Stephen E.; Taylor, Scott Edward

2018-05-08

The present invention provides for a composition comprising an inorganic scintillator comprising an alkali metal hafnate, optionally cerium-doped, having the formula A2HfO3:Ce; wherein A is an alkali metal having a valence of 1, such as Li or Na; and the molar percent of cerium is 0% to 100%. The alkali metal hafnate are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

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

International Nuclear Information System (INIS)

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

1979-01-01

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

Validation of ion chromatography for the determination of transition metal ions along with alkali, alkaline earth metal elements for uranium oxide fuel

International Nuclear Information System (INIS)

Kelkar, Anoop; Prakash, Amrit; Afzal, Mohd.; Panakkal, J.P.

2009-02-01

The present report describes the use of Ion chromatography (IC) methods with spectrophotometric and direct conductivity detection for the determination of transition metal elements and alkali alkaline earth metal ions in UO 2 pellets. Transmet analytical column and Metrosep- cation 1-2 column were used for the separation of transition metal elements and alkali and alkaline earth metal elements respectively. Oxalic acid and mixture of pyridine 2,6-dicarboxylic acid (PDCA), Na 2 SO 4 and NaCl were used as mobile phase for the separation of transition metal ions and monitored after post - column reaction with 4,2-pyridylazo resorcinol (PAR) at 520nm spectrophotometrically. In the determination of alkali and alkaline earth metal ions the interference of transition metals are removed by complexing them with PDCA. Mixture of tartaric acid and PDCA employed in the separation of alkali and alkaline earth metal ions and monitored on direct conductivity detector. Mobile phase composition was optimised for the base line separation. Calibration plots of Fe 3+ , Cu 2+ , Ni 2+ , Co 2+ , Cd 2+ , Mn 2+ , Li + , Na + , K + , Mg 2+ , Ca 2+ and Sr 2+ were linear over a wide dynamic range with regression coefficient better than 0.999. Detection limit of above ions were between 5-30ppb. To prevent the overloading of the cation exchange column, uranium matrix was removed from UO 2 sample by solvent extraction with 30% TBP - TOPO/CCl 4 . Ten sintered UO2 pellets of same lot were analysed and R.S.D. ±10% was obtained. These methods were validated by analysis of ILCE standards of UO 2 . (author)

Chemistry of alkali cation exchanged faujasite and mesoporous NaX using alkyl halides and phosphates

Science.gov (United States)

Lee, Min-Hong

The purpose of this work was to increase the reactivity of Faujasite X (NaX) zeolite toward the reactive decontamination of materials subject to nucleophilic attack by means of zeolite cation optimization and by means of the synthesis of mesoporous Faujasite X. Primary alkyl halides and trialkyl phosphates have been the test materials on which the cation-optimized and mesoporous zeolites have been tested. In the alkali cation optimization work, reactions of methyl iodide and 1-chloropropane with alkali metal cation exchanged Faujasite zeolite X were investigated at room temperature. The reactivity of the framework and the product formation were shown to depend on zeolite framework counter-cation. A quantitative study of zeolite product formation has been carried out, primarily using solid-state NMR spectroscopy. Large alkali cations showed preference toward substitution chemistry. In contrast, alkyl halide exposed LiX and NaX zeolites underwent both substitution and elimination. Subsequently introduced water molecules led to hydrolysis of framework species that was sensitive to framework counter-cation. The mesoporous NaX zeolites work undertakes to test whether an improvement in surface chemical reactivity can be achieved by introducing mesopores into the already reactive nucleophilic microporous NaX zeolite. Incorporation of the polydiallyl dimethyl ammonium chloride (PDADMAC) template and the formation of mesopores in Faujasite X zeolite (NaX) were successful and well-characterized. The mesopores are proposed to have occurred from incorporation of the cationic PDADMAC polymer into the zeolite by compensating zeolite framework charge. Subsequent sodium cation exchange of calcined mesoporous NaX was shown to restore the chemical reactivity characteristic of as-synthesized NaX. Trialkyl organophosphorous compounds underwent substitution reactions. The reactivity of both microporous and mesoporous Faujasite zeolite X and the product formation was shown to depend on

Synthesis and Characterization of Novel Ternary and Quaternary Alkali Metal Thiophosphates

KAUST Repository

Alahmary, Fatimah S.

2014-05-01

The ongoing development of nonlinear optical (NLO) crystals such as coherent mid-IR sources focuses on various classes of materials such as ternary and quaternary metal chalcophosphates. In case of thiophosphates, the connection between PS4-tetrahedral building blocks and metals gives rise to a broad structural variety where approximately one third of all known ternary (A/P/S) and quaternary (A/M/P/S) (A = alkali metal, M = metal) structures are acentric and potential nonlinear optical materials. The molten alkali metal polychalcophosphate fluxes are a well-established method for the synthesis of new ternary and quaternary thiophosphate and selenophosphate compounds. It has been a wide field of study and investigation through the last two decades. Here, the flux method is used for the synthesis of new quaternary phases containing Rb, Ag, P and S. Four new alkali metal thiophosphates, Rb4P2S10, RbAg5(PS4), Rb2AgPS4 and Rb3Ag9(PS4)4, have been synthesized successfully from high purity elements and binary starting materials. The new compounds were characterized by single crystal and powder X-ray diffraction, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), ultraviolet-visible (UV-VIS), Raman spectroscopy, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). These compounds show interesting structural variety and physical properties. The crystal structures feature 3D anionic framework built up of PS4 tetrahedral units and charge balanced by Ag and alkali metal cations. All prepared compounds are semiconductors with band gap between 2.3 eV to 2.6 eV and most of them are thermally stable up to 600ºC.

Coprecipitation of alkali metal ions with calcium carbonate

International Nuclear Information System (INIS)

Okumura, Minoru; Kitano, Yasushi

1986-01-01

The coprecipitation of alkali metal ions Li + , Na + , K + and Rb + with calcium carbonate has been studied experimentally and the following results have been obtained: (1) Alkali metal ions are more easily coprecipitated with aragonite than with calcite. (2) The relationship between the amounts of alkali metal ions coprecipitated with aragonite and their ionic radii shows a parabolic curve with a peak located at Na + which has approximately the same ionic radius as Ca 2+ . (3) However, the amounts of alkali metal ions coprecipitated with calcite decrease with increasing ionic radius of alkali metals. (4) Our results support the hypothesis that (a) alkali metals are in interstitial positions in the crystal structure of calcite and do not substitute for Ca 2+ in the lattice, but (b) in aragonite, alkali metals substitute for Ca 2+ in the crystal structure. (5) Magnesium ions in the parent solution increase the amounts of alkali metal ions (Li + , Na + , K + and Rb + ) coprecipitated with calcite but decrease those with aragonite. (6) Sodium-bearing aragonite decreases the incorporation of other alkali metal ions (Li + , K + and Rb + ) into the aragonite. (author)

Method for the safe disposal of alkali metal

International Nuclear Information System (INIS)

Johnson, T.R.

1977-01-01

Alkali metals such as those employed in liquid metal coolant systems can be safely reacted to form hydroxides by first dissolving the alkali metal in relatively inert metals such as lead or bismuth. The alloy thus formed is contacted with a molten salt including the alkali metal hydroxide and possibly the alkali metal carbonate in the presence of oxygen. This oxidizes the alkali metal to an oxide which is soluble within the molten salt. The salt is separated and contacted with steam or steam--CO 2 mixture to convert the alkali metal oxide to the hydroxide. These reactions can be conducted with minimal hydrogen evolution and with the heat of reaction distributed between the several reaction steps. 5 claims, 1 figure

Method of handling radioactive alkali metal waste

Science.gov (United States)

Wolson, R.D.; McPheeters, C.C.

Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1.

Method of handling radioactive alkali metal waste

International Nuclear Information System (INIS)

Mcpheeters, C.C.; Wolson, R.D.

1980-01-01

Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1

Charge transfer in gold--alkali-metal systems

International Nuclear Information System (INIS)

Watson, R.E.; Weinert, M.

1994-01-01

Based on conventional electronegativity arguments, gold--alkali-metal compounds are expected to be among the most ''ionic'' of metallic compounds. The concepts of ionicity and charge transfer are difficult to quantify. However, the changes in bonding in the 50/50 Au--alkali-metal systems between the elemental metals and the compounds are so severe that observations can readily be made concerning their character. The results, as obtained from self-consistent electronic-structure calculations, lead to the apparently odd observation that the electron density at the alkali-metal sites in the compound increases significantly and this involves high l componennts in the charge density. This increase, however, can be attributed to Au-like orbitals spatially overlapping the alkali-metal sites. In a chemical sense, it is reasonable to consider the alkali-metal transferring charge to these Au orbitals. While normally the difference in heats of formation between muffin-tin and full-potential calculations for transition-metal--transition-metal and transition-metal--main-group (e.g., Al) compounds having high site symmetry are small, for the gold--alkali-metal systems, the changes in bonding in the compounds cause differences of ∼0.5 eV/atom between the two classes of potential. Any serious estimate of the electronic structure in these systems must account for these aspherical bonding charges. The origin of the semiconducting behavior of the heavy-alkali-metal Au compounds is shown to arise from a combination of the Au-Au separations and the ionic character of the compounds; the light-alkali-metal Au compounds, with their smaller Au-Au separations, do not have a semiconducting gap. Core-level shifts and isomer shifts are also briefly discussed

Quantum Chemical and FTIR Spectroscopic Studies on the Linkage Isomerism of Carbon Monoxide in Alkali-Metal-Exchanged Zeolites: A Review of Current Research

OpenAIRE

E. Garrone; A. A. Tsyganenko; G. Turnes Palomino; C. Otero Areán

2002-01-01

Abstract: When adsorbed (at a low temperature) on alkali-metal-exchanged zeolites, CO forms both M(CO)+ and M(OC)+ carbonyl species with the extra-framework alkali-metal cation of the zeolite. Both quantum chemical and experimental results show that C-bondend adducts are characterized by a C−O stretching IR band at a frequency higher than that of 2143 cm-1 for free CO, while for O-bonded adducts this IR band appears below 2143 cm-1. The cation-CO interaction energy is higher for M(CO)+ t...

40 CFR 721.4740 - Alkali metal nitrites.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal nitrites. 721.4740... Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject to reporting. (1) The category of chemical substances which are nitrites of the alkali metals (Group IA in the...

Quantum Chemical and FTIR Spectroscopic Studies on the Linkage Isomerism of Carbon Monoxide in Alkali-Metal-Exchanged Zeolites: A Review of Current Research

Directory of Open Access Journals (Sweden)

E. Garrone

2002-07-01

Full Text Available Abstract: When adsorbed (at a low temperature on alkali-metal-exchanged zeolites, CO forms both M(CO+ and M(OC+ carbonyl species with the extra-framework alkali-metal cation of the zeolite. Both quantum chemical and experimental results show that C-bondend adducts are characterized by a C−O stretching IR band at a frequency higher than that of 2143 cm-1 for free CO, while for O-bonded adducts this IR band appears below 2143 cm-1. The cation-CO interaction energy is higher for M(CO+ than for M(OC+ carbonyls, although the corresponding difference decreases substantially when going from Li+ to Cs+. By means of variable-temperature FTIR spectroscopy, this energy difference was determined for several alkali-metal cations, and the existence of a thermal equilibrium between M(CO+ and M(OC+ species was established. The current state of research in this field is reviewed here, with a view to gain more insight into the thermal isomerization process.

Upgrading platform using alkali metals

Science.gov (United States)

Gordon, John Howard

2014-09-09

A process for removing sulfur, nitrogen or metals from an oil feedstock (such as heavy oil, bitumen, shale oil, etc.) The method involves reacting the oil feedstock with an alkali metal and a radical capping substance. The alkali metal reacts with the metal, sulfur or nitrogen content to form one or more inorganic products and the radical capping substance reacts with the carbon and hydrogen content to form a hydrocarbon phase. The inorganic products may then be separated out from the hydrocarbon phase.

The effect of specific solvent-solute interactions on complexation of alkali-metal cations by a lower-rim calix[4]arene amide derivative.

Science.gov (United States)

Horvat, Gordan; Stilinović, Vladimir; Kaitner, Branko; Frkanec, Leo; Tomišić, Vladislav

2013-11-04

Complexation of alkali-metal cations with calix[4]arene secondary-amide derivative, 5,11,17,23-tetra(tert-butyl)-25,26,27,28-tetra(N-hexylcarbamoylmethoxy)calix[4]arene (L), in benzonitrile (PhCN) and methanol (MeOH) was studied by means of microcalorimetry, UV and NMR spectroscopies, and in the solid state by X-ray crystallography. The inclusion of solvent molecules (including acetonitrile, MeCN) in the calixarene hydrophobic cavity was also investigated. The classical molecular dynamics (MD) simulations of the systems studied were carried out. By combining the results obtained using the mentioned experimental and computational techniques, an attempt was made to get an as detailed insight into the complexation reactions as possible. The thermodynamic parameters, that is, equilibrium constants, reaction Gibbs energies, enthalpies, and entropies, of the investigated processes were determined and discussed. The stability constants of the 1:1 (metal:ligand) complexes measured by different methods were in very good agreement. Solution Gibbs energies of the ligand and its complexes with Na(+) and K(+) in methanol and acetonitrile were determined. It was established that from the thermodynamic point of view, apart from cation solvation, the most important reason for the huge difference in the stability of these complexes in the two solvents lay in the fact that the transfer of complex species from MeOH to MeCN was quite favorable. That could be at least partly explained by a more exergonic inclusion of the solvent molecule in the complexed calixarene cone in MeCN as compared to MeOH, which was supported by MD simulations. Molecular and crystal structures of the lithium cation complex of L with the benzonitrile molecule bound in the hydrophobic calixarene cavity were determined by single-crystal X-ray diffraction. As far as we are aware, for the first time the alkali-metal cation was found to be coordinated by the solvent nitrile group in a calixarene adduct. According to

Controlled in-situ dissolution of an alkali metal

Science.gov (United States)

Jones, Jeffrey Donald; Dooley, Kirk John; Tolman, David Donald

2012-09-11

A method for the controllable dissolution of one or more alkali metals from a vessel containing a one or more alkali metals and/or one or more partially passivated alkali metals. The vessel preferably comprising a sodium, NaK or other alkali metal-cooled nuclear reactor that has been used. The alkali metal, preferably sodium, potassium or a combination thereof, in the vessel is exposed to a treatment liquid, preferably an acidic liquid, more preferably citric acid. Preferably, the treatment liquid is maintained in continuous motion relative to any surface of unreacted alkali metal with which the treatment liquid is in contact. The treatment liquid is preferably pumped into the vessel containing the one or more alkali metals and the resulting fluid is extracted and optionally further processed. Preferably, the resulting off-gases are processed by an off-gas treatment system and the resulting liquids are processed by a liquid disposal system. In one preferred embodiment, an inert gas is pumped into the vessel along with the treatment liquid.

Alkali Metal Ion Complexes with Phosphates, Nucleotides, Amino Acids, and Related Ligands of Biological Relevance. Their Properties in Solution.

Science.gov (United States)

Crea, Francesco; De Stefano, Concetta; Foti, Claudia; Lando, Gabriele; Milea, Demetrio; Sammartano, Silvio

2016-01-01

Alkali metal ions play very important roles in all biological systems, some of them are essential for life. Their concentration depends on several physiological factors and is very variable. For example, sodium concentrations in human fluids vary from quite low (e.g., 8.2 mmol dm(-3) in mature maternal milk) to high values (0.14 mol dm(-3) in blood plasma). While many data on the concentration of Na(+) and K(+) in various fluids are available, the information on other alkali metal cations is scarce. Since many vital functions depend on the network of interactions occurring in various biofluids, this chapter reviews their complex formation with phosphates, nucleotides, amino acids, and related ligands of biological relevance. Literature data on this topic are quite rare if compared to other cations. Generally, the stability of alkali metal ion complexes of organic and inorganic ligands is rather low (usually log K  Na(+) > K(+) > Rb(+) > Cs(+). For example, for citrate it is: log K ML = 0.88, 0.80, 0.48, 0.38, and 0.13 at 25 °C and infinite dilution. Some considerations are made on the main aspects related to the difficulties in the determination of weak complexes. The importance of the alkali metal ion complexes was also studied in the light of modelling natural fluids and in the use of these cations as probes for different processes. Some empirical relationships are proposed for the dependence of the stability constants of Na(+) complexes on the ligand charge, as well as for correlations among log K values of NaL, KL or LiL species (L = generic ligand).

Method of making alkali metal hydrides

Science.gov (United States)

Pecharsky, Vitalij K.; Gupta, Shalabh; Pruski, Marek; Hlova, Ihor; Castle, Andra

2017-05-30

A method is provided for making alkali metal hydrides by mechanochemically reacting alkali metal and hydrogen gas under mild temperature (e.g room temperature) and hydrogen pressure conditions without the need for catalyst, solvent, and intentional heating or cooling.

Interaction of Cu(+) with cytosine and formation of i-motif-like C-M(+)-C complexes: alkali versus coinage metals.

Science.gov (United States)

Gao, Juehan; Berden, Giel; Rodgers, M T; Oomens, Jos

2016-03-14

The Watson-Crick structure of DNA is among the most well-known molecular structures of our time. However, alternative base-pairing motifs are also known to occur, often depending on base sequence, pH, or the presence of cations. Pairing of cytosine (C) bases induced by the sharing of a single proton (C-H(+)-C) may give rise to the so-called i-motif, which occurs primarily in expanded trinucleotide repeats and the telomeric region of DNA, particularly at low pH. At physiological pH, silver cations were recently found to stabilize C dimers in a C-Ag(+)-C structure analogous to the hemiprotonated C-dimer. Here we use infrared ion spectroscopy in combination with density functional theory calculations at the B3LYP/6-311G+(2df,2p) level to show that copper in the 1+ oxidation state induces an analogous formation of C-Cu(+)-C structures. In contrast to protons and these transition metal ions, alkali metal ions induce a different dimer structure, where each ligand coordinates the alkali metal ion in a bidentate fashion in which the N3 and O2 atoms of both cytosine ligands coordinate to the metal ion, sacrificing hydrogen-bonding interactions between the ligands for improved chelation of the metal cation.

Liquid alkali metals and alkali-based alloys as electron-ion plasmas

International Nuclear Information System (INIS)

Tosi, M.P.

1981-06-01

The article reviews the theory of thermodynamic and structural properties of liquid alkali metals and alkali-based alloys, within the framework of linear screening theory for the electron-ion interactions. (author)

Ternary alkali-metal and transition metal or metalloid acetylides as alkali-metal intercalation electrodes for batteries

Science.gov (United States)

Nemeth, Karoly; Srajer, George; Harkay, Katherine C; Terdik, Joseph Z

2015-02-10

Novel intercalation electrode materials including ternary acetylides of chemical formula: A.sub.nMC.sub.2 where A is alkali or alkaline-earth element; M is transition metal or metalloid element; C.sub.2 is reference to the acetylide ion; n is an integer that is 0, 1, 2, 3 or 4 when A is alkali element and 0, 1, or 2 when A is alkaline-earth element. The alkali elements are Lithium (Li), Sodium (Na), Potassium (K), Rubidium (Rb), Cesium (Cs) and Francium (Fr). The alkaline-earth elements are Berilium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba), and Radium (Ra). M is a transition metal that is any element in groups 3 through 12 inclusive on the Periodic Table of Elements (elements 21 (Sc) to element 30 (Zn)). In another exemplary embodiment, M is a metalloid element.

40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for the...

The 4843 Alkali Metal Storage Facility Closure Plan

International Nuclear Information System (INIS)

1991-06-01

The 4843 AMSF has been used primarily to provide a centralized building to receive and store dangerous and mixed alkali metal waste, including sodium and lithium, which has been generated at the Fast Flux Test Facility and at various other Hanford Site operations that used alkali metals. Most of the dangerous and mixed alkali metal waste received consists of retired equipment from liquid sodium processes. The unit continues to store material. In general, only solid alkali metal waste that is water reactive is stored at the 4843 AMSF. The 4843 AMSF will be closed in a manner consistent with Ecology guidelines and regulations (WAC 173-303-610). The general closure procedure is detailed as follows

The extraction of alkali metal picrates with dibenzo-18-crown-6

International Nuclear Information System (INIS)

Sadakane, Akira; Toei, Kyoji; Iwachido, Tadashi.

1975-01-01

The distribution of alkali metal picrate complexes of macrocyclic polyether (dibenzo-18-crown-6) between water and benzene was investigated. The polyether-cation complexes were found to be of a 1:1 stoichiometry. The formation of 2:1 complexes was recognized for Rb and Cs in a large excess of the polyether. The extractability of complex cation-picrate ion-pairs decreases in this sequence: K>Rb>Cs>Na>Li. The values of the extraction constants (log Ksub(ex)) were determined to be 4.65, 3.75, and 3.07 for K, Rb, and Cs compounds respectively. The thermodynamic quantities for the extraction process were calculated from the change in the extraction constants with the temperature. The extraction reactions are all exothermic, accompanied by an entropy decrease. (auth.)

Two-phase alkali-metal experiments in reduced gravity

International Nuclear Information System (INIS)

Antoniak, Z.I.

1986-06-01

Future space missions envision the use of large nuclear reactors utilizing either a single or a two-phase alkali-metal working fluid. The design and analysis of such reactors require state-of-the-art computer codes that can properly treat alkali-metal flow and heat transfer in a reduced-gravity environment. A literature search of relevant experiments in reduced gravity is reported on here, and reveals a paucity of data for such correlations. The few ongoing experiments in reduced gravity are noted. General plans are put forth for the reduced-gravity experiments which will have to be performed, at NASA facilities, with benign fluids. A similar situation exists regarding two-phase alkali-metal flow and heat transfer, even in normal gravity. Existing data are conflicting and indequate for the task of modeling a space reactor using a two-phase alkali-metal coolant. The major features of past experiments are described here. Data from the reduced-gravity experiments with innocuous fluids are to be combined with normal gravity data from the two-phase alkali-metal experiments. Analyses undertaken here give every expectation that the correlations developed from this data base will provide a valid representation of alkali-metal heat transfer and pressure drop in reduced gravity

Studies on indigenous ion exchange resins: alkali metal ions-hydrogen ion exchange equilibria

International Nuclear Information System (INIS)

Shankar, S.; Kumar, Surender; Venkataramani, B.

2001-01-01

With a view to select a suitable ion exchange resin for the removal of radionuclides (such as cesium, strontium etc.) from low level radioactive effluents, alkali metal ion -H' exchanges on nine indigenous gel- and macroporous-type and nuclear grade resins have been studied at a total ionic strength of 0.1 mol dm .3 (in the case ofCs' -H' exchange it was 0.05 mol dm .3 ). The expected theoretical capacities were not attained by all the resins for the alkali metal ions. The water content (moles/equiv.) of the fully swollen resins for different alkali metal ionic forms do not follow the usual sequence of greater the tendency of the cation to hydrate the higher the water uptake, but a reverse trend. The ion exchange isotherms (plots of equivalent fractions of the ion in resin phase, N M1 to that in solution, N M ) were not satisfactory and sorption of cations, for most of the resins, was possible only when the acidity of the solution was lowered. The variations of the selectivity coefficient, K, with N M show that the resins are highly cross linked and the selectivity sequence: Cs + >K + >Na + >Li + , obtained for all the resins indicate that hydrated ions were involved in the exchange process. However, the increase in the selectivity was not accompanied by the release of water, but unusual uptake of water, during the exchange process. The characteristics of macroporous resins were not significantly different from those of the gel-type resins. The results are discussed in terms of heterogeneity in the polymer net work, improper sulphonation process resulting in the formation of functional groups at inaccessible sites with weak acidic character and the overall lack of control in the preparation of different resins. (author)

Process for the disposal of alkali metals

International Nuclear Information System (INIS)

Lewis, L.C.

1977-01-01

Large quantities of alkali metals may be safely reacted for ultimate disposal by contact with a hot concentrated caustic solution. The alkali metals react with water in the caustic solution in a controlled reaction while steam dilutes the hydrogen formed by the reaction to a safe level. 6 claims

The solvent extraction of alkali metal ions with β-diketones

International Nuclear Information System (INIS)

Munakata, Megumu; Niina, Syozo; Shimoji, Noboru

1974-01-01

This work was undertaken to investigate effects of solvent and chelating-agent on the solvent extraction of alkali metal ions by seven β-diketones, acetylacetone (Acac), benzoylacetone (BzA), dipivaloylmethane (DPM), dibenzoylmethane (DBM), thenoyltrifluoloacetone (TTA), benzoyltrifluoroacetone (BFA) and hexafluoroacetylacetone (HFA), and to separate lithium from alkali metals. The extraction of alkali metals increase with increasing donor power of the solvent: i.e., benzene Na>K>Rb>Cs, which is also the order in which the adduct formation of these β-diketone chelates with donor solvents increase. The adduct formations between β-diketone chelates of alkali metals and donor solvents markedly enhance the solubilities of the chelates in solvents and, consequently, the extractabilities of alkali metals with β-diketones. Lithium was extracted with TTA in ether at such a low base concentration that sodium, potassium, rubidium and cesium were hardly extracted, and this enabled to separate lithium from other metals by the use of rubidium hydroxide (0.02 M). An attempt has been made to isolate alkali metal β-diketone chelates and some chelates have been obtained as crystals. The infrared absorption bands arising from C=O and C.=C of TTA shift to lower frequencies in the alkali metal chelates with TTA, and consequently, β-diketones is suggested to coordinate to alkali metal as a bidentate ligand. (JPN)

High-performance ion-exchange chromatography of alkali metals with conductivity detection

International Nuclear Information System (INIS)

Ahmad, M.; Khan, A.R.

1981-01-01

High-performance ion-exchange chromatography of alkali metal and ammonium ions was studied using a conductivity meter as detector. Elution with 0.003 N mitric acid gave excellent resolution. Sensitivity levels, for a 200 micro litre injection, vary from 5 ppm for potassium to 0.1 ppm for lithium. A method to decrease retention times by reducing the exchange capacity of the cation exchange column used by loading it with calciumions, without affecting the resolation, has been described. Application of the method to water, soil and uranium dioxide samples has been demonstrated. (author)

Recent materials compatibility studies in refractory metal-alkali metal systems for space power applications.

Science.gov (United States)

Harrison, R. W.; Hoffman, E. E.; Davies, R. L.

1972-01-01

Advanced Rankine and other proposed space power systems utilize refractory metals in contact with both single-phase and two-phase alkali metals at elevated temperatures. A number of recent compatibility experiments are described which emphasize the excellent compatibility of refractory metals with the alkali metals, lithium, sodium, and potassium, under a variety of environmental conditions. The alkali metal compatibilities of tantalum-, columbium-, molybdenum-, and tungsten-base alloys are discussed.

An Integrated approach (thermodynamic, structural, and computational) to the study of complexation of alkali-metal cations by a lower-rim calix[4]arene amide derivative in acetonitrile.

Science.gov (United States)

Horvat, Gordan; Stilinović, Vladimir; Hrenar, Tomica; Kaitner, Branko; Frkanec, Leo; Tomišić, Vladislav

2012-06-04

The calix[4]arene secondary-amide derivative L was synthesized, and its complexation with alkali-metal cations in acetonitrile (MeCN) was studied by means of spectrophotometric, NMR, conductometric, and microcalorimetric titrations at 25 °C. The stability constants of the 1:1 (metal/ligand) complexes determined by different methods were in excellent agreement. For the complexation of M(+) (M = Li, Na, K) with L, both enthalpic and entropic contributions were favorable, with their values and mutual relations being quite strongly dependent on the cation. The enthalpic and overall stability was the largest in the case of the sodium complex. Molecular and crystal structures of free L, its methanol and MeCN solvates, the sodium complex, and its MeCN solvate were determined by single-crystal X-ray diffraction. The inclusion of a MeCN molecule in the calixarene hydrophobic cavity was observed both in solution and in the solid state. This specific interaction was found to be stronger in the case of metal complexes compared to the free ligand because of the better preorganization of the hydrophobic cone to accept the solvent molecule. Density functional theory calculations showed that the flattened cone conformation (C(2) point group) of L was generally more favorable than the square cone conformation (C(4) point group). In the complex with Na(+), L was in square cone conformation, whereas in its adduct with MeCN, the conformation was slightly distorted from the full symmetry. These conformations were in agreement with those observed in the solid state. The classical molecular dynamics simulations indicated that the MeCN molecule enters the L hydrophobic cavity of both the free ligand and its alkali-metal complexes. The inclusion of MeCN in the cone of free L was accompanied by the conformational change from C(2) to C(4) symmetry. As in solution studies, in the case of ML(+) complexes, an allosteric effect was observed: the ligand was already in the appropriate square cone

Hydration number of alkali metal ions determined by insertion in a conducting polymer

DEFF Research Database (Denmark)

Skaarup, Steen

2008-01-01

of all other water molecules whose properties are still influenced significantly by the cation. Knowing the hydration number is important when considering, for instance, the transport of Na+ and K+ in biological cell membranes, since their different behavior may depend on the details of ion hydration....... The solvation of alkali metal ions has been discussed for many years without a clear consensus. This work presents a systematic study of the hydration numbers of the 5 alkali metal ions, using the electrochemical insertion of the ions in a conducting polymer (polypyrrole containing the large immobile anion DBS...... direct calculation of the number of M+ ions entering the film, and therefore the inserted M+ mass. The mass of the water molecules is calculated as a difference. The results yield the following primary hydration numbers: Li+: 5.5-5.6; Na+: 4.0-4.1; K+: 2.0-2.5; Rb+: 0.6-1.2; Cs+: ~0. The most important...

Determination of membrane hydration numbers of alkali metal ions by insertion in a conducting polymer

DEFF Research Database (Denmark)

Skaarup, Steen; Junaid Mohamed Jafeen, Mohamed; Careem, M.A.

2010-01-01

, and a secondary (or outer) solvation shell, consisting of all other water molecules whose properties are still influenced significantly by the cation. Knowing the hydration number is important when considering, for instance, the transport of Na+ and K+ in biological cell membranes, since their different behavior...... may depend on the details of ion hydration. Although the solvation of alkali metal ions in aqueous solution has been discussed for many years, there is still no clear consensus. Part of the discrepancy is simply that different methods measure over different time scales, and therefore do...... not necessarily define the same hydration shell. This work presents a systematic study of one special variant of the hydration numbers of the 5 alkali metal ions, using the electrochemical insertion of the ions in a conducting polymer (polypyrrole containing the large immobile anion DBS-). The technique...

Effect of alkali ion on relaxation properties of binary alkali-borate glasses

International Nuclear Information System (INIS)

Lomovskoj, V.A.; Bartenev, G.M.

1992-01-01

Method of relaxation spectrometry were used to analyze the data on internal friction spectra of lithium, sodium, potassium and rubidium alkali-borate glasses in wide range of temperatures and frequencies. The nature of two relaxation processes was clarified: β m -process, related with mobility of alkaline metal cations, and α-process (vitrification), conditioned by system transformation from viscous-flow to vitreous state. It is shown that atomic-molecular mechanism of vitrification process changes when passing from vitreous B 2 O 3 to alkali-borate glasses

Molecular Dynamics Study of Crystalline Swelling of Montmorillonite as Affected by Interlayer Cation Hydration

Science.gov (United States)

Li, Hongliang; Song, Shaoxian; Dong, Xianshu; Min, Fanfei; Zhao, Yunliang; Peng, Chenliang; Nahmad, Yuri

2018-04-01

Swelling of montmorillonite (Mt) is an important factor for many industrial applications. In this study, crystalline swelling of alkali-metal- and alkaline-earth-metal-Mt has been studied through energy optimization and molecular dynamics simulations using the clay force field by Materials Studio 8.0. The delamination and exfoliation of Mt are primarily realized by crystalline swelling caused by the enhanced interlayer cation hydration. The initial position of the interlayer cations and water molecules is the dominated factor for the accuracy of the Mt simulations. Crystalline swelling can be carried out in alkali-metal-Mt and Mg-Mt but with difficulty in Ca-Mt, Sr-Mt and Ba-Mt. The crystalline swelling capacity values are in the order Na-Mt > K-Mt > Cs-Mt > Mg-Mt. This order of crystalline swelling of Mt in the same group can be attributed to the differences between the interlayer cation hydration strengths. In addition, the differences in the crystalline swelling between the alkali-metal-Mt and alkaline-earth-metal-Mt can be primarily attributed to the valence of the interlayer cations.

Interaction of alkali metal nitrates with calcium carbonate and kyanite

International Nuclear Information System (INIS)

Protsyuk, A.P.; Malakhov, A.I.; Karabanov, V.P.; Lebedeva, L.P.

1978-01-01

Thermographic, thermodynamic and X-ray phase studies have been made into the interaction of alkali metal nitrates with calcium carbonate and kyanite. Examined among other things was the effect of water vapor and carbon dioxide on the interaction between alkali metal nitrates and kyanite. The chemical mechanism of the occurring processes has been established. The interaction with calcium carbonates results in the formation of alkali metal carbonates and calcium oxide with liberation of nitrogen oxide and oxygen. The products of the interaction with kyanite are shown to be identical with the compounds forming when alkali metal carbonates are used

Alkali metal control over N-N cleavage in iron complexes.

Science.gov (United States)

Grubel, Katarzyna; Brennessel, William W; Mercado, Brandon Q; Holland, Patrick L

2014-12-03

Though N2 cleavage on K-promoted Fe surfaces is important in the large-scale Haber-Bosch process, there is still ambiguity about the number of Fe atoms involved during the N-N cleaving step and the interactions responsible for the promoting ability of K. This work explores a molecular Fe system for N2 reduction, particularly focusing on the differences in the results obtained using different alkali metals as reductants (Na, K, Rb, Cs). The products of these reactions feature new types of Fe-N2 and Fe-nitride cores. Surprisingly, adding more equivalents of reductant to the system gives a product in which the N-N bond is not cleaved, indicating that the reducing power is not the most important factor that determines the extent of N2 activation. On the other hand, the results suggest that the size of the alkali metal cation can control the number of Fe atoms that can approach N2, which in turn controls the ability to achieve N2 cleavage. The accumulated results indicate that cleaving the triple N-N bond to nitrides is facilitated by simultaneous approach of least three low-valent Fe atoms to a single molecule of N2.

Amperometric Ion-Selective Electrode for Alkali Metal Cations Based on a Room-Temperature Ionic Liquid Membrane

Czech Academy of Sciences Publication Activity Database

Langmaier, Jan; Trojánek, Antonín; Samec, Zdeněk

2009-01-01

Roč. 21, 17-18 (2009), s. 1977-1983 ISSN 1040-0397 R&D Projects: GA MŠk ME08098; GA AV ČR IAA400400704 Institutional research plan: CEZ:AV0Z40400503 Keywords : room-temperature ionic liquid * alkali metals * Crown ether * cyclic voltammetry * amperometric ion-selective elkectrode Subject RIV: CG - Electrochemistry Impact factor: 2.630, year: 2009

Crown Ether Complexes of Alkali-Metal Chlorides from SO2.

Science.gov (United States)

Reuter, Kirsten; Rudel, Stefan S; Buchner, Magnus R; Kraus, Florian; von Hänisch, Carsten

2017-07-18

The structures of alkali-metal chloride SO 2 solvates (Li-Cs) in conjunction with 12-crown-4 or 1,2-disila-12-crown-4 show strong discrepancies, despite the structural similarity of the ligands. Both types of crown ethers form 1:1 complexes with LiCl to give [Li(1,2-disila-12-crown-4)(SO 2 Cl)] (1) and [Li(12-crown-4)Cl]⋅4 SO 2 (2). However, 1,2-disila-12-crown-4 proved unable to coordinate cations too large for the cavity diameter, for example, by the formation of sandwich-type complexes. As a result, 12-crown-4 reacts exclusively with the heavier alkali-metal chlorides NaCl, KCl and RbCl. Compounds [Na(12-crown-4) 2 ]Cl⋅4 SO 2 (3) and [M(12-crown-4) 2 (SO 2 )]Cl⋅4 SO 2 (4: M=K; 5: M=Rb) all showed S-coordination to the chloride ions through four SO 2 molecules. Compounds 4 and 5 additionally exhibit the first crystallographically confirmed non-bridging O,O'-coordination mode of SO 2 . Unexpectedly, the disila-crown ether supports the dissolution of RbCl and CsCl in the solvent and gives the homoleptic SO 2 -solvated alkali-metal chlorides [MCl⋅3 SO 2 ] (6: M=Rb; 7: M=Cs), which incorporate bridging μ-O,O'-coordinating moieties and the unprecedented side-on O,O'-coordination mode. All compounds were characterised by single-crystal X-ray diffraction. The crown ether complexes were additionally studied by using NMR spectroscopy, and the presence of SO 2 at ambient temperature was revealed by IR spectroscopy of the neat compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gradients of electric fields and effective charges in alkali metal permanganates on NMR data

International Nuclear Information System (INIS)

Tarasov, V.P.; Kirakosyan, G.A.; Meladze, M.A.; German, K.Eh.

1993-01-01

Pulse method of 55 Mn, 39 K, 87 Rb, 133 Cs NMR in 7.04 T field was used to study polycrystal permanganates of alkali metals KMnO 4 , RbMnO 4 , CsMnO 4 in 100-440 K range. Qaudrupole bond constants, parameters of tensor asymmetry of electric field gradient (EFG) and isotropic values of chemical shifts were determined in result of analysis of resonance line shape. Cation positions in RbMnO 4 and CsMnO 4 are characterized by two nonequivalent states with 1:1 occupation. Effective charges on oxygen and manganese atoms were calculated in the framework of point charge model, using structural data and experimental EFG values on cation nuclei

Vibrations of alkali metal overlayers on metal surfaces

International Nuclear Information System (INIS)

Rusina, G G; Eremeev, S V; Borisova, S D; Echenique, P M; Chulkov, E V; Benedek, G

2008-01-01

We review the current progress in the understanding of vibrations of alkalis adsorbed on metal surfaces. The analysis of alkali vibrations was made on the basis of available theoretical and experimental results. We also include in this discussion our recent calculations of vibrations in K/Pt(111) and Li(Na)/Cu(001) systems. The dependence of alkali adlayer localized modes on atomic mass, adsorption position and coverage as well as the dependence of vertical vibration frequency on the substrate orientation is discussed. The square root of atomic mass dependence of the vertical vibration energy has been confirmed by using computational data for alkalis on the Al(111) and Cu(001) substrates. We have confirmed that in a wide range of submonolayer coverages the stretch mode energy remains nearly constant while the energy of in-plane polarized modes increases with the increase of alkali coverage. It was shown that the spectrum of both stretch and in-plane vibrations can be very sensitive to the adsorption position of alkali atoms and substrate orientation

40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting under...

40 CFR 721.4660 - Alcohol, alkali metal salt.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alcohol, alkali metal salt. 721.4660 Section 721.4660 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4660 Alcohol, alkali metal sal...

40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

Science.gov (United States)

2010-07-01

... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under this... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fluorinated carboxylic acid alkali...

40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty alkyl phosphate, alkali metal... Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... as a fatty alkyl phosphate, alkali metal salt (PMN P-99-0385) is subject to reporting under this...

Maternal exposure to alkali, alkali earth, transition and other metals: Concentrations and predictors of exposure

International Nuclear Information System (INIS)

Hinwood, A.L.; Stasinska, A.; Callan, A.C.; Heyworth, J.; Ramalingam, M.; Boyce, M.; McCafferty, P.; Odland, J.Ø.

2015-01-01

Most studies of metals exposure focus on the heavy metals. There are many other metals (the transition, alkali and alkaline earth metals in particular) in common use in electronics, defense industries, emitted via combustion and which are naturally present in the environment, that have received limited attention in terms of human exposure. We analysed samples of whole blood (172), urine (173) and drinking water (172) for antimony, beryllium, bismuth, cesium, gallium, rubidium, silver, strontium, thallium, thorium and vanadium using ICPMS. In general most metals concentrations were low and below the analytical limit of detection with some high concentrations observed. Few factors examined in regression models were shown to influence biological metals concentrations and explained little of the variation. Further study is required to establish the source of metals exposures at the high end of the ranges of concentrations measured and the potential for any adverse health impacts in children. - This study has demonstrated exposure to alkali, alkali earth and transition metals in pregnant women with factors such as breastfeeding, fish oil use and diet affecting exposures

Local structure of alkalis in mixed-alkali borate glass to elucidate the origin of mixed-alkali effect

Directory of Open Access Journals (Sweden)

Yomei Tokuda

2015-12-01

Full Text Available We report the structural analysis of Na+ and Cs+ in sodium cesium borate crystals and glasses using 23Na and 133Cs magic-angle spinning nuclear magnetic resonance (MAS NMR spectroscopy. The composition dependence of NMR spectra of the borate was similar to that of the silicate: (1 the peak position of cesium borate crystals shifted to upfield for structures with larger Cs+ coordination numbers, (2 the MAS NMR spectra of xNa2O-yCs2O-3B2O3 (x = 0, 0.25, 0.5, 0.75, 1.0, x + y = 1 glass showed that the average coordination number (CN of both the alkali cations decreases with increasing Cs+/(Na+ + Cs+ ratio. However, the degree of decrement in borates is much smaller than that in silicates. We have considered that the small difference in CN is due to 4-coordinated B, because it is electrically compensated by the alkali metal ions resulting in the restriction of having various coordinations of O to alkali metal.

Density functional study of ferromagnetism in alkali metal thin films

Indian Academy of Sciences (India)

thickness uniform jellium model (UJM), and it is argued that within LSDA or GGA, alkali metal thin films cannot be claimed to have an FM ground state. Relevance of these results to the experiments on transition metal-doped alkali metal thin films ...

Clustering of nucleosides in the presence of alkali metals: Biologically relevant quartets of guanosine, deoxyguanosine and uridine observed by ESI-MS/MS.

Science.gov (United States)

Aggerholm, Tenna; Nanita, Sergio C; Koch, Kim J; Cooks, R Graham

2003-01-01

Electrospray ionization (ESI) mass spectra of nucleosides, recorded in the presence of alkali metals, display alkali metal ion-bound quartets and other clusters that may have implications for understanding non-covalent interactions in DNA and RNA. The tetramers of guanosine and deoxyguanosine and also their metaclusters (clusters of clusters), cationized by alkali metals, were observed as unusually abundant magic number clusters. The observation of these species in the gas phase parallels previous condensed-phase studies, which show that guanine derivatives can form quartets and metaclusters of quartets in solution in the presence of metal cations. This parallel behavior and also internal evidence suggest that bonding in the guanosine tetramers involves the bases rather than the sugar units. The nucleobases thymine and uracil are known to form magic number pentameric adducts with K+, Cs+ and NH4+ in the gas phase. In sharp contrast, we now show that the nucleosides uridine and deoxythymidine do not form the pentameric clusters characteristic of the corresponding bases. More subtle effects of the sugars are evident in the fact that adenosine and cytidine form numerous higher order clusters with alkali metals, whereas deoxyadenosine and deoxycytidine show no clustering. It is suggested that hydrogen bonding between the bases in the tetramers of dG and rG are the dominant interactions in the clusters, hence changing the ribose group to deoxyribose (and vice versa) generally has little effect. However, the additional hydroxyl group of RNA nucleosides enhances the non-selective formation of higher-order aggregates for adenosine and cytidine and results in the lack of highly stable magic number clusters. Some clusters are the result of aggregation in the course of ionization (ESI) whereas others appear to be intrinsic to the solution being examined. Copyright 2003 John Wiley & Sons, Ltd.

Complexes in polyvalent metal - Alkali halide melts

International Nuclear Information System (INIS)

Akdeniz, Z.; Tosi, M.P.

1991-03-01

Experimental evidence is available in the literature on the local coordination of divalent and trivalent metal ions by halogens in some 140 liquid mixtures of their halides with alkali halides. After brief reference to classification criteria for main types of local coordination, we focus on statistical mechanical models that we are developing for Al-alkali halide mixtures. Specifically, we discuss theoretically the equilibrium between (AlF 6 ) 3- and (AlF 4 ) - complexes in mixtures of AlF 3 and NaF as a function of composition in the NaF-rich region, the effect of the alkali counterion on this equilibrium, the possible role of (AlF 5 ) 2- as an intermediate species in molten cryolite, and the origin of the different complexing behaviours of Al-alkali fluorides and chlorides. We also present a theoretical scenario for processes of structure breaking and electron localization in molten cryolite under addition of sodium metal. (author). 26 refs, 2 tabs

Metal induced gap states at alkali halide/metal interface

International Nuclear Information System (INIS)

Kiguchi, Manabu; Yoshikawa, Genki; Ikeda, Susumu; Saiki, Koichiro

2004-01-01

The electronic state of a KCl/Cu(0 0 1) interface was investigated using the Cl K-edge near-edge X-ray absorption fine structure (NEXAFS). A pre-peak observed on the bulk edge onset of thin KCl films has a similar feature to the peak at a LiCl/Cu(0 0 1) interface, which originates from the metal induced gap state (MIGS). The present result indicates that the MIGS is formed universally at alkali halide/metal interfaces. The decay length of MIGS to an insulator differs from each other, mainly due to the difference in the band gap energy of alkali halide

Metal cation dependence of interactions with amino acids: bond dissociation energies of Rb(+) and Cs(+) to the acidic amino acids and their amide derivatives.

Science.gov (United States)

Armentrout, P B; Yang, Bo; Rodgers, M T

2014-04-24

Metal cation-amino acid interactions are key components controlling the secondary structure and biological function of proteins, enzymes, and macromolecular complexes comprising these species. Determination of pairwise interactions of alkali metal cations with amino acids provides a thermodynamic vocabulary that begins to quantify these fundamental processes. In the present work, we expand a systematic study of such interactions by examining rubidium and cesium cations binding with the acidic amino acids (AA), aspartic acid (Asp) and glutamic acid (Glu), and their amide derivatives, asparagine (Asn) and glutamine (Gln). These eight complexes are formed using electrospray ionization and their bond dissociation energies (BDEs) are determined experimentally using threshold collision-induced dissociation with xenon in a guided ion beam tandem mass spectrometer. Analyses of the energy-dependent cross sections include consideration of unimolecular decay rates, internal energy of the reactant ions, and multiple ion-neutral collisions. Quantum chemical calculations are conducted at the B3LYP, MP2(full), and M06 levels of theory using def2-TZVPPD basis sets, with results showing reasonable agreement with experiment. At 0 and 298 K, most levels of theory predict that the ground-state conformers for M(+)(Asp) and M(+)(Asn) involve tridentate binding of the metal cation to the backbone carbonyl, amino, and side-chain carbonyl groups, although tridentate binding to the carboxylic acid group and side-chain carbonyl is competitive for M(+)(Asn). For the two longer side-chain amino acids, Glu and Gln, multiple structures are competitive. A comparison of these results to those for the smaller alkali cations, Na(+) and K(+), provides insight into the trends in binding energies associated with the molecular polarizability and dipole moment of the side chain. For all four metal cations, the BDEs are inversely correlated with the size of the metal cation and follow the order Asp < Glu

40 CFR 721.10098 - Disubstituted benzoic acid, alkali metal salt (generic).

Science.gov (United States)

2010-07-01

... New Uses for Specific Chemical Substances § 721.10098 Disubstituted benzoic acid, alkali metal salt... identified generically as disubstituted benzoic acid, alkali metal salt (PMN P-03-643) is subject to... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Disubstituted benzoic acid, alkali...

A New Alkali-Stable Phosphonium Cation Based on Fundamental Understanding of Degradation Mechanisms.

Science.gov (United States)

Zhang, Bingzi; Kaspar, Robert B; Gu, Shuang; Wang, Junhua; Zhuang, Zhongbin; Yan, Yushan

2016-09-08

Highly alkali-stable cationic groups are a critical component of hydroxide exchange membranes (HEMs). To search for such cations, we studied the degradation kinetics and mechanisms of a series of quaternary phosphonium (QP) cations. Benzyl tris(2,4,6-trimethoxyphenyl)phosphonium [BTPP-(2,4,6-MeO)] was determined to have higher alkaline stability than the benchmark cation, benzyl trimethylammonium (BTMA). A multi-step methoxy-triggered degradation mechanism for BTPP-(2,4,6-MeO) was proposed and verified. By replacing methoxy substituents with methyl groups, a superior QP cation, methyl tris(2,4,6-trimethylphenyl)phosphonium [MTPP-(2,4,6-Me)] was developed. MTPP-(2,4,6-Me) is one of the most stable cations reported to date, with <20 % degradation after 5000 h at 80 °C in a 1 m KOD in CD3 OD/D2 O (5:1 v/v) solution. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Study of Complexation-ability of Neutral Schiff Bases to Some Metal Cations

Directory of Open Access Journals (Sweden)

Umit Cakir

2007-09-01

Full Text Available The constants of the extraction equilibrium and the distribution fordichloromethane as an organic solvent having low dielectric constant of metal cations withchiral Schiff bases, benzaldehydene-(S-2-amino-3-phenylpropanol (I, o- benzaldehydene-(S-2-hydroxybenzaldehydene-(S-2-amino-3-phenyl-propanol (II,amino-3-methylbutanol (III with anionic dyes [4-(2-pyridylazo-resorcinol mono sodiummonohydrate (NaPar, sodium picrat (NaPic and potassium picrat (KPic] and some heavymetal chlorides were determined at 25 oC. All the ligands have given strongestcomplexation for NaPar. In contrast, similar behaviour for both alkali metal picrates is notapparent in the complexation of corresponding ligands.

Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals.

Science.gov (United States)

Liu, Yuanyue; Merinov, Boris V; Goddard, William A

2016-04-05

It is well known that graphite has a low capacity for Na but a high capacity for other alkali metals. The growing interest in alternative cation batteries beyond Li makes it particularly important to elucidate the origin of this behavior, which is not well understood. In examining this question, we find a quite general phenomenon: among the alkali and alkaline earth metals, Na and Mg generally have the weakest chemical binding to a given substrate, compared with the other elements in the same column of the periodic table. We demonstrate this with quantum mechanics calculations for a wide range of substrate materials (not limited to C) covering a variety of structures and chemical compositions. The phenomenon arises from the competition between trends in the ionization energy and the ion-substrate coupling, down the columns of the periodic table. Consequently, the cathodic voltage for Na and Mg is expected to be lower than those for other metals in the same column. This generality provides a basis for analyzing the binding of alkali and alkaline earth metal atoms over a broad range of systems.

Poly(vinyl chloride) membrane alkali metal ion-selective electrodes based on crystalline synthetic zeolite of the Faujasite type

International Nuclear Information System (INIS)

Aghai, H.; Giahi, M.; Arvand Barmehi, M.

2002-01-01

Potentiometric electrodes based on the incorporation of zeolite particle in to poly (vinyl chloride) (pvc) membranes are described. The electrodes characteristics are evaluated regarding the response towards alkali ions. Pvc membranes plasticised with dibutyl phthalate and without lipophilic additives (co-exchanger) were used throughout this study. The electrode exhibits a Nernst ion response over the alkali metal cations concentration a range of 1.0x10 - 4 - 1.0 x 10 1 M with a slop of 57.0 ± 0.9 mV per decade of concentration a working ph range (3.0- 9.0) and a fast response time (≤15 c). The selective coefficients for cesium ion as test species with respect to alkaline earth, ammonium and some heavy metal ions were determined. Zeolite-PVC electrodes were applied to the determination of ionic surfactant

A procedure for preparing alkali metal hydrides

International Nuclear Information System (INIS)

Lemieux, R.U.; Sanford, C.E.; Prescott, J.F.

1976-01-01

A plain low cost, procedure for the continuous, low temperature preparation of sodium or potassium hydrides using cheap reagents is presented. Said invention is especially concerned with a process of purifying of a catalytic exchange liquid used for deuterium enrichment, in which an alkali metal hydride is produced as intermediate product. The procedure for producing the sodium and potassium hydrides consists in causing high pressure hydrogen to be absorbed by a mixture of at least a lower monoalkylamine and an alkylamide of an alkali metal from at least one of said amines [fr

Neuropsychiatric manifestations of alkali metal deficiency and excess

Energy Technology Data Exchange (ETDEWEB)

Yung, C.Y.

1984-01-01

The alkali metals from the Group IA of the periodic table (lithium, sodium, potassium, rubidium, cesium and francium) are reviewed. The neuropsychiatric aspects of alkali metal deficiencies and excesses (intoxications) are described. Emphasis was placed on lithium due to its clinical uses. The signs and symptoms of these conditions are characterized by features of an organic brain syndrome with delirium and encephalopathy prevailing. There are no clinically distinctive features that could be reliably used for diagnoses. Sodium and potassium are two essential alkali metals in man. Lithium is used as therapeutic agent in bipolar affective disorders. Rubidium has been investigated for its antidepressant effect in a group of psychiatric disorders. Cesium is under laboratory investigation for its role in carcinogenesis and in depressive illness. Very little is known of francium due to its great instability for experimental study.

Liquid-solid extraction of metallic cations by cationic amphiphiles

International Nuclear Information System (INIS)

Mueller, Wolfram; Sievers, Torsten K.; Zemb, Thomas; Diat, Olivier; Sievers, Torsten K.; Dejugnat, Christophe

2012-01-01

In the field of selective metal ion separation, liquid-liquid extraction is usually conducted through an emulsion mixing of hydrophobic complexants dispersed in an organic phase and acidic water containing the ionic species. Recently, it has been shown that amphiphilic complexants could influence strongly extraction efficiency by enhancing the interfacial interaction between the metal ion in the aqueous and the complexant in the organic phase. Moreover, these amphiphiles can also substitute the organic phase if an appropriate aliphatic chain is chosen. The dispersion of such amphiphilic complexants in an aqueous solution of salt mixtures is not only attractive for studying specific interactions but also to better the understanding of complex formation in aqueous solution of multivalent metal ions, such as lanthanides and actinides. This understanding is of potential interest for a broad range of industries including purification of rare earth metals and pollute treatment e.g. of fission byproducts. This principle can also be applied to liquid-solid extraction, where the final state of the separation is a solid phase containing the selectively extracted ions. Indeed, a novel solid-liquid extraction method exploits the selective precipitation of metal ions from an aqueous salt mixture using a cationic surfactant, below its Krafft point (temperature below which the long aliphatic chains of surfactant crystallize). This technique has been proven to be highly efficient for the separation of actinides and heavy metal using long chain ammonium or pyridinium amphiphiles. The most important point in this process is the recognition of cationic metal ions by cationic surfactants. By computing the free energy of the polar head group per micelle as a function of the different counter-anions, we have demonstrated for the first time that different interactions exist between the micellar surface and the ions. These interactions depend on the nature of the cation but also on

Crystal-structural study of zirconium chelates with alkali metals of composition A2[Zr(Nta)2]·xH2O (A=Li, Na, K, Rb, Cs or CH3H6)

International Nuclear Information System (INIS)

Sadikov, G.G.; Antsyshkina, A.S.; Sergienko, V.S.

1997-01-01

Some zirconium complexes with nitrile triacetate and with alkali metal in the external sphere were studied crystalostructurally. Packing of complexes and extra-sphere cations was studied. Plane or slightly corrugated anion layers of two essentially different types arranged according to the principle of trigonal and square grids represent the standard element of crystal structure. Water molecules are located both in anion and cation layers. CN and coordination polyhedron of cations are different even in case of stereotype nature of reasons of their location in the interlayer space. In Cs-, Rb- and K- compounds polyhedrons of alkali metal form specific doubled chains. These compounds are not isomorphous ones and are characterized by a specific way of water molecule location. Structure of sodium compound differs fundamentally from other ones. Ionic conductivity may be expected in crystals. 4 refs., 6 figs., 2 tabs

Melt cationic and anionic composition effect on titanium group metal corrosion in halogenides of alkali earths

International Nuclear Information System (INIS)

Tkhaj, V.; Kovalik, O.Yu.; Dikunov, Yu.G.; P'yankova, S.P.

1997-01-01

A study was made on interaction of titanium group metals with melts of chlorides and chloride-fluorides of alkaline earth metals and magnesium. It was revealed that the rate of metal corrosion increased from BaCl 2 2 2 2 in chloride series. It is explained by amplification of oxidation activity of salt cation in the series: Ba 2+ 2+ 2+ 2+ . It was also determined that corrosion rate of titanium exceeded the one of zirconium and hafnium, became reducing power of titanium was the highest in the given group

Alkali Metal Coolants. Proceedings of the Symposium on Alkali Metal Coolants - Corrosion Studies and System Operating Experience

Energy Technology Data Exchange (ETDEWEB)

NONE

1967-06-15

Proceedings of a Symposium organized by the IAEA and held in Vienna, 28 November - 2 December 1966. The meeting was attended by 107 participants from 16 countries and two international organizations. Contents: Review papers (2 papers); Corrosion of steels and metal alloys (6 papers); Mass transfer in alkali metal systems, behaviour of carbon (5 papers); Effects of sodium environment on mechanical properties of materials (3 papers); Effect of water leakage into sodium systems (2 papers); Design-and operation of testing apparatus (6 papers); Control, measurements and removal of impurities (13 papers); Corrosion by other alkali metals: NaK, K, Li, Cs (6 papers); Behaviour of fission products (3 papers). Each paper is in its original language (32 English, 6 French and 8 Russian) and is preceded by an abstract in English and one in the original language if this is not English. Discussions are in English. (author)

Alkali Metal Coolants. Proceedings of the Symposium on Alkali Metal Coolants - Corrosion Studies and System Operating Experience

International Nuclear Information System (INIS)

1967-01-01

Proceedings of a Symposium organized by the IAEA and held in Vienna, 28 November - 2 December 1966. The meeting was attended by 107 participants from 16 countries and two international organizations. Contents: Review papers (2 papers); Corrosion of steels and metal alloys (6 papers); Mass transfer in alkali metal systems, behaviour of carbon (5 papers); Effects of sodium environment on mechanical properties of materials (3 papers); Effect of water leakage into sodium systems (2 papers); Design-and operation of testing apparatus (6 papers); Control, measurements and removal of impurities (13 papers); Corrosion by other alkali metals: NaK, K, Li, Cs (6 papers); Behaviour of fission products (3 papers). Each paper is in its original language (32 English, 6 French and 8 Russian) and is preceded by an abstract in English and one in the original language if this is not English. Discussions are in English. (author)

Structural and Magnetic Diversity in Alkali-Metal Manganate Chemistry: Evaluating Donor and Alkali-Metal Effects in Co-complexation Processes.

Science.gov (United States)

Uzelac, Marina; Borilovic, Ivana; Amores, Marco; Cadenbach, Thomas; Kennedy, Alan R; Aromí, Guillem; Hevia, Eva

2016-03-24

By exploring co-complexation reactions between the manganese alkyl Mn(CH2SiMe3)2 and the heavier alkali-metal alkyls M(CH2SiMe3) (M=Na, K) in a benzene/hexane solvent mixture and in some cases adding Lewis donors (bidentate TMEDA, 1,4-dioxane, and 1,4-diazabicyclo[2,2,2] octane (DABCO)) has produced a new family of alkali-metal tris(alkyl) manganates. The influences that the alkali metal and the donor solvent impose on the structures and magnetic properties of these ates have been assessed by a combination of X-ray, SQUID magnetization measurements, and EPR spectroscopy. These studies uncover a diverse structural chemistry ranging from discrete monomers [(TMEDA)2 MMn(CH2SiMe3)3] (M=Na, 3; M=K, 4) to dimers [{KMn(CH2SiMe3)3 ⋅C6 H6}2] (2) and [{NaMn(CH2SiMe3)3}2 (dioxane)7] (5); and to more complex supramolecular networks [{NaMn(CH2SiMe3)3}∞] (1) and [{Na2Mn2 (CH2SiMe3)6 (DABCO)2}∞] (7)). Interestingly, the identity of the alkali metal exerts a significant effect in the reactions of 1 and 2 with 1,4-dioxane, as 1 produces coordination adduct 5, while 2 forms heteroleptic [{(dioxane)6K2Mn2 (CH2SiMe3)4(O(CH2)2OCH=CH2)2}∞] (6) containing two alkoxide-vinyl anions resulting from α-metalation and ring opening of dioxane. Compounds 6 and 7, containing two spin carriers, exhibit antiferromagnetic coupling of their S=5/2 moments with varying intensity depending on the nature of the exchange pathways. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphite-based detectors of alkali metals for nuclear power plants

International Nuclear Information System (INIS)

Kalandarishvili, A.G.; Kuchukhidze, V.A.; Sordiya, T.D.; Shartava, Sh.Sh.; Stepennov, B.S.

1993-01-01

The coolants most commonly used in today's fast reactors are alkali metals or their alloys. A major problem in nuclear plant design is leakproofing of the liquid-metal cooling system, and many leak detection methods and safety specifications have been developed as a result. Whatever the safety standards adopted for nuclear plants in different countries, they all rely on the basic fact that control of the contamination and radiation hazards involved requires reliable monitoring equipment. Results are presented of trials with some leak detectors for the alkali-metal circuits of nuclear reactors. The principal component affecting the detector performance is the sensing element. In the detectors graphite was employed, whose laminar structure enables it to absorb efficiently alkali-metal vapors at high temperatures (320--500 K). This produces a continuous series of alkali-metal-graphite solid solutions with distinct electrical, thermal, and other physical properties. The principle of operation of the detectors resides in the characteristic reactions of the metal-graphite system. One detector type uses the change of electrical conductivity of the graphite-film sensor when it is exposed to alkali-metal vapor. In order to minimize the effect of temperature on the resistance the authors prepared composite layers of graphite intercalated with a donor impurity (cesium or barium), and a graphite-nickel material. The addition of a small percentage of cesium, barium, or nickel produces a material whose temperature coefficient of resistance is nearly zero. Used as a sensing element, such a material can eliminate the need for thermostatic control of the detector

Molybdenum/alkali metal/ethylene glycol complexes useful as epoxidation catalysts

International Nuclear Information System (INIS)

Marquis, E.T.; Sanderson, J.R.; Keating, K.P.

1987-01-01

This patent describes a clear, storage stable solution of a molybdenum/alkali metal/ethylene glycol complex in ethylene glycol made by the process comprising: reacting at an elevated temperature between about 25 0 and 150 0 C a solid ammonium molybdate or a hydrate thereof and a solid alkali metal molybdate or a hydrate thereof with ethylene glycol, such that the ratio of moles of ethylene glycol to total gram atoms of molybdenum in the molybdates ranges from about 7:10 to 10:1, and the ratio of gram atoms of molybdenum in the ammonium molybdate or hydrate thereof to gram atoms of molybdenum in the alkali metal molybdate is from about 1:1 to about 20:1 to thereby provide a reaction product composed of a solution of an alkali metal-containing complex of molybdenum, alkali metal and ethylene glycol and by-products, including water, in the ethylene glycol and subsequently stripping the solution at a reduced pressure to remove from about 5 to about 25% of the reaction product, as distillate, to thereby provide a storage stable solution of the complex in the ethylene glycol having a molybdenum content of about 6 wt. % to about 20 wt. %, a water concentration of about 0.1 wt. % to about 6 wt. % and an acid number of more than about 60

Device for removing alkali metal residues from heat exchanger

International Nuclear Information System (INIS)

Matal, O.

1987-01-01

The main parts of the facility consists of a condensing vessel and a vacuum pump unit interconnected via a vacuum pipe. The heat exchanger is heated to a temperature at which the alkali metal residues evaporate. Metal vapors are collected in the condensing vessel where they condense. The removal of the alkali metal residues from the heat exchanger pipes allows thorough inspection of the pipe inside during scheduled nuclear power plant shutdowns. The facility can be used especially with reverse steam generators. (E.S.). 1 fig

Selectivity of externally facing ion-binding sites in the Na/K pump to alkali metals and organic cations.

Science.gov (United States)

Ratheal, Ian M; Virgin, Gail K; Yu, Haibo; Roux, Benoît; Gatto, Craig; Artigas, Pablo

2010-10-26

The Na/K pump is a P-type ATPase that exchanges three intracellular Na(+) ions for two extracellular K(+) ions through the plasmalemma of nearly all animal cells. The mechanisms involved in cation selection by the pump's ion-binding sites (site I and site II bind either Na(+) or K(+); site III binds only Na(+)) are poorly understood. We studied cation selectivity by outward-facing sites (high K(+) affinity) of Na/K pumps expressed in Xenopus oocytes, under voltage clamp. Guanidinium(+), methylguanidinium(+), and aminoguanidinium(+) produced two phenomena possibly reflecting actions at site III: (i) voltage-dependent inhibition (VDI) of outwardly directed pump current at saturating K(+), and (ii) induction of pump-mediated, guanidinium-derivative-carried inward current at negative potentials without Na(+) and K(+). In contrast, formamidinium(+) and acetamidinium(+) induced K(+)-like outward currents. Measurement of ouabain-sensitive ATPase activity and radiolabeled cation uptake confirmed that these cations are external K(+) congeners. Molecular dynamics simulations indicate that bound organic cations induce minor distortion of the binding sites. Among tested metals, only Li(+) induced Na(+)-like VDI, whereas all metals tested except Na(+) induced K(+)-like outward currents. Pump-mediated K(+)-like organic cation transport challenges the concept of rigid structural models in which ion specificity at site I and site II arises from a precise and unique arrangement of coordinating ligands. Furthermore, actions by guanidinium(+) derivatives suggest that Na(+) binds to site III in a hydrated form and that the inward current observed without external Na(+) and K(+) represents cation transport when normal occlusion at sites I and II is impaired. These results provide insights on external ion selectivity at the three binding sites.

Asymmetric cation-binding catalysis

DEFF Research Database (Denmark)

Oliveira, Maria Teresa; Lee, Jiwoong

2017-01-01

The employment of metal salts is quite limited in asymmetric catalysis, although it would provide an additional arsenal of safe and inexpensive reagents to create molecular functions with high optical purity. Cation chelation by polyethers increases the salts' solubility in conventional organic...... solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...... highly enantioselective silylation reactions in polyether-generated chiral environments, and leading to a record-high turnover in asymmetric organocatalysis. This can lead to further applications by the asymmetric use of other inorganic salts in various organic transformations....

Immobilization of Alkali Metal Fluorides via Recrystallization in a Cationic Lamellar Material, [Th(MoO4)(H2O)4Cl]Cl·H2O.

Science.gov (United States)

Lin, Jian; Bao, Hongliang; Qie, Meiying; Silver, Mark A; Yue, Zenghui; Li, Xiaoyun; Zhu, Lin; Wang, Xiaomei; Zhang, Linjuan; Wang, Jian-Qiang

2018-06-05

Searching for cationic extended materials with a capacity for anion exchange resulted in a unique thorium molybdate chloride (TMC) with the formula of [Th(MoO 4 )(H 2 O) 4 Cl]Cl·H 2 O. The structure of TMC is composed of zigzagging cationic layers [Th(MoO 4 )(H 2 O) 4 Cl] + with Cl - as interlamellar charge-balancing anions. Instead of performing ion exchange, alkali thorium fluorides were formed after soaking TMC in AF (A = Na, K, and Cs) solutions. The mechanism of AF immobilization is elucidated by the combination of SEM-EDS, PXRD, FTIR, and EXAFS spectroscopy. It was observed that four water molecules coordinating with the Th 4+ center in TMC are vulnerable to competition with F - , due to the formation of more favorable Th-F bonds compared to Th-OH 2 . This leads to a single crystal-to-polycrystalline transformation via a pathway of recrystallization to form alkali thorium fluorides.

40 CFR 721.10097 - Disubstituted benzenesulfonic acid, alkali metal salt (generic).

Science.gov (United States)

2010-07-01

... chemical substance identified generically as disubstituted benzenesulfonic acid, alkali metal salt (PMN P... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Disubstituted benzenesulfonic acid, alkali metal salt (generic). 721.10097 Section 721.10097 Protection of Environment ENVIRONMENTAL...

Cation-Size-Dependent Conformational Locking of Glutamic Acid by Alkali Ions: Infrared Photodissociation Spectroscopy of Cryogenic Ions.

Science.gov (United States)

Klyne, Johanna; Bouchet, Aude; Ishiuchi, Shun-Ichi; Fujii, Masaaki; Dopfer, Otto

2018-03-01

Consolidated knowledge of conformation and stability of amino acids and their clusters is required to understand their biochemical recognition. Often, alkali ions interact with amino acids and proteins. Herein, infrared photodissociation (IRPD) spectra of cryogenic metalated glutamic acid ions (GluM + , M = Li-Cs) are systematically analyzed in the isomer-specific fingerprint and XH stretch ranges (1100-1900, 2600-3600 cm -1 ) to provide a direct measure for cation-size-dependent conformational locking. GluM + ions are generated by electrospray ionization and cooled down to 15 K in a cryogenic quadrupole ion trap. The assignment of the IRPD spectra is supported by density functional theory calculations at the dispersion-corrected B3LYP-D3/aug-cc-pVTZ level. In the global minimum of GluM + , the flexibility of Glu is strongly reduced by the formation of rigid ionic CO···M + ···OC metal bridges, corresponding to charge solvation. The M + binding energy decreases monotonically with increasing cation size from D 0 = 314 to 119 kJ/mol for Li-Cs. Whereas for Li and Na only the global minimum of GluM + is observed, for K-Cs at least three isomers exist at cryogenic temperature. The IRPD spectra of cold GluM + ions are compared to IR multiple-photon dissociation spectra measured at room temperature. Furthermore, we elucidate the differences of the impact of protonation and metalation on the structure and conformational locking of Glu.

Exploration of the catalytic use of alkali metal bases

OpenAIRE

Bao, Wei

2017-01-01

This PhD thesis project was concerned with the use of alkali metal amide Brønsted bases and alkali metal alkoxide Lewis bases in (asymmetric) catalysis. The first chapter deals with formal allylic C(sp3)–H bond activation of aromatic and functionalized alkenes for subsequent C–C and C–H bond formations. The second chapter is focused on C(sp3)–Si bond activation of fluorinated pro-nucleophiles in view of C–C bond formations. In the first chapter, a screening of various metal amides...

An alternative picture of alkali-metal-mediated metallation: cleave and capture chemistry.

Science.gov (United States)

Mulvey, Robert E

2013-05-21

This perspective article takes an alternative look at alkali-metal-mediated chemistry (exchange of a relatively inert C-H bond for a more reactive C-metal bond by a multicomponent reagent usually containing an alkali metal and a less electropositive metal such as magnesium or zinc). It pictures that the cleavage of selected C-H bonds can be accompanied by the capturing of the generated anion by the multi (Lewis acid)-(Lewis base) character of the residue of the bimetallic base. In this way small atoms or molecules (hydrides, oxygen-based anions) as well as sensitive organic anions (of substituted aromatic compounds, ethers or alkenes) can be captured. Cleave and capture reactions which occur in special positions on the organic substrate are also included.

Long-range interactions among three alkali-metal atoms

International Nuclear Information System (INIS)

Marinescu, M.; Starace, A.F.

1996-01-01

The long-range asymptotic form of the interaction potential surface for three neutral alkali-metal atoms in their ground states may be expressed as an expansion in inverse powers of inter-nuclear distances. The first leading powers are proportional to the dispersion coefficients for pairwise atomic interactions. They are followed by a term responsible for a three body dipole interaction. The authors results consist in evaluation of the three body dipole interaction coefficient between three alkali-metal atoms. The generalization to long-range n atom interaction terms will be discussed qualitatively

Method and composition for testing for the presence of an alkali metal

International Nuclear Information System (INIS)

Guon, J.

1981-01-01

A method and composition for detecting the presence of an alkali metal on the surface of a body such as a metal plate, tank, pipe or the like is provided. The method comprises contacting the surface with a thin film of a liquid composition comprising a light-colored pigment, an acid-base indicator, and a nonionic wetting agent dispersed in a liquid carrier comprising a minor amount of water and a major amount of an organic solvent selected from the group consisting of the lower aliphatic alcohols, ketones and ethers. Any alkali metal present on the surface in elemental form or as an alkali metal hydroxide or alkali metal carbonate will react with the acid-base indicator to produce a contrasting color change in the thin film, which is readily discernible by visual observation or automatic techniques

The alkali and alkaline earth metal doped ZnO nanotubes: DFT studies

International Nuclear Information System (INIS)

Peyghan, Ali Ahmadi; Noei, Maziar

2014-01-01

Doping of several alkali and alkaline earth metals into sidewall of an armchair ZnO nanotube has been investigated by employing the density functional theory in terms of energetic, geometric, and electronic properties. It has been found that doping processes of the alkali and alkaline metals are endothermic and exothermic, respectively. Based on the results, contrary to the alkaline metal doping, the electronic properties of the tube are much more sensitive to alkali metal doping so that it is transformed from intrinsic semiconductor with HOMO–LUMO energy gap of 3.77 eV to an extrinsic semiconductor with the energy gap of ∼1.11–1.95 eV. The doping of alkali and alkaline metals increases and decreases the work function of the tube, respectively, which may influence the electron emission from the tube surface

Electrochemical insertion in solid media of alkali cations in carbonated host structures (polyacetylene, fullerene and graphite)

International Nuclear Information System (INIS)

Lemont, Sylvain

1994-01-01

This research thesis reports the investigation of electrochemical insertion of alkali cations in different host carbon containing structures (polyacetylene, fullerene, graphite). After a recall of the main characteristics of the three considered compounds, the author reports a bibliographical survey, describes the different compounds which can be used as solid electrolytes and explains the choice of the studied compounds with respect to their phase diagrams, ionic conductivity, electrochemical stability range. He describes the experimental methods, discusses the results obtained by intercalation of alkali cations (Li + , Na + , K + ) in polyacetylene. He discusses the electrochemical and structural results obtained on intercalation compounds of lithium and sodium ions in fullerene. The structures of several phases have been obtained by electron diffraction. Preliminary studies of electron energy loss spectrometry (EELS) are reported. The last part compares the results obtained on two types of graphite: pellets and spherules [fr

Corrosion and compatibility in liquid alkali metals

International Nuclear Information System (INIS)

Anon.

1978-01-01

The literature dealing with liquid alkali metal corrosion of vanadium and its alloys is reviewed in the following subsections. Attention is given to both lithium and sodium data. Preceding this review, a brief outline of the current state of understanding of liquid metal corrosion mechanisms is provided

Saturated vapor pressure over molten mixtures of GaCl{sub 3} and alkali metal chlorides; Davlenie nasyshchennykh parov rasplavlennykh smesej CaCl{sub 3} s khloridami shchelochnykh metallov

Energy Technology Data Exchange (ETDEWEB)

Salyulev, A B; Smolenskij, V V; Moskalenko, N I [UrO RAN, Inst. Vysokotemperaturnoj Ehlektrokhimii, Elaterinburg (Russian Federation)

2004-07-01

Volatilities of GaCl{sub 3} and alkali metal chlorides over diluted (up to 3 mol %) solutions of GaCl{sub 3} in LiCl, NaCl, KCl, RbCl, and CsCl were measured at 1100 K by dynamic and indirect static methods. Chemical composition of saturated vapor over the mixed melts was determined. Partial pressures of the components were calculated. Their values depend essentially on specific alkali metal cation and on concentration of GaCl{sub 3}; their variation permits altering parameters of GaCl{sub 3} distillation from the salt melt in a wide range.

Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilino Ligand.

Science.gov (United States)

Fuentes, M Ángeles; Zabala, Andoni; Kennedy, Alan R; Mulvey, Robert E

2016-10-10

Bulky amido ligands are precious in s-block chemistry, since they can implant complementary strong basic and weak nucleophilic properties within compounds. Recent work has shown the pivotal importance of the base structure with enhancement of basicity and extraordinary regioselectivities possible for cyclic alkali metal magnesiates containing mixed n-butyl/amido ligand sets. This work advances alkali metal and alkali metal magnesiate chemistry of the bulky arylsilyl amido ligand [N(SiMe 3 )(Dipp)] - (Dipp=2,6-iPr 2 -C 6 H 3 ). Infinite chain structures of the parent sodium and potassium amides are disclosed, adding to the few known crystallographically characterised unsolvated s-block metal amides. Solvation by N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) or N,N,N',N'-tetramethylethylenediamine (TMEDA) gives molecular variants of the lithium and sodium amides; whereas for potassium, PMDETA gives a molecular structure, TMEDA affords a novel, hemi-solvated infinite chain. Crystal structures of the first magnesiate examples of this amide in [MMg{N(SiMe 3 )(Dipp)} 2 (μ-nBu)] ∞ (M=Na or K) are also revealed, though these breakdown to their homometallic components in donor solvents as revealed through NMR and DOSY studies. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Mechanisms and kinetics of electrodeposition of alkali metals on solid and liquid mercury electrodes

Energy Technology Data Exchange (ETDEWEB)

Lu, Wenzhe.

1993-01-01

Electroreduction of alkali metal ions at mercury is an important area in electrochemistry related to the battery industry. In this work, four major topics were considered: alkali metal/mercury interactions; electrosorption of alkali metal ions on solid mercury; electroreduction of alkali metal/crown ether complexes; and ammonium amalgam formation. The formation of alkali metal-mercury intermetallic compounds was studied on liquid and frozen thin layer mercury electrodes. The stoichiometry of the compounds produced under these conditions was determined using cyclic voltammetry. As expected, formation of a new phase was preceded by nucleation phenomena, which were particularly easy to monitor at solid Hg electrodes. The nucleation kinetics were studied using the chronoamperometric method. At very low temperatures, when the mobility of mercury atoms was restricted, the electrosorption of alkali metal ions on solid mercury electrodes was noted. Subsequent study allowed determination of the electrosorption parameters. The free energy of electrosorption is discussed in terms of interactions between alkali metals and mercury. The effect of crown ethers on the kinetics of alkali metal ion reduction was studied at both standard size and ultramicro-mercury electrodes in nonaqueous solutions using ultrafast cyclic voltammetry and ac voltammetry. The usefulness of ultrafast cyclic voltammetry with ultramicroelectrodes in measurements of the kinetics of amalgam formation was verified in a brief study of cadmium ion reduction. The mechanism of the complex reduction at mercury was analyzed based on the free energy changes before and after the activation state. In addition, the stoichiometry and formation constants of the crown ether/alkali metal complexes were determined using cyclic voltammetry. The mechanism of electroreduction of ammonium ions at mercury electrodes in non-aqueous media was analyzed.

Synthesis and structural characterization of alkali metal arsinoamides.

Science.gov (United States)

Chen, Xiao; Gamer, Michael T; Roesky, Peter W

2017-12-20

The aminoarsane Mes 2 AsN(H)Ph was prepared from Mes 2 AsCl and aniline in good yields. Deprotonation of Mes 2 AsN(H)Ph with suitable alkali metal bases resulted in the corresponding alkali metal derivatives. Thus, reaction of Mes 2 AsN(H)Ph with nBuLi, NaN(SiMe 3 ) 2 , or KH gave the metal complexes [(Mes 2 AsNPh){Li(OEt 2 ) 2 }], [(Mes 2 AsNPh){Na(OEt 2 )}] 2 , and [(Mes 2 AsNPh){K(THF)}] 2 . These are the first metal complexes ligated by an arsinoamide. All solid-state structures were established by single crystal X-ray diffraction. The lithium compounds form a monomer in the solid-state, whereas the sodium and the potassium derivatives are dimers. In the dimeric compounds intra- and intermolecular π-interaction of the aromatic rings with the metal atoms is observed.

Long-range interactions between excited helium and alkali-metal atoms

KAUST Repository

Zhang, J.-Y.

2012-12-03

The dispersion coefficients for the long-range interaction of the first four excited states of He, i.e., He(2 1,3S) and He(2 1,3P), with the low-lying states of the alkali-metal atoms Li, Na, K, and Rb are calculated by summing over the reduced matrix elements of the multipole transition operators. For the interaction between He and Li the uncertainty of the calculations is 0.1–0.5%. For interactions with other alkali-metal atoms the uncertainty is 1–3% in the coefficient C5, 1–5% in the coefficient C6, and 1–10% in the coefficients C8 and C10. The dispersion coefficients Cn for the interaction of He(2 1,3S) and He(2 1,3P) with the ground-state alkali-metal atoms and for the interaction of He(2 1,3S) with the alkali-metal atoms in their first 2P states are presented in this Brief Report. The coefficients for other pairs of atomic states are listed in the Supplemental Material.

Intermetallic Competition in the Fragmentation of Trimetallic Au-Zn-Alkali Complexes.

Science.gov (United States)

Lang, Johannes; Cayir, Merve; Walg, Simon P; Di Martino-Fumo, Patrick; Thiel, Werner R; Niedner-Schatteburg, Gereon

2016-02-12

Cationization is a valuable tool to enable mass spectrometric studies on neutral transition-metal complexes (e.g., homogenous catalysts). However, knowledge of potential impacts on the molecular structure and catalytic reactivity induced by the cationization is indispensable to extract information about the neutral complex. In this study, we cationize a bimetallic complex [AuZnCl3 ] with alkali metal ions (M(+) ) and investigate the charged adducts [AuZnCl3 M](+) by electrospray ionization mass spectrometry (ESI-MS). Infrared multiple photon dissociation (IR-MPD) in combination with density functional theory (DFT) calculations reveal a μ(3) binding motif of all alkali ions to the three chlorido ligands. The cationization induces a reorientation of the organic backbone. Collision-induced dissociation (CID) studies reveal switches of fragmentation channels by the alkali ion and by the CID amplitude. The Li(+) and Na(+) adducts prefer the sole loss of ZnCl2 , whereas the K(+) , Rb(+) , and Cs(+) adducts preferably split off MCl2 ZnCl. Calculated energetics along the fragmentation coordinate profiles allow us to interpret the experimental findings to a level of subtle details. The Zn(2+) cation wins the competition for the nitrogen coordination sites against K(+) , Rb(+) , and Cs(+) , but it loses against Li(+) and Na(+) in a remarkable deviation from a naive hard and soft acids and bases (HSAB) concept. The computations indicate expulsion of MCl2 ZnCl rather than of MCl and ZnCl2 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

New quaternary alkali metal cadmium selenites, A2Cd(SeO3)2 (A = K, Rb, and Cs) and Li2Cd3(SeO3)4

Science.gov (United States)

Lü, Minfeng; Jo, Hongil; Oh, Seung-Jin; Ok, Kang Min

2017-12-01

A series of new alkali metal cadmium selenites, A2Cd(SeO3)2 (A = K, Rb, and Cs) and Li2Cd3(SeO3)4 have been synthesized in phase pure forms through hydrothermal and solid-state reactions. Structural analyses using single crystal X-ray diffraction indicate that while A2Cd(SeO3)2 and Li2Cd3(SeO3)4 reveal layered structures consisting of CdO6 and SeO3 polyhedra, their symmetry, bonding modes, and the orientation of lone pairs on Se4+ cations are different. A closer examination suggests that the observed structural variations found in the reported materials are attributed to the structure-directing effect of alkali metal cations with different sizes. Scanning electron microscopy/energy dispersive analysis by X-ray, thermogravimetric analysis, Infrared and UV-vis diffuse reflectance spectroscopy, transformation reactions under hydrothermal conditions, and local dipole moment calculations for the reported materials are also reported.

Long-range interactions between excited helium and alkali-metal atoms

KAUST Repository

Zhang, J.-Y.; Schwingenschlö gl, Udo; Shi, T.-Y.; Tang, L.-Y.; Yan, Z.-C.

2012-01-01

–5% in the coefficient C6, and 1–10% in the coefficients C8 and C10. The dispersion coefficients Cn for the interaction of He(2 1,3S) and He(2 1,3P) with the ground-state alkali-metal atoms and for the interaction of He(2 1,3S) with the alkali-metal atoms in their first

DFT study of the interaction between DOTA chelator and competitive alkali metal ions.

Science.gov (United States)

Frimpong, E; Skelton, A A; Honarparvar, B

2017-09-01

1, 4, 7, 10-tetraazacyclododecane-1, 4, 7, 10-tetracetic acid (DOTA) is an important chelator for radiolabeling of pharmaceuticals. The ability of alkali metals found in the body to complex with DOTA and compete with radio metal ions can alter the radiolabeling process. Non-covalent interactions between DOTA complexed with alkali metals Li + , Na + , K + and Rb + , are investigated with density functional theory using B3LYP and ωB97XD functionals. Conformational possibilities of DOTA were explored with a varying number of carboxylic pendant arms of DOTA in close proximity to the ions. It is found that the case in which four arms of DOTA are interacting with ions is more stable than other conformations. The objective of this study is to explore the electronic structure properties upon complexation of alkali metals Li + Na + , K + and Rb + with a DOTA chelator. Interaction energies, relaxation energies, entropies, Gibbs free energies and enthalpies show that the stability of DOTA, complexed with alkali metals decreases down the group of the periodic table. Implicit water solvation affects the complexation of DOTA-ions leading to decreases in the stability of the complexes. NBO analysis through the natural population charges and the second order perturbation theory, revealed a charge transfer between DOTA and alkali metals. Conceptual DFT-based properties such as HOMO/LUMO energies, ΔE HOMO-LUMO and chemical hardness and softness indicated a decrease in the chemical stability of DOTA-alkali metal complexes down the alkali metal series. This study serves as a guide to researchers in the field of organometallic chelators, particularly, radiopharmaceuticals in finding the efficient optimal match between chelators and various metal ions. Copyright © 2017 Elsevier Inc. All rights reserved.

The role of halide ions on the electrochemical behaviour of iron in alkali solutions

Science.gov (United States)

Begum, S. Nathira; Muralidharan, V. S.; Basha, C. Ahmed

2008-02-01

Active dissolution and passivation of transition metals in alkali solutions is of technological importance in batteries. The performance of alkaline batteries is decided by the presence of halides as they influence passivation. Cyclic voltammetric studies were carried out on iron in different sodium hydroxide solutions in presence of halides. In alkali solutions iron formed hydroxo complexes and their polymers in the interfacial diffusion layer. With progress of time they formed a cation selective layer. The diffusion layer turned into bipolar ion selective layer consisted of halides, a selective inner sublayer to the metal side and cation selective outer layer to the solution side. At very high anodic potentials, dehydration and deprotonation led to the conversion of salt layer into an oxide.

Binding properties of oxacalix[4]arenes derivatives toward metal cations

International Nuclear Information System (INIS)

Mellah, B.

2006-11-01

The objective of this work was to establish the binding properties of oxacalix[4]arene derivatives with different numbers of the oxa bridges, functional groups (ketones, pyridine, ester, amide and methoxy) and conformations. Their interactions with alkali and alkaline-earth, heavy and transition metal cations have been evaluated according to different approaches: (i) extraction of corresponding picrates from an aqueous phase into dichloromethane; (ii) determination of the thermodynamic parameters of complexation in methanol and/or acetonitrile by UV-spectrophotometry and micro-calorimetry; (iii) determination of the stoichiometry of the complexes by ESI-MS; (iv) 1 H-NMR titrations allowing to localize the metal ions in the ligand cavity. In a first part dealing on homo-oxacalix[4]arenes, selectivities for Na + , K + , Ca 2+ , Pb 2+ and Mn 2+ of ketones derivatives was shown. The presence of oxa bridge in these derivatives increases their efficiency while decreasing their selectivity with respect to related calixarenes. The pyridine derivative prefers transition and heavy metal cations, in agreement with the presence of the soft nitrogen atoms. In the second part, di-oxacalix[4]arene ester and secondary amide derivatives were shown to be less effective than tertiary amide counterparts but to present high selectivities for Li + , Ba 2+ , Zn 2+ and Hg 2+ . A third part devoted to the octa-homo-tetra-oxacalix[4]arene tetra-methoxy shows that the 1:1 metal complexes formed are generally more stable than those of calixarenes, suggesting the participation of the oxygen atoms of the bridge in the complexation. Selectivity for Cs + , Ba 2+ , Cu 2+ and Hg 2+ were noted. (author)

Micelle formation during extraction of alkali elements from strongly alkaline mediums

International Nuclear Information System (INIS)

Apanasenko, V.V.; Reznik, A.M.; Bukin, V.I.; Brodskaya, A.V.

1988-01-01

Extraction of potassium, rubidium and cesium by phenol reagents in hydrocarbon solvents from strongly alkakine solutions was considered. Tendency of prepared alkali metal phenolates to form micelles in aqueous and organic phases was revealed. Phenolates tendency to form micelles is dictated mainly by the size and position of hydrocarbon substituent in molecule. It is shown that when micelles form in organic phase, alkali elements can be extracted both according to cation-exchange mechanism and according to micellar one. It is noted that alkai element extraction from strongly alkaline media requires the correct choice of extractant: alkali metal phenolate shouldn't form micelles in aqueous solution. n-Alkyl- and arylphenoldisulfides and polysulfides are most preferable for solvent extraction among considered phenol derivatives

Tuning the electronic structure of graphene through alkali metal and halogen atom intercalation

Science.gov (United States)

Ahmad, Sohail; Miró, Pere; Audiffred, Martha; Heine, Thomas

2018-04-01

The deposition, intercalation and co-intercalation of heavy alkali metals and light halogens atoms in graphene mono- and bilayers have been studied using first principles density-functional calculations. Both the deposition and the intercalation of alkali metals gives rise to n-type doping due to the formation of M+-C- pairs. The co-intercalation of a 1:1 ratio of alkali metals and halogens derives into the formation of ionic pairs among the intercalated species, unaltering the electronic structure of the layered material.

Upgrading of petroleum oil feedstocks using alkali metals and hydrocarbons

Science.gov (United States)

Gordon, John Howard

2014-09-09

A method of upgrading an oil feedstock by removing heteroatoms and/or one or more heavy metals from the oil feedstock composition. This method reacts the oil feedstock with an alkali metal and an upgradant hydrocarbon. The alkali metal reacts with a portion of the heteroatoms and/or one or more heavy metals to form an inorganic phase separable from the organic oil feedstock material. The upgradant hydrocarbon bonds to the oil feedstock material and increases the number of carbon atoms in the product. This increase in the number of carbon atoms of the product increases the energy value of the resulting oil feedstock.

Method for preparation of melts of alkali metal chlorides with highly volatile polyvalent metal chlorides

International Nuclear Information System (INIS)

Salyulev, A.B.; Kudyakov, V.Ya.

1990-01-01

A method for production of alkali metal (Cs, Rb, K) chloride melts with highly volatile polyvalent metal chlorides is suggested. The method consists, in saturation of alkali metal chlorides, preheated to the melting point, by volatile component vapours (titanium tetrachloride, molybdenum or tantalum pentachloride) in proportion, corresponding to the composition reguired. The saturation is realized in an evacuated vessel with two heating areas for 1-1.5 h. After gradual levelling of temperature in both areas the product is rapidly cooled. 1 fig.; 1 tab

Highly reproducible alkali metal doping system for organic crystals through enhanced diffusion of alkali metal by secondary thermal activation.

Science.gov (United States)

Lee, Jinho; Park, Chibeom; Song, Intek; Koo, Jin Young; Yoon, Taekyung; Kim, Jun Sung; Choi, Hee Cheul

2018-05-16

In this paper, we report an efficient alkali metal doping system for organic single crystals. Our system employs an enhanced diffusion method for the introduction of alkali metal into organic single crystals by controlling the sample temperature to induce secondary thermal activation. Using this system, we achieved intercalation of potassium into picene single crystals with closed packed crystal structures. Using optical microscopy and Raman spectroscopy, we confirmed that the resulting samples were uniformly doped and became K 2 picene single crystal, while only parts of the crystal are doped and transformed into K 2 picene without secondary thermal activation. Moreover, using a customized electrical measurement system, the insulator-to-semiconductor transition of picene single crystals upon doping was confirmed by in situ electrical conductivity and ex situ temperature-dependent resistivity measurements. X-ray diffraction studies showed that potassium atoms were intercalated between molecular layers of picene, and doped samples did not show any KH- nor KOH-related peaks, indicating that picene molecules are retained without structural decomposition. During recent decades, tremendous efforts have been exerted to develop high-performance organic semiconductors and superconductors, whereas as little attention has been devoted to doped organic crystals. Our method will enable efficient alkali metal doping of organic crystals and will be a resource for future systematic studies on the electrical property changes of these organic crystals upon doping.

Removal of oxides from alkali metal melts by reductive titration to electrical resistance-change end points

Science.gov (United States)

Tsang, Floris Y.

1980-01-01

Alkali metal oxides dissolved in alkali metal melts are reduced with soluble metals which are converted to insoluble oxides. The end points of the reduction is detected as an increase in electrical resistance across an alkali metal ion-conductive membrane interposed between the oxide-containing melt and a material capable of accepting the alkali metal ions from the membrane when a difference in electrical potential, of the appropriate polarity, is established across it. The resistance increase results from blocking of the membrane face by ions of the excess reductant metal, to which the membrane is essentially non-conductive.

Compression-Driven Enhancement of Electronic Correlations in Simple Alkali Metals

Science.gov (United States)

Fabbris, Gilberto; Lim, Jinhyuk; Veiga, Larissa; Haskel, Daniel; Schilling, James

2015-03-01

Alkali metals are the best realization of the nearly free electron model. This scenario appears to change dramatically as the alkalis are subjected to extreme pressure, leading to unexpected properties such as the departure from metallic behavior in Li and Na, and the occurrence of remarkable low-symmetry crystal structures in all alkalis. Although the mechanism behind these phase transitions is currently under debate, these are believed to be electronically driven. In this study the high-pressure electronic and structural ground state of Rb and Cs was investigated through low temperature XANES and XRD measurements combined with ab initio calculations. The results indicate that the pressure-induced localization of the conduction band triggers a Peierls-like mechanism, inducing the low symmetry phases. This localization process is evident by the pressure-driven increase in the number of d electrons, which takes place through strong spd hybridization. These experimental results indicate that compression turns the heavy alkali metals into strongly correlated electron systems. Work at Argonne was supported by DOE No. DE-AC02-06CH11357. Research at Washington University was supported by NSF DMR-1104742 and CDAC/DOE/NNSA DE-FC52-08NA28554.

Process for the recovery of alkali metal salts from aqueous solutions thereof

International Nuclear Information System (INIS)

Vitner, J.

1984-01-01

In an integrated process for the recovery of alkakli metal phenates and carboxylates from aqueous solutions thereof, the aqueous solution is spray dried and the drying gas stream is contacted with an aqueous alkali metal salt solution which dissolves the particles of the alkali metal salt that were entrained in the drying gas stream. The salt-free inert gas stream is then dried, heated, and returned to the spray dryer

Spin-rotation interaction of alkali-metal endash He-atom pairs

International Nuclear Information System (INIS)

Walker, T.G.; Thywissen, J.H.; Happer, W.

1997-01-01

A treatment of the spin-rotation coupling between alkali-metal atoms and He atoms is presented. Rotational distortions are accounted for in the wave function using a Coriolis interaction in the rotating frame. The expectation value of the spin-orbit interaction gives values of the spin-rotation coupling that explain previous experimental results. For spin-exchange optical pumping, the results suggest that lighter alkali-metal atoms would be preferred spin-exchange partners, other factors being equal. copyright 1997 The American Physical Society

Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

Science.gov (United States)

Doeff, Marca M.; Peng, Marcus Y.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard C.

1996-01-01

An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M.sub.x Z.sub.y Mn.sub.(1-y) O.sub.2, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell.

Alkali metal-refractory metal biphase electrode for AMTEC

Science.gov (United States)

Williams, Roger M. (Inventor); Bankston, Clyde P. (Inventor); Cole, Terry (Inventor); Khanna, Satish K. (Inventor); Jeffries-Nakamura, Barbara (Inventor); Wheeler, Bob L. (Inventor)

1989-01-01

An electrode having increased output with slower degradation is formed of a film applied to a beta-alumina solid electrolyte (BASE). The film comprises a refractory first metal M.sup.1 such as a platinum group metal, suitably platinum or rhodium, capable of forming a liquid or a strong surface adsorption phase with sodium at the operating temperature of an alkali metal thermoelectric converter (AMTEC) and a second refractory metal insoluble in sodium or the NaM.sup.1 liquid phase such as a Group IVB, VB or VIB metal, suitably tungsten, molybdenum, tantalum or niobium. The liquid phase or surface film provides fast transport through the electrode while the insoluble refractory metal provides a structural matrix for the electrode during operation. A trilayer structure that is stable and not subject to deadhesion comprises a first, thin layer of tungsten, an intermediate co-deposited layer of tungsten-platinum and a thin surface layer of platinum.

Chemistry and physics at liquid alkali metal/solid metal interfaces

International Nuclear Information System (INIS)

Barker, M.G.

1977-01-01

This paper describes the chemistry of processes which take place at the interface between liquid alkali metals and solid metal surfaces. A brief review of wetting data for liquid sodium is given and the significance of critical wetting temperatures discussed on the basis of an oxide-film reduction mechanism. The reactions of metal oxides with liquid metals are outlined and a correlation with wetting data established. The transfer of dissolved species from the liquid metal across the interface to form solid phases on the solid metal surface is well recognised. The principal features of such processes are described and a simple thermodynamic explanation is outlined. The reverse process, the removal of solid material into solution, is also considered. (author)

Plasma assisted measurements of alkali metal concentrations in pressurized combustion processes

International Nuclear Information System (INIS)

Hernberg, R.; Haeyrinen, V.

1995-01-01

The plasma assisted method for continuous measurement of alkali metal concentrations in product gas flows of pressurized energy processes will be tested and applied at the 1.6 MW PFBC/G facility at Delft University of Technology in the Netherlands. Measurements will be performed during 1995 and 1996 at different stages of the research programme. The results are expected to give information about the influence of different process conditions on the generation of alkali metal vapours, the comparison of different methods for alkali measurement and the specific performance of our system. The project belongs to the Joule II extension program under contract JOU2-CT93-0431. (author)

Influence of alkali metal cations/type of activator on the structure of alkali-activated fly ash - ATR-FTIR studies

Science.gov (United States)

Król, M.; Rożek, P.; Chlebda, D.; Mozgawa, W.

2018-06-01

Coal fly ash as a secondary aluminosiliceous raw material that is commonly used in the so-called geopolymerization process has been activated with different alkali hydroxides solutions: LiOH, NaOH and KOH. Changes in the aluminosilicate structure of the material during alkali-activation have been analyzed in detail on the basis of ATR/FT-IR spectra. These changes mainly affect both the integral intensity and FWHM of bands in the range of 1200-950 cm-1, however dehydration and carbonation process can be also analyzed based on obtaining results.

Evaluation of complexing agents and column temperature in ion chromatographic separation of alkali metals, alkaline earth metals and transition metals ion

International Nuclear Information System (INIS)

Kelkar, Anoop; Pandey, Ashish; Name, Anil B.; Das, D.K.; Behere, P.G.; Mohd Afzal

2015-01-01

The aim of ion chromatography method development is the resolution of all metal ions of interests. Resolution can be improved by changing the selectivity. Selectivity in chromatography can be altered by changes in mobile phase (eg eluent type, eluent strength) or through changes in stationary phase. Temperature has been used in altering the selectivity of particularly in reversed phase liquid chromatography and ion exchange chromatography. Present paper describe the retention behaviour of alkali metals, alkaline earth metals and transition metal ions on a silica based carboxylate function group containing analyte column. Alkali metals, alkaline earth metals and transition metal ions were detected by ion conductivity and UV-VIS detectors respectively

Neutron scattering investigation of layer-bending modes in alkali-metal--graphite intercalation compounds

International Nuclear Information System (INIS)

Zabel, H.; Kamitakahara, W.A.; Nicklow, R.M.

1982-01-01

Phonon dispersion curves for low-frequency transverse modes propagating in the basal plane have been measured in the alkali-metal--graphite intercalation compounds KC 8 , CsC 8 , KC 24 , and RbC 24 by means of neutron spectroscopy. The acoustic branches show an almost quadratic dispersion relation at small q, characteristic of strongly layered materials. The optical branches of stage-1 compounds can be classified as either graphitelike branches showing dispersion, or as almost dispersionless alkali-metal-like modes. Macroscopic shear constants C 44 and layer-bending moduli have been obtained for the intercalation compounds by analyzing the data in terms of a simple semicontinuum model. In stage-2 compounds, a dramatic softening of the shear constant by about a factor of 8 compared with pure graphite has been observed. Low-temperature results on KC 24 indicate the opening of a frequency gap near the alkali-metal Brillouin-zone boundary, possibly due to the formation of the alkali-metal superstructure

Thermochemistry of uranium(VI), arsenic, and alkali metal triple oxides

International Nuclear Information System (INIS)

Karyakin, N.V.; Chernorukov, G.N.

1994-01-01

The standard enthalpies of reactions of stoichiometric mixtures of potassium dyhydrogen orthoarsenate, uranium(VI) oxide, alkali metal nitrates, and of mixtures of triple oxides with the general formula M I AsUO 6 (M I =Li, Na, K, Rb, and Cs) and potassium nitrate with aqueous solution of hydrofluoric acid were determined an an adiabatic calorimeter at 298.15 K. The standard enthalpies of formation of uranium(VI), arsenic, and alkali metal triple oxides at 298.15 K were calculated form the data obtained. 8 refs., 1 tab

50 years of superbases made from organolithium compounds and heavier alkali metal alkoxides

Czech Academy of Sciences Publication Activity Database

Lochmann, Lubomír; Janata, Miroslav

2014-01-01

Roč. 12, č. 5 (2014), s. 537-548 ISSN 1895-1066 R&D Projects: GA ČR GAP106/12/0844 Institutional support: RVO:61389013 Keywords : superbases * heavier alkali metal compounds * lithium -heavier alkali metal interchange Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.329, year: 2013

Selective adsorption and ion exchange of metal cations and anions with silico-titanates and layered titanates

International Nuclear Information System (INIS)

Anthony, R.G.; Philip, C.V.

1993-01-01

Metal ions may be removed from aqueous wastes from metal processing plants and from refineries. They may also be used in concentrating radioactive elements found in dilute, aqueous, nuclear wastes. A new series of silico-titanates and alkali titanates are shown to have specific selectivity for cations of lead, mercury, and cadmium and the dichromate anion in solutions with low and high pH. Furthermore, one particular silico-titanate, TAM-5, was found to be highly selective for Cs + and Sr 2+ in solutions of 5.7 M Na + and 0.6 M Oh - . A high potential exists for these materials for removing Cs + and Sr 2+ from radioactive aqueous wastes containing high concentrations of Na + at high and low pH

Separation of alkali, alkaline earth and rare earth cations by liquid membranes containing macrocyclic carriers. Third progress report, September 1, 1980-April 1, 1981

International Nuclear Information System (INIS)

Christensen, J.J.

1981-01-01

The overall objective of this project is to study the use of liquid membrane systems employing macrocyclic ligand carriers in making separations among metal cations. During the third year of the project, work continued in the development of a mathematical model to describe cation transport. The model was originally developed to describe the relationship between cation transport rate (J/sub M/) and the cation-macrocycle stability constant (K). The model was tested by determining the rates of transport of alkali and alkaline earth cations through chloroform membranes containing carrier ligands where the stability constants for their reaction with cations in methanol were known. From the results, it is clear that the model correctly describes the dependence of J/sub M/ on log K. The model also correctly describes the effect of cation concentration and carrier concentration on cation transport rates, as detailed in the previous progress report. During the third year of the project, the transport model was expanded so as to apply to competitive transport of cations from mixtures of two cations in the source aqueous phase. Data were collected under these conditions and the ability of the model to predict the flux of each cation was tested. Representative data of this type are presented along with corresponding data which were obtained when each cation was transported by the same carrier from a source phase containing only that cation. Comparison of transport rates determined under the two experimental conditions indicates that the relationship between the two sets of data is complex. To date, a few of these data involving transport from binary cation mixtures have been tested against the transport model. It was found that the model correctly predicts the cation fluxes from cation mixtures. These preliminary results indicate that the transport model can successfully predict separation factors when cation mixtures are used

Electronic nature of zwitterionic alkali metal methanides, silanides and germanides - a combined experimental and computational approach.

Science.gov (United States)

Li, H; Aquino, A J A; Cordes, D B; Hase, W L; Krempner, C

2017-02-01

Zwitterionic group 14 complexes of the alkali metals of formula [C(SiMe 2 OCH 2 CH 2 OMe) 3 M], (M- 1 ), [Si(SiMe 2 OCH 2 CH 2 OMe) 3 M], (M- 2 ), [Ge(SiMe 2 OCH 2 CH 2 OMe) 3 M], (M- 3 ), where M = Li, Na or K, have been prepared, structurally characterized and their electronic nature was investigated by computational methods. Zwitterions M- 2 and M- 3 were synthesized via reactions of [Si(SiMe 2 OCH 2 CH 2 OMe) 4 ] ( 2 ) and [Ge(SiMe 2 OCH 2 CH 2 OMe) 4 ] ( 3 ) with MOBu t (M = Li, Na or K), resp., in almost quantitative yields, while M- 1 were prepared from deprotonation of [HC(SiMe 2 OCH 2 CH 2 OMe) 3 ] ( 1 ) with LiBu t , NaCH 2 Ph and KCH 2 Ph, resp. X-ray crystallographic studies and DFT calculations in the gas-phase, including calculations of the NPA charges confirm the zwitterionic nature of these compounds, with the alkali metal cations being rigidly locked and charge separated from the anion by the internal OCH 2 CH 2 OMe donor groups. Natural bond orbital (NBO) analysis and the second order perturbation theory analysis of the NBOs reveal significant hyperconjugative interactions in M- 1 -M- 3 , primarily between the lone pair and the antibonding Si-O orbitals, the extent of which decreases in the order M- 1 > M- 2 > M- 3 . The experimental basicities and the calculated gas-phase basicities of M- 1 -M- 3 reveal the zwitterionic alkali metal methanides M- 1 to be significantly stronger bases than the analogous silanides M- 2 and germanium M- 3 .

Metal analyses of ash derived alkalis from banana and plantain ...

African Journals Online (AJOL)

The objective of this work was to determine the metal content of plantain and banana peels ash derived alkali and the possibility of using it as alternate and cheap source of alkali in soap industry. This was done by ashing the peels and dissolving it in de-ionised water to achieve the corresponding hydroxides with pH above ...

Review of alkali metal and refractory alloy compatibility for Rankine cycle applications

International Nuclear Information System (INIS)

DiStefano, J.R.

1989-01-01

The principal corrosion mechanisms in refractory metal-alkali systems are dissolution, mass transfer, and impurity reactions. In general, niobium, tantalum, molybdenum, and tungsten have low solubilities in the alkali metals, even to very high temperatures, and static corrosion studies have verified that the systems are basically compatible. Loop studies with niobium and tantalum based alloys do not indicate any serious problems due to temperature gradient mass transfer. Above 1000 K, dissimilar metal mass transfer is noted between the refractory metals and iron or nickel based alloys. The most serious corrosion problems encountered are related to impurity reactions associated with oxygen

Inclusion Extraction of Alkali Metals by Emulsion Liquid Membranes and Nano-baskets of p-tert-Calix[4]arene Bearing Di-[N-(X)sulfonyl Carboxamide] and Di-(1-propoxy) in ortho-cone Conformation

Energy Technology Data Exchange (ETDEWEB)

Mokhtari, Bahram; Pourabdollah, Kobra [Islamic Azad University, Province (Iran, Islamic Republic of)

2012-05-15

Nano-assisted inclusion separation of alkali metals from basic solutions was reported by inclusion-facilitated emulsion liquid membrane process. The novelty of this study is application of nano-baskets of calixarene in the selective and efficient separation of alkali metals as both the carrier and the surfactant. For this aim, four derivatives of p-tert-calix[4]arene bearing different sulfonamide moieties were synthesized and their inclusionextraction parameters were optimized including the calixarene scaffold 3 (4 wt %) as the carrier/demulsifier, the commercial kerosene as diluent in membrane, sulphonic acid (0.2 M) and ammonium carbonate (0.4 M) as the strip and the feed phases, the phase and the treat ratios of 0.8 and 0.3, mixing speed (300 rpm), and initial solute concentration (100 mg/L). The selectivity of membrane over more than ten interfering cations was examined and the results reveled that under the optimized operating condition, the degree of inclusionextraction of alkali metals was as high as 98-99%.

Inclusion Extraction of Alkali Metals by Emulsion Liquid Membranes and Nano-baskets of p-tert-Calix[4]arene Bearing Di-[N-(X)sulfonyl Carboxamide] and Di-(1-propoxy) in ortho-cone Conformation

International Nuclear Information System (INIS)

Mokhtari, Bahram; Pourabdollah, Kobra

2012-01-01

Nano-assisted inclusion separation of alkali metals from basic solutions was reported by inclusion-facilitated emulsion liquid membrane process. The novelty of this study is application of nano-baskets of calixarene in the selective and efficient separation of alkali metals as both the carrier and the surfactant. For this aim, four derivatives of p-tert-calix[4]arene bearing different sulfonamide moieties were synthesized and their inclusionextraction parameters were optimized including the calixarene scaffold 3 (4 wt %) as the carrier/demulsifier, the commercial kerosene as diluent in membrane, sulphonic acid (0.2 M) and ammonium carbonate (0.4 M) as the strip and the feed phases, the phase and the treat ratios of 0.8 and 0.3, mixing speed (300 rpm), and initial solute concentration (100 mg/L). The selectivity of membrane over more than ten interfering cations was examined and the results reveled that under the optimized operating condition, the degree of inclusionextraction of alkali metals was as high as 98-99%

Alkali metals in fungi of forest soil

International Nuclear Information System (INIS)

Vinichuk, M.; Taylor, A.; Rosen, K.; Nikolova, I.; Johanson, K.J.

2009-01-01

The high affinity of forest soil fungi for alkali metals such as potassium, rubidium, caesium as well as radiocaesium is shown and discussed. Good positive correlation was found between K: Rb concentration ratios in soil and in fungi, when correlation between K: Cs concentration ratios was less pronounced. (LN)

Heat transfer characteristics of alkali metals flowing across tube banks

International Nuclear Information System (INIS)

Sugiyama, K.; Ishiguro, R.; Kojima, Y.; Kanaoka, H.

2004-01-01

For the purpose of getting heat transfer coefficients of alkali metals flowing across tube banks at an acceptable level, we propose to use an inviscid-irrotational flow model, which is based on our flow visualization experiment. We show that the heat transfer coefficients obtained for the condition where only the test rod is heated in tube banks considerably differ from those obtained for the condition where all the rods are heated, because of interference between thick thermal boundary layers of alkali metals. We also confirm that the analytical values obtained by this flow model are in a reasonable agreement with experimental values. (author)

Volume dependence of the melting temperature for alkali metals with Debye's model

International Nuclear Information System (INIS)

Soma, T.; Kagaya, H.M.; Nishigaki, M.

1983-01-01

Using the volume dependence of the Grueneisen constant at higher temperatures, the volume effect on the melting temperature of alkali metals is studied by Lindeman's melting law and Debye's model. The obtained melting curve increases as a function of the compressed volume and shows the maximum of the melting point at the characteristic volume. The resultant data are qualitatively in agreement with the observed tendency for alkali metals. (author)

Alkali-crown ether complexes at metal surfaces

Energy Technology Data Exchange (ETDEWEB)

Thontasen, Nicha; Deng, Zhitao; Rauschenbach, Stephan [Max Planck Institute for Solid State Research, Stuttgart (Germany); Levita, Giacomo [University of Trieste, Trieste (Italy); Malinowski, Nikola [Max Planck Institute for Solid State Research, Stuttgart (Germany); Bulgarian Academy of Sciences, Sofia (Bulgaria); Kern, Klaus [Max Planck Institute for Solid State Research, Stuttgart (Germany); EPFL, Lausanne (Switzerland)

2010-07-01

Crown ethers are polycyclic ethers which, in solution, selectively bind cations depending on the size of the ring cavity. The study of a single host-guest complex is highly desirable in order to reveal the characteristics of these specific interactions at the atomic scale. Such detailed investigation is possible at the surface where high resolution imaging tools like scanning tunneling microscopy (STM) can be applied. Here, electrospray ion beam deposition (ES-IBD) is employed for the deposition of Dibenzo-24-crown-8 (DB24C8)-H{sup +}, -Na{sup +} and -Cs{sup +} complexes on a solid surface in ultrahigh vacuum (UHV). Where other deposition techniques have not been successful, this deposition technique combines the advantages of solution based preparation of the complex ions with a highly clean and controlled deposition in UHV. Single molecular structures and the cation-binding of DB24C8 at the surface are studied in situ by STM and MALDI-MS (matrix assisted laser desorption ionization mass spectrometry). The internal structure of the complex, i.e. ring and cavity, is observable only when alkali cations are incorporated. The BD24C8-H{sup +} complex in contrast appears as a compact feature. This result is in good agreement with theoretical models based on density functional theory calculations.

Polarizabilities and hyperpolarizabilities of the alkali metal atoms

Energy Technology Data Exchange (ETDEWEB)

Fuentealba, P. (Chile Univ., Santiago (Chile). Departamento de Fisica and Centro de Mecanica Cuantica Aplicada (CMCA)); Reyes, O. (Chile Univ., Santiago (Chile). Dept. de Fisica)

1993-08-14

The electric static dipole polarizability [alpha], quadrupole polarizability C, dipole-quadrupole polarizability B, and the second dipole hyperpolarizability [gamma] have been calculated for the alkali metal atoms in the ground state. The results are based on a pseudopotential which is able to incorporate the very important core-valence correlation effect through a core polarization potential, and, in an empirical way, the main relativistic effects. The calculated properties compare very well with more elaborated calculations for the Li atom, excepting the second hyperpolarizability [gamma]. For the other atoms, there is neither theoretical nor experimental information about most of the higher polarizabilities. Hence, the results of this paper should be seen as a first attempt to give a complete account of the series expansion of the interaction energy of an alkali metal atom and a static electric field. (author).

Polarizabilities and hyperpolarizabilities of the alkali metal atoms

International Nuclear Information System (INIS)

Fuentealba, P.; Reyes, O.

1993-01-01

The electric static dipole polarizability α, quadrupole polarizability C, dipole-quadrupole polarizability B, and the second dipole hyperpolarizability γ have been calculated for the alkali metal atoms in the ground state. The results are based on a pseudopotential which is able to incorporate the very important core-valence correlation effect through a core polarization potential, and, in an empirical way, the main relativistic effects. The calculated properties compare very well with more elaborated calculations for the Li atom, excepting the second hyperpolarizability γ. For the other atoms, there is neither theoretical nor experimental information about most of the higher polarizabilities. Hence, the results of this paper should be seen as a first attempt to give a complete account of the series expansion of the interaction energy of an alkali metal atom and a static electric field. (author)

Energy loss spectroscopy study of Si(111)--alkali metal interfaces at low temperatures

International Nuclear Information System (INIS)

Avci, R.

1986-01-01

Studies are made at approx.150 K under ultrahigh vacuum conditions on a wide range of alkali metal coverages on Si(111)-7 x 7. Negative second-derivative backscattered electron energy loss spectroscopy is used with 100 eV primary electrons. The interaction of the alkali metals with the silicon substrate goes through two stages as a function of alkali coverage: In the initial coverages, for less than approx.0.3 monolayer of alkali atoms, the basic reaction is that of charge transfer from the alkali atoms to the Si surface with a loss peak at approx.3.3 eV associated with the charge transfer states. The second stage of reaction: starting after the depletion of all the Si surface states: falls in a coverage range between approx.0.3 and approx.1 monolayer, in which the formation of a metallic layer with a coverage-dependent loss feature at about 2 eV is observed. At still higher coverages, multiple surface and bulk plasmon excitations and their combinations are dominant. In the overall scattering processes most of the parallel momentum (approx.3 A -1 ) is transferred to the sample during the elastic backscattering from the surface, and all the losses are essentially attributed to the forward inelastic scattering before and/or after the elastic process takes place near the metal/Si interface

Solubility and solvation of alkali metal perchlorates, tetramethyl and tetraethylammonium in aqua-ketone solvents

International Nuclear Information System (INIS)

Kireev, A.A.; Pak, T.G.; Bezuglyj, V.D.

1998-01-01

The KClO 4 , RbClO 4 , CsClO 4 , (CH 3 ) 4 NClO 4 , (C 2 H 5 ) 4 NClO 4 solubility in water and water-acetone, water-methylethylketone mixtures is determined through the method of isothermal saturation at 298.15 K. Dissociation constants of alkali metals perchlorates in acetone and its 90% mixtures (by volume) are determined conductometrically. Solubility products and standard energies of the Gibbs transfer of the studied electrolytes from water into water-acetone and water-methylethylketone solvents. It is established that the Gibbs standard energies of Na + , K + , Rb + and Cs + cations transfer from water to water-ketone solvents are close to each other. It is shown that the effect of acetone and methylethylketone on solvation of the studied electrolytes is practically similar

Pma1 is an alkali/alkaline earth metal cation ATPase that preferentially transports Na(+) and K(+) across the Mycobacterium smegmatis plasma membrane.

Science.gov (United States)

Ayala-Torres, Carlos; Novoa-Aponte, Lorena; Soto, Carlos Y

2015-07-01

Mycobacterium smegmatis Pma1 is the orthologue of M. tuberculosis P-type ATPase cation transporter CtpF, which is activated under stress conditions, such as hypoxia, starvation and response to antituberculous and toxic substances. The function of Pma1 in the mycobacterial processes across the plasma membrane has not been characterised. In this work, bioinformatic analyses revealed that Pma1 likely contains potential sites for, Na(+), K(+) and Ca(2+) binding and transport. Accordingly, RT-qPCR experiments showed that M. smegmatis pma1 transcription is stimulated by sub-lethal doses of Na(+), K(+) and Ca(2+); in addition, the ATPase activity of plasma membrane vesicles in recombinant Pma1-expressing M. smegmatis cells is stimulated by treatment with these cations. In contrast, M. smegmatis cells homologously expressing Pma1 displayed tolerance to high doses of Na(+) and K(+) but not to Ca(2+) ions. Consistently, the recombinant protein Km embedded in plasma membrane demonstrated that Ca(2+) has more affinity for Pma1 than Na(+) and K(+) ions; furthermore, the estimation of Vmax/Km suggests that Na(+) and K(+) ions are more efficiently translocated than Ca(2+). Thus, these results strongly suggest that Pma1 is a promiscuous alkali/alkaline earth cation ATPase that preferentially transports Na(+) and/or K(+) across the mycobacterial plasma membrane. Copyright © 2015 Elsevier GmbH. All rights reserved.

ADSORPTION METHOD FOR SEPARATING METAL CATIONS

Science.gov (United States)

Khym, J.X.

1959-03-10

The chromatographic separation of fission product cations is discussed. By use of this method a mixture of metal cations containing Zr, Cb, Ce, Y, Ba, and Sr may be separated from one another. Mentioned as preferred exchange adsorbents are resins containing free sulfonic acid groups. Various eluants, such as tartaric acid, HCl, and citric acid, used at various acidities, are employed to effect the selective elution and separation of the various fission product cations.

Liquid-solid extraction of cationic metals by cationic amphiphiles

International Nuclear Information System (INIS)

Muller, W.

2010-01-01

In the field of selective separation for recycling of spent nuclear fuel, liquid-liquid extraction processes are widely used (PUREX, DIAMEX..) in industrial scale. In order to guarantee a sustainable nuclear energy for the forthcoming generations, alternative reprocessing techniques are under development. One of them bases on the studies from Heckmann et al in the 80's and consists in selectively precipitating actinides from aqueous waste solutions by cationic surfactants (liquid-solid extraction). This technique has some interesting advantages over liquid-liquid extraction techniques, because several steps are omitted like stripping or solvent washing. Moreover, the amount of waste is decreased considerably, since no contaminated organic solvent is produced. In this thesis, we have carried out a physico-chemical study to understand the specific interactions between the metallic cations with the cationic surfactant. First, we have analysed the specific effect of the different counter-ions (Cl - , NO 3 - , C 2 O 4 2- ) and then the effect of alkaline cations on the structural properties of the surfactant aggregation in varying thermodynamical conditions. Finally, different multivalent cations (Cu 2+ , Zn 2+ , UO 2 2+ , Fe 3+ , Nd 3+ , Eu 3+ , Th 4+ ) were considered; we have concluded that depending on the anionic complex of these metals formed in acidic media, we can observe either an adsorption at the micellar interface or not. This adsorption has a large influence of the surfactant aggregation properties and determines the limits of the application in term of ionic strength, temperature and surfactant concentration. (author) [fr

Binding properties of oxacalix[4]arenes derivatives toward metal cations; Interactions entre cations metalliques et derives des oxacalix[4]arenes

Energy Technology Data Exchange (ETDEWEB)

Mellah, B

2006-11-15

The objective of this work was to establish the binding properties of oxacalix[4]arene derivatives with different numbers of the oxa bridges, functional groups (ketones, pyridine, ester, amide and methoxy) and conformations. Their interactions with alkali and alkaline-earth, heavy and transition metal cations have been evaluated according to different approaches: (i) extraction of corresponding picrates from an aqueous phase into dichloromethane; (ii) determination of the thermodynamic parameters of complexation in methanol and/or acetonitrile by UV-spectrophotometry and micro-calorimetry; (iii) determination of the stoichiometry of the complexes by ESI-MS; (iv) {sup 1}H-NMR titrations allowing to localize the metal ions in the ligand cavity. In a first part dealing on homo-oxacalix[4]arenes, selectivities for Na{sup +}, K{sup +}, Ca{sup 2+}, Pb{sup 2+} and Mn{sup 2+} of ketones derivatives was shown. The presence of oxa bridge in these derivatives increases their efficiency while decreasing their selectivity with respect to related calixarenes. The pyridine derivative prefers transition and heavy metal cations, in agreement with the presence of the soft nitrogen atoms. In the second part, di-oxacalix[4]arene ester and secondary amide derivatives were shown to be less effective than tertiary amide counterparts but to present high selectivities for Li{sup +}, Ba{sup 2+}, Zn{sup 2+} and Hg{sup 2+}. A third part devoted to the octa-homo-tetra-oxacalix[4]arene tetra-methoxy shows that the 1:1 metal complexes formed are generally more stable than those of calixarenes, suggesting the participation of the oxygen atoms of the bridge in the complexation. Selectivity for Cs{sup +}, Ba{sup 2+}, Cu{sup 2+} and Hg{sup 2+} were noted. (author)

Separation of alkali and alkaline earth metals by polyethers using extraction chromatography

International Nuclear Information System (INIS)

Smulek, W.; Lada, W.A.

1979-01-01

The separation of alkali and alkaline earth metals by means of an acyclic polyether, 1,13-bis(8-chinolinyl)-1, 4, 7, 10, 13-pentaoxatridecane (CPOD), and cyclic polyethers, benzo-15-crown-5 (BC), dibenzo-18-crown-6 (DBC) and dicyclohexyl-18-crown-6 (DCHC), using extraction chromatography has been studied. The alkali metals can be effectively separated using SCN - as the accompanying ion. For alkaline earth metals, the best results were obtained with ClO 4 - ions. Different elution sequences for these groups were observed using chloroform and/meen=/ sitylene as diluents for the polyethers. (author)

Alkali and heavy metals emissions of the PCFB-process

International Nuclear Information System (INIS)

Kuivalainen, R.; Eriksson, T.; Koskinen, J.; Lehtonen, P.

1995-01-01

Pressurized Circulating Fluidized Bed (PCFB) combustion technology has been developed by A. Ahlstrom Corporation since 1986. As a part of the development, a 10 MV PCFB Test Facility was constructed at Hans Ahlstrom Laboratory in Karhula, Finland in 1989. The Test Facility has been used for performance testing with different coal types through the years 1990-1994 for obtaining data for design and commercialization of the high-efficiency low-emission PCFB combustion technology. The project Y44 'Alkali and heavy metal emissions of the PCFB-process' is part of national LIEKKI 2 research program and it continues the work started under alkali measurement project Y33 in 1994. The objective of the project is to measure vapor phase alkali and heavy metal concentrations in the PCFB flue gas after high-temperature high-pressure particulate filter and to investigate the effects of process conditions and sorbents on alkali release. The measured Na concentrations were between 0,03 and 0,21 ppm(w). The results of K were between 0,01 and 0,08 ppm(w). The accuracy of the results is about +-50 percent at this concentration range. The scatter of the data covers the effects of different process variables on the alkali emission. The measured emissions at 800-850 deg C are at the same order of magnitude as the guideline emission limits given by gas turbine manufacturers for flue gas at 1000-1200 deg C. The measurements and development of the analyses methods are planned to be continued during PCFB test runs in autumn 1995 in cooperation with laboratories of VTT Energy and Tampere University of Technology. (author)

Method for intercalating alkali metal ions into carbon electrodes

Science.gov (United States)

Doeff, Marca M.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard

1995-01-01

A low cost, relatively flexible, carbon electrode for use in a secondary battery is described. A method is provided for producing same, including intercalating alkali metal salts such as sodium and lithium into carbon.

High-pressure phase transition of alkali metal-transition metal deuteride Li2PdD2

Science.gov (United States)

Yao, Yansun; Stavrou, Elissaios; Goncharov, Alexander F.; Majumdar, Arnab; Wang, Hui; Prakapenka, Vitali B.; Epshteyn, Albert; Purdy, Andrew P.

2017-06-01

A combined theoretical and experimental study of lithium palladium deuteride (Li2PdD2) subjected to pressures up to 50 GPa reveals one structural phase transition near 10 GPa, detected by synchrotron powder x-ray diffraction, and metadynamics simulations. The ambient-pressure tetragonal phase of Li2PdD2 transforms into a monoclinic C2/m phase that is distinct from all known structures of alkali metal-transition metal hydrides/deuterides. The structure of the high-pressure phase was characterized using ab initio computational techniques and from refinement of the powder x-ray diffraction data. In the high-pressure phase, the PdD2 complexes lose molecular integrity and are fused to extended [PdD2]∞ chains. The discovered phase transition and new structure are relevant to the possible hydrogen storage application of Li2PdD2 and alkali metal-transition metal hydrides in general.

Alkali Metal Heat Pipe Life Issues

International Nuclear Information System (INIS)

Reid, Robert S.

2004-01-01

One approach to fission power system design uses alkali metal heat pipes for the core primary heat-transfer system. Heat pipes may also be used as radiator elements or auxiliary thermal control elements. This synopsis characterizes long-life core heat pipes. References are included where information that is more detailed can be found. Specifics shown here are for demonstration purposes and do not necessarily reflect current Nasa Project Prometheus point designs. (author)

Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism

OpenAIRE

Boughlala, Z.; Guerra, C.F.; Bickelhaupt, F.M.

2016-01-01

Abstract We have analyzed the structure and bonding of gas?phase Cl?X and [HCl?X]+ complexes for X+=?H+, CH3 +, Li+, and Na+, using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl? and HCl for the various cations. The Cl?X bond becomes longer and weaker along X+?=?H+, CH3 +, Li+, and Na+. Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence ...

Survival probability in small angle scattering of low energy alkali ions from alkali covered metal surfaces

International Nuclear Information System (INIS)

Neskovic, N.; Ciric, D.; Perovic, B.

1982-01-01

The survival probability in small angle scattering of low energy alkali ions from alkali covered metal surfaces is considered. The model is based on the momentum approximation. The projectiles are K + ions and the target is the (001)Ni+K surface. The incident energy is 100 eV and the incident angle 5 0 . The interaction potential of the projectile and the target consists of the Born-Mayer, the dipole and the image charge potentials. The transition probability function corresponds to the resonant electron transition to the 4s projectile energy level. (orig.)

Ion conducting polymers and polymer blends for alkali metal ion batteries

Science.gov (United States)

DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra

2017-08-29

Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.

A brief history of residual alkali metal destruction development in the UK

International Nuclear Information System (INIS)

Fletcher, Brian

2014-01-01

The reactors at Dounreay are being decommissioned and there is a need to remove all the residual alkali metal before they can be dismantled. When the Prototype Fast Reactor was shut down work was started to remove the bulk sodium and development of the Water Vapour Nitrogen (WVN) process for the destruction of the residual alkali metal commenced. This development has been ongoing to the present day. Trials began with small amounts of sodium and NaK before moving to larger scale experiments. The development raised a number of issues. As knowledge was built up, the development was expanded to deal with NaK pools in the DFR. Differences in the behaviour of NaK and sodium led to various different processes being developed. This paper presents a brief history of the alkali metal destruction process development within the UK and highlights some of the lessons learnt for future application during reactor decommissioning (authors)

Effects of metallic cations in the beryl flotation

International Nuclear Information System (INIS)

Lima Leonel, C.M. de; Peres, A.E.C.

1984-01-01

The beryl zeta potential in microelectrophoretic cell is studied in the presence of neutral electrolyte, cations of calcium, magnesium and iron. The petroleum sulfonate is used how collector in Hallimond tube. Hydroxy complex of metallic cations seems activate the ore and precipitates of colloidal metallic hidroxies seems lower him when added to the mixture. (M.A.C.) [pt

Recent progress in rechargeable alkali metalâair batteries

OpenAIRE

Xin Zhang; Xin-Gai Wang; Zhaojun Xie; Zhen Zhou

2016-01-01

Rechargeable alkali metalâair batteries are considered as the most promising candidate for the power source of electric vehicles (EVs) due to their high energy density. However, the practical application of metalâair batteries is still challenging. In the past decade, many strategies have been purposed and explored, which promoted the development of metalâair batteries. The reaction mechanisms have been gradually clarified and catalysts have been rationally designed for air cathodes. In this ...

A simple alkali-metal and noble gas ion source for SIMS equipments with mass separation of the primary ions

International Nuclear Information System (INIS)

Duesterhoeft, H.; Pippig, R.

1986-01-01

An alkali-metal ion source working without a store of alkali-metals is described. The alkali-metal ions are produced by evaporation of alkali salts and ionization in a low-voltage arc discharge stabilized with a noble gas plasma or in the case of small alkali-metal ion currents on the base of the well known thermic ionization at a hot tungsten wire. The source is very simple in construction and produces a stable ion current of 0.3 μA for more than 100 h. It is possible to change the ion species in a short time. This source is applicable to all SIMS equipments using mass separation for primary ions. (author)

In situ formation of coal gasification catalysts from low cost alkali metal salts

Science.gov (United States)

Wood, Bernard J.; Brittain, Robert D.; Sancier, Kenneth M.

1985-01-01

A carbonaceous material, such as crushed coal, is admixed or impregnated with an inexpensive alkali metal compound, such as sodium chloride, and then pretreated with a stream containing steam at a temperature of 350.degree. to 650.degree. C. to enhance the catalytic activity of the mixture in a subsequent gasification of the mixture. The treatment may result in the transformation of the alkali metal compound into another, more catalytically active, form.

Evaluation of Ce3+ and alkali metal ions Co-doped LiSrAlF6 crystalline scintillators

International Nuclear Information System (INIS)

Wakahara, Shingo; Yanagida, Takayuki; Fujimoto, Yutaka; Yokota, Yuui; Pejchal, Jan; Kurosawa, Shunsuke; Suzuki, Shotaro; Kawaguchi, Noriaki; Fukuda, Kentaro; Yoshikawa, Akira

2013-01-01

High scintillation efficiency of Eu-doped LiSrAlF 6 (LiSAF) and LiCaAlF 6 (LiCAF) codoped with alkali metal ions has been reported in our recent studies. Thus in this paper, we demonstrated the scintillation properties of 1% Ce-doped LiSAF crystals with 1% alkali metal ions co-doping to increase the light yield and understand the scintillation mechanism. The crystals showed intense emission band corresponding to the 5d-4f transition of Ce 3+ , and their light yields under thermal neutron excitation were higher than that of the Ce only doped crystal. Especially, the light yield of Ce–Na co-doped crystal exceeded about two times that of Ce only doped one. -- Highlights: ► Ce-doped and alkali metal co-doped LiSAF crystals were grown by μ-PD method. ► Alkali metal co-doped crystals showed higher light yield than Ce only doped crystal. ► Decay time of alkali metal co-doped LiSAF were longer than that of Ce only doped one

Uranium metalla-allenes with carbene imido R_2C=U"I"V=NR' units (R=Ph_2PNSiMe_3; R'=CPh_3): alkali-metal-mediated push-pull effects with an amido auxiliary

International Nuclear Information System (INIS)

Lu, Erli; Tuna, Floriana; Kaltsoyannis, Nikolas; Liddle, Stephen T.; Lewis, William

2016-01-01

We report uranium(IV)-carbene-imido-amide metalla-allene complexes [U(BIPM"T"M"S)(NCPh_3)(NHCPh_3)(M)] (BIPM"T"M"S=C(PPh_2NSiMe_3)_2; M=Li or K) that can be described as R_2C=U=NR' push-pull metalla-allene units, as organometallic counterparts of the well-known push-pull organic allenes. The solid-state structures reveal that the R_2C=U=NR' units adopt highly unusual cis-arrangements, which are also reproduced by gas-phase theoretical studies conducted without the alkali metals to remove their potential structure-directing roles. Computational studies confirm the double-bond nature of the U=NR' and U=CR_2 interactions, the latter increasingly attenuated by potassium then lithium when compared to the hypothetical alkali-metal-free anion. Combined experimental and theoretical data show that the push-pull effect induced by the alkali metal cations and amide auxiliary gives a fundamental and tunable structural influence over the C=U"I"V=N units. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Capillary electrochromatography of inorganic cations in open tubular columns with a controllable capacity multilayered stationary phase architecture.

Science.gov (United States)

Kubán, Pavel; Kubán, Petr; Kubán, Vlastimil; Hauser, Peter C; Bocek, Petr

2008-05-09

In this paper capillary electrochromatography of alkali and alkaline-earth metal cations in open tubular capillary columns is described. Capillary columns are prepared by coating fused silica capillaries of 75 microm I.D. with poly(butadiene-maleic acid) copolymer (PBMA) in multiple layers. Thermally initiated radical polymerization is used to crosslink the stationary phase. Capillary columns with different number of stationary phase layers can be prepared and allow for the adjustment of separation selectivity in the electrochromatographic mode. Fast and sensitive separations of common inorganic cations are achieved in less than 6 min in a 60 cm capillary column with on-column capacitively coupled contactless conductivity detector. Limits of detection (S/N=3) for the determination of alkali and alkaline-earth metal cations range from 0.3 to 2.5 microM and repeatability is better than 0.5, 4.5 and 6.1% for migration times, peak heights and peak areas, respectively.

An assessment of the melting, boiling, and critical point data of the alkali metals

International Nuclear Information System (INIS)

Ohse, R.W.; Babelot, J.-F.; Magill, J.

1985-01-01

The paper reviews the measured melting, boiling and critical point data of alkali metals. A survey of the static heat generation methods for density and pressure-volume-temperature measurements is given. Measured data on the melting and boiling temperatures of lithium, sodium, potassium, rubidium and caesium are summarised. Also measured critical point data for the same five alkali metals are presented, and discussed. (U.K.)

Alkali metal protective garment and composite material

Science.gov (United States)

Ballif, III, John L.; Yuan, Wei W.

1980-01-01

A protective garment and composite material providing satisfactory heat resistance and physical protection for articles and personnel exposed to hot molten alkali metals, such as sodium. Physical protection is provided by a continuous layer of nickel foil. Heat resistance is provided by an underlying backing layer of thermal insulation. Overlying outer layers of fireproof woven ceramic fibers are used to protect the foil during storage and handling.

Inner-shell excitation of alkali-metal atoms

International Nuclear Information System (INIS)

Tiwary, S.N.

1987-06-01

Inner-shell excitation of alkali-metal atoms, which leads to auto-ionization, is reviewed. The validity of quantum mechanical approximation is analyzed and the importance of exchange and correlation is demonstrated. Basic difficulties in making accurate calculations for inner-shell excitation process are discussed. Suggestions are made for further study of inner-shell process in atoms and ions. (author). 26 refs, 4 figs, 1 tab

In Situ Measurement of Alkali Metals in an MSW Incinerator Using a Spontaneous Emission Spectrum

Directory of Open Access Journals (Sweden)

Weijie Yan

2017-03-01

Full Text Available This paper presents experimental investigations of the in situ diagnosis of the alkali metals in the municipal solid waste (MSW flame of an industrial grade incinerator using flame emission spectroscopy. The spectral radiation intensities of the MSW flame were obtained using a spectrometer. A linear polynomial fitting method is proposed to uncouple the continuous spectrum and the characteristic line. Based on spectra processing and a non-gray emissivity model, the flame temperature, emissivity, and intensities of the emission of alkali metals were calculated by means of measuring the spectral radiation intensities of the MSW flame. Experimental results indicate that the MSW flame contains alkali metals, including Na, K, and even Rb, and it demonstrates non-gray characteristics in a wavelength range from 500 nm to 900 nm. Peak intensities of the emission of the alkali metals were found to increase when the primary air was high, and the measured temperature varied in the same way as the primary air. The temperature and peak intensities of the lines of emission of the alkali metals may be used to adjust the primary airflow and to manage the feeding of the MSW to control the alkali metals in the MSW flame. It was found that the peak intensity of the K emission line had a linear relationship with the peak intensity of the Na emission line; this correlation may be attributed to their similar physicochemical characteristics in the MSW. The variation trend of the emissivity of the MSW flame and the oxygen content in the flue gas were almost opposite because the increased oxygen content suppressed soot formation and decreased soot emissivity. These results prove that the flame emission spectroscopy technique is feasible for monitoring combustion in the MSW incinerator in situ.

Structural properties of low-density liquid alkali metals

Indian Academy of Sciences (India)

The static structure factors of liquid alkali metals have been modelled at temperatures close to their melting points and a few higher temperatures using the reverse Monte Carlo (RMC) method. The positions of 5000 atoms in a box, with full periodicity, were altered until the experimental diffraction data of the structure factor ...

Interaction of calcium oxide with molten alkali metal chlorides

International Nuclear Information System (INIS)

Volkovich, A.V.; Zhuravlev, V.I.; Ermakov, D.S.; Magurina, M.V.

1999-01-01

Calcium oxide solubility in molten lithium, sodium, potassium, cesium chlorides and their binary mixtures is determined in a temperature range of 973-1173 K by the method of isothermal saturation. Mechanisms of calcium oxide interaction with molten alkali metal chlorides are proposed

CO hydrogenation on zeolite-supported Ru: Effect of neutralizing cations

International Nuclear Information System (INIS)

Oukaci, R.; Wu, J.C.S.; Goodwin, J.G. Jr.

1986-01-01

Previous results for zeolite-supported Ru prepared by ion exchange suggested a possible effect of the nature and concentration of the neutralizing cations in the zeolite on the catalytic properties of the metal. However, the interpretation of these results was complicated by the fact that a series of zeolites with different Si/Al ratios was used. The present study was undertaken to investigate systematically the influence of the nature of alkali neutralizing cations on CO hydrogenation over ion-exchanged Y-zeolite-supported ruthenium catalysts

Density functional theory based screening of ternary alkali-transition metal borohydrides: A computational material design project

DEFF Research Database (Denmark)

Hummelshøj, Jens Strabo; Landis, David; Voss, Johannes

2009-01-01

We present a computational screening study of ternary metal borohydrides for reversible hydrogen storage based on density functional theory. We investigate the stability and decomposition of alloys containing 1 alkali metal atom, Li, Na, or K (M1); and 1 alkali, alkaline earth or 3d/4d transition...

Chemical compatibility of structural materials in alkali metals

International Nuclear Information System (INIS)

Natesan, K.; Rink, D.L.; Haglund, R.

1995-01-01

The objectives of this task are to (a) evaluate the chemical compatibility of structural alloys such as V-5 wt.%Cr-5 wt.%Ti alloy and Type 316 stainless steel for application in liquid alkali metals such as lithium and sodium-78 wt.% potassium (NaK) at temperatures in the range that are of interest for International Thermonuclear Experimental Reactor (ITER); (b) evaluate the transfer of nonmetallic elements such as oxygen, nitrogen, carbon, and hydrogen between structural materials and liquid metals; and (c) evaluate the effects of such transfers on the mechanical and microstructural characteristics of the materials for long-term service in liquid-metal-environments

Coprecipitation of rare earths in systems of three heterovalent ions with sulfates of alkali and alkaline-earth metals

International Nuclear Information System (INIS)

Bobrik, V.M.

1977-01-01

Co-precipitation of rare earth elements (REE) in milligram amounts (3x10 -3 -3x10 -1 M) with alkali earth (AEE) sulfates in presence of alkali metal ions has been studied, the AEE:REE ratios between the co-precipitator and a REE (up to 50:1) the latter can be co-precipitated quantitatively in presence of corresponding alkali metals linked with the AEE in the Periodic table by a diagonal, i.e. in presence of sodium in co-precipitation with calcium sulfate, potassium with strontium sulfate and rubidium with barium sulfate. Co-precipitation with sulfates of sodium and calcium occurs at temperatures above 85 deg C and presumably involves calcium semihydrate. In presence of an alkali metal REE co-precipitation with AEE becomes isomorphic, i.e. at different AEE:REE ratios the co-precipitation coefficient remains constant. In presence of corresponding alkali metals the decrease in effectiveness of co-precipitation with AEE in the La-Lu series is more pronounced

Ion conducting fluoropolymer carbonates for alkali metal ion batteries

Science.gov (United States)

DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Balsara, Nitash P.; Thelen, Jacob; Devaux, Didier

2017-09-05

Liquid or solid electrolyte compositions are described that comprise a homogeneous solvent system and an alkali metal salt dissolved in said solvent system. The solvent system may comprise a fluoropolymer, having one or two terminal carbonate groups covalently coupled thereto. Batteries containing such electrolyte compositions are also described.

Macroscopic and bulk-controlled elastic modes in an interaction of interstitial alcali metal cations within a face-centered cubic crystalline fullerine

Energy Technology Data Exchange (ETDEWEB)

Tatarenko, V.A.; Tsysman, C.L.; Oltarzhevskaya, Y.T. [Institute for Metal Physics, Kiev (Ukraine)

1994-12-31

The calculations in a majority of previous works for the fulleride (AqC{sub 60}) crystals were performed within the framework of the rigid-lattice model, neglecting the distoration relaxation of the host fullerene (C{sub 60}) crystal caused by the interstitial alkali-metal (A) cations. However, an each cation is a source of a static distoration field, and the resulting field is a superposition of such fields generated by all cations. This is a reason why the host-crystal distortions depend on the A-cations configurations, i.e. on a type of a spatial bulk distribution of interstitial cations. This paper seeks to find a functional relation between the amplitudes of the doping-induced structure-distortion waves and of statistic concentration ones. A semiphenomenological model is constructed here within the scope of statistical-thermodynamic treatment and using the lattice-statistics simulation method. In this model the effects due to the presence of q solute A cations over available interstices (per unit cell) on the statistic inherent reorientation and/or displacements of the solvent molecules from the average-lattice sites as well as on the lattice parameter a of the elastically-anysotropic cubic C{sub 60} crystal are taken into account.

Recyclable hydrogen storage system composed of ammonia and alkali metal hydride

Energy Technology Data Exchange (ETDEWEB)

Yamamoto, Hikaru [Department of Quantum Matter, AdSM, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8530 (Japan); Miyaoka, Hiroki; Hino, Satoshi [Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8530 (Japan); Nakanishi, Haruyuki [Higashi-Fuji Technical Center, Toyota Motor Corporation, 1200 Misyuku, Susono, Shizuoka 410-1193 (Japan); Ichikawa, Takayuki; Kojima, Yoshitsugu [Department of Quantum Matter, AdSM, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8530 (Japan); Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8530 (Japan)

2009-12-15

Ammonia (NH{sub 3}) reacts with alkali metal hydrides MH (M = Li, Na, and K) in an exothermic reaction to release hydrogen (H{sub 2}) at room temperature, resulting that alkali metal amides (MNH{sub 2}) which are formed as by-products. In this work, hydrogen desorption properties of these systems and the condition for the recycle from MNH{sub 2} back to MH were investigated systematically. For the hydrogen desorption reaction, the reactivities of MH with NH{sub 3} were better following the atomic number of M on the periodic table, Li < Na < K. It was confirmed that the hydrogen absorption reaction of all the systems proceeded under 0.5 MPa of H{sub 2} flow condition below 300 C. (author)

Adsorption of alkali and alkaline-earth metal atoms on stanene: A first-principles study

Energy Technology Data Exchange (ETDEWEB)

Kadioglu, Yelda; Ersan, Fatih [Department of Physics, Adnan Menderes University, 09100 Aydın (Turkey); Gökoğlu, Gökhan [Department of Physics, Karabük University, 78050 Karabük (Turkey); Aktürk, Olcay Üzengi [Department of Electrical & Electronics Engineering, Adnan Menderes University, 09100 Aydın (Turkey); Nanotechnology Application and Research Center, Adnan Menderes University, 09100 Aydın (Turkey); Aktürk, Ethem, E-mail: ethem.akturk@adu.edu.tr [Department of Physics, Adnan Menderes University, 09100 Aydın (Turkey); Nanotechnology Application and Research Center, Adnan Menderes University, 09100 Aydın (Turkey)

2016-09-01

This paper presents a study on the adsorption of alkali and alkaline-earth metal atoms on single-layer stanene with different levels of coverage using first-principles plane wave calculations within spin-polarized density functional theory. The most favorable adsorption site for alkali atoms (Li, Na, K) were found to be the hollow site similar to other group IV single-layers, but the case of alkaline-earths on stanene is different from silicene and germanene. Whereas Mg and Ca are bound to stanene at hollow site, the bridge site is found to be energetically favorable for Be adatom. All adsorbed atoms are positively charged due to the charge transfer from adatom to stanene single-layer. The semimetallic bare stanene become metallic except for Be adsorption. The Beryllium adsorption give rise to non-magnetic semiconducting ground state. Our results illustrate that stanene has a reactive and functionalizable surface similar to graphene or silicene. - Highlights: • Alkali and alkaline-earth metal atoms form stronger bonds with stanene compared to other group IV monolayers. • Semi-metallic stanene becomes nonmagnetic metal for Li, Na, K, Mg, and Ca atoms adsorption. • Semi-metallic stanene becomes nonmagnetic semiconductor with 94 meV band gap for Be atom adsorption.

Effect of thermal annealing on the redistribution of alkali metals in Cu(In,Ga)Se2 solar cells on glass substrate

Science.gov (United States)

Kamikawa, Yukiko; Nishinaga, Jiro; Ishizuka, Shogo; Tayagaki, Takeshi; Guthrey, Harvey; Shibata, Hajime; Matsubara, Koji; Niki, Shigeru

2018-03-01

The precise control of alkali-metal concentrations in Cu(In,Ga)Se2 (CIGS) solar cells via post deposition treatment (PDT) has recently attracted attention. When PDT is performed at an elevated temperature, an accompanying annealing effect is expected. Here, we investigate how thermal annealing affects the redistribution of alkali metals in CIGS solar cells on glass substrates and the properties of the solar cells. In addition, we investigate the origin of non-homogeneous alkali-metal depth profiles that are typical of CIGS grown using a three-stage process. In particular, we use secondary-ion mass spectrometry measurements of the ion concentration as a function of distance from the CIGS surface to investigate the impact of thermal annealing on the distribution of alkali metals (Na, Ka, and Rb) and constituent elements (Ga and In) in the CIGS absorbers. We find that the depth profiles of the alkali metals strongly reflect the density of sites that tend to accommodate alkali metals, i.e., vacancies. Annealing at elevated temperature caused a redistribution of the alkali metals. The thermal-diffusion kinetics of alkali metals depends strongly on the species involved. We introduced low flux potassium fluoride (KF) to study a side effect of KF-PDT, i.e., Na removal from CIGS, separately from its predominant effects such as surface modification. When sufficient amounts of Na are supplied from the soda lime glass via annealing at an elevated temperature, the negative effect was not apparent. Conversely, when the Na supply was not sufficient, it caused a deterioration of the photovoltaic properties.

Effect of Thermal Annealing on the Redistribution of Alkali Metals in Cu(In,Ga)Se2 Solar Cells on Glass Substrate

Energy Technology Data Exchange (ETDEWEB)

Guthrey, Harvey L [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Kamikawa, Yukiko [National Institute of Advanced Industrial Science and Technology (AIST); Nishinaga, Jiro [National Institute of Advanced Industrial Science and Technology (AIST); Ishizuka, Shogo [National Institute of Advanced Industrial Science and Technology (AIST); Tayagaki, Takeshi [National Institute of Advanced Industrial Science and Technology (AIST); Shibata, Hajime [National Institute of Advanced Industrial Science and Technology (AIST); Matsubara, Koji [National Institute of Advanced Industrial Science and Technology (AIST); Niki, Shigeru [National Institute of Advanced Industrial Science and Technology (AIST)

2018-03-02

The precise control of alkali-metal concentrations in Cu(In,Ga)Se2 (CIGS) solar cells via post deposition treatment (PDT) has recently attracted attention. When PDT is performed at an elevated temperature, an accompanying annealing effect is expected. Here, we investigate how thermal annealing affects the redistribution of alkali metals in CIGS solar cells on glass substrates and the properties of the solar cells. In addition, we investigate the origin of non-homogeneous alkali-metal depth profiles that are typical of CIGS grown using a three-stage process. In particular, we use secondary-ion mass spectrometry measurements of the ion concentration as a function of distance from the CIGS surface to investigate the impact of thermal annealing on the distribution of alkali metals (Na, Ka, and Rb) and constituent elements (Ga and In) in the CIGS absorbers. We find that the depth profiles of the alkali metals strongly reflect the density of sites that tend to accommodate alkali metals, i.e., vacancies. Annealing at elevated temperature caused a redistribution of the alkali metals. The thermal-diffusion kinetics of alkali metals depends strongly on the species involved. We introduced low flux potassium fluoride (KF) to study a side effect of KF-PDT, i.e., Na removal from CIGS, separately from its predominant effects such as surface modification. When sufficient amounts of Na are supplied from the soda lime glass via annealing at an elevated temperature, the negative effect was not apparent. Conversely, when the Na supply was not sufficient, it caused a deterioration of the photovoltaic properties.

The influence of chlorine on the fate and activity of alkali metals during the gasification of wood

Energy Technology Data Exchange (ETDEWEB)

Struis, R; Scala, C von; Schuler, A; Stucki, S [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1999-08-01

Chlorine clearly inhibits the CO{sub 2}-gasification reaction of charcoal at 800{sup o}C. From this and other observations the picture emerges that the reduction in the gasification reactivity of the charcoal is intimately related to the deactivation of the catalytically active alkali metals residing in the wood due to the formation of the chloride salt. It is argued that the heavy metal chlorides will likely transfer the chlorine to the indigenous alkali metals during the pyrolysis stage of the wood. The fate of the thus formed alkali metal chlorides can then be either their removal from the sample (evaporation), or, when present at the gasification stage, re-activation (i.e., de-chlorination) under our gasification conditions. (author) 3 figs., 4 refs.

Competitive/co-operative interactions in acid base sandwich: role of cation vs. substituents.

Science.gov (United States)

Kalpana, Ayyavoo; Akilandeswari, Lakshminarayanan

2017-11-15

The cation-π interaction can be envisaged as a lewis acid base interaction, and it is in line with Pearson's acid base concept. The critical examination of interactions between the π-acids (alkali metal cations - Li + , Na + and alkaline earth metal cations Mg 2+ , Ca 2+ ) on one face and tripodal Cr(CO) 3 moiety on the other π face of substituted arenes demonstrates the role of cation and substitutents in manipulating the interactions between them. The interaction of the two π acids on both faces of arene is not expectedly additive, rather it shows either depreciation of interaction energy revealing the competition of acids toward the base or enhancement of interaction energy denoting a cooperative effect. Among the metal cations under study, Mg 2+ shows a cooperative gesture. Although the substituents play a meek role, they unfailingly exert their electronic effects and are amply documented by excellent correlation of various parameters with the Hammett constant σ m . The elusive switching of λ max from the UV to IR region on binding Mg 2+ with substituted arene-Cr(CO) 3 complex is a characteristic clue that TDDFT can help design the ionic sensors for Mg 2+ cations.

Surface enhanced spectroscopic investigations of adsorption of cations on electrochemical interfaces.

Science.gov (United States)

Dunwell, M; Wang, Junhua; Yan, Y; Xu, B

2017-01-04

The adsorption of alkali and tetraalkylammonium cations on Pt is investigated using surface enhanced infrared absorption spectroscopy and carbon monoxide as a probe molecule. Alkali cations exhibit a stronger adsorption than organic cations, with potassium showing the strongest effect, followed by sodium and lithium.

Determination of a various ions such as alkali metals in leaves, stems, roots and seeds of the radish and their distribution

International Nuclear Information System (INIS)

Fujino, Osamu; Matsui, Masakazu.

1995-01-01

Determination, uptake and distribution of various ions such as alkali metals in three different parts (leaf, stem and root) and seeds of radish (Kaiware daikon) were examined using flame emission spectrometry and ICP-AES. In order to examine the influence of concentration alkali metal ion concentration in the radish culture solution on the uptake and distribution of these metals, the radish was grown at pH 5.6 in solutions containing alkali metal chloride at concentrations ranging from 10 -5 to 10 -1 mol dm -3 . When the radish were grown in culture solution with alkali metal ions of low concentrations (10 -5 and 10 -4 mol dm -3 ), Na, K, Rb and trace Li were detected in leaves, stems and roots while Cs was scarcely detected. However, the contents of Na, K, Li in these organs were the same as those in radish cultivated in pure water. An increase of Rb uptake was observed with an increased Rb concentration. In the case of high concentrations (10 -3 and 10 -2 mol dm -3 ) of alkali metals in culture solution, the all alkali ions uptake of all alkali ions suddenly accelerated. Moreover, at concentrations higher than 0.1 mol dm -3 , the radish germinated poorly and did not completely mature. (author)

Tunable electronic and magnetic properties in germanene by alkali, alkaline-earth, group III and 3d transition metal atom adsorption.

Science.gov (United States)

Li, Sheng-shi; Zhang, Chang-wen; Ji, Wei-xiao; Li, Feng; Wang, Pei-ji; Hu, Shu-jun; Yan, Shi-shen; Liu, Yu-shen

2014-08-14

We performed first-principles calculations to study the adsorption characteristics of alkali, alkali-earth, group III, and 3d transition-metal (TM) adatoms on germanene. We find that the adsorption of alkali or alkali-earth adatoms on germanene has minimal effects on geometry of germanene. The significant charge transfer from alkali adatoms to germanene leads to metallization of germanene, whereas alkali-earth adatom adsorption, whose interaction is a mixture of ionic and covalent, results in semiconducting behavior with an energy gap of 17-29 meV. For group III adatoms, they also bind germanene with mixed covalent and ionic bonding character. Adsorption characteristics of the transition metals (TMs) are rather complicated, though all TM adsorptions on germanene exhibit strong covalent bonding with germanene. The main contributions to the strong bonding are from the hybridization between the TM 3d and Ge pz orbitals. Depending on the induced-TM type, the adsorbed systems can exhibit metallic, half-metallic, or semiconducting behavior. Also, the variation trends of the dipole moment and work function with the adsorption energy across the different adatoms are discussed. These findings may provide a potential avenue to design new germanene-based devices in nanoelectronics.

Solubility and Standard Gibb's energies of transfer of alkali metal perchlorates, tetramethyl- and tetraethylammonium from water to aqua-acetone solvents

International Nuclear Information System (INIS)

Kireev, A.A.; Pak, T.G.; Bezuglyj, V.D.

1996-01-01

Solubilities of KClO 4 , RbClO 4 , CsClO 4 , (CH 3 ) 4 NClO 4 , (C 2 M 5 ) 4 NClO 4 in water and water-acetone mixtures are determined by the method of isothermal saturation at 298.15 K. Dissociation constants of alkali metal perchlorates are found by conductometric method. Solubility products and standard Gibbs energies of transfer of corresponding electrolytes from water into water-acetone solvents are calculated. The character of transfer Gibbs energy dependence on solvent composition is explained by preferred solvation of cations by acetone molecules and anions-by water molecules. Features of tetraalkyl ammonium ions are explained by large changes in energy of cavity formation for these ions

Structure of liquid alkali metals as electron-ion plasmas

International Nuclear Information System (INIS)

Chaturvedi, D.K.; Senatore, G.; Tosi, M.P.

1980-08-01

The static structure factor of liquid alkali metals near freezing, and its dependence on temperature and pressure, are evaluated in an electron-ion plasma model from an accurate theoretical determination of the structure factor of the one-component classical plasma and electron-screening theory. Very good agreement is obtained with the available experimental data. (author)

Pair potentials and structure factors of liquid alkali metals

International Nuclear Information System (INIS)

Kumaravadivel, R.; Tosi, M.P.

1984-03-01

Measured structure factors of liquid alkali metals are examined in the framework of screened-pair-potentials theory. Information on the main attractive well in the effective pair potential is obtained from the structural data by an approximate method stemming from an optimized random phase treatment of the indirect ion-ion attraction. The results are compared with a variety of theoretical pair potentials in the cases of sodium and potassium, after a test of the method against computer simulation data on a model for rubidium. Results for the other alkali metals are also given and discussed. The small-angle scattering region is then examined in considerable detail, with special attention to the possibility of a linear term in a series expansion of the structure factor at very small momentum transfer. Although sensitivity to both the bare electron-ion coupling and the local field factor in the screening function is demonstrated and analyzed, no linear term of the magnitude reported in recent X-ray diffraction experiments is found in the present theoretical framework. (author)

Ion chromatography of transition metals: specific alteration of retention by complexation reactions in the mobile and on the stationary phase

International Nuclear Information System (INIS)

Baumgartner, S.

1992-05-01

Ion chromatography of mono- and bivalent cations was performed on a conventional cation exchanger. The pH influence of an ethylene-diamine/citrate eluent was significant for the retention of alkaline earth and transition metals, but negligible for alkali ions. This was dealt with from a mechanistic point of view. Mobile phase optimization allowed fast isocratic analysis of mono- and bivalent cations and the separation of the radionuclides Cs-137 and Sr-90. A newly synthesized stationary phase containing iminodiacetate (IDA) function was investigated for cation chromatography using ethylenediamine/citrate eluents, polyhydroxy acid and dipicolinic acid. The column's high selectivity for transition metal ions in comparison to alkali and alkaline earth metals may be governed by the choice of complexing ability and pH of the eluent. Applications verified by atomic absorption spectroscopy include alkaline earth metals in beverages and the determination of Co, Cd and Zn in solutions containing more than 10 14 -fold excess of Na and Mg, such as sea water

Structure peculiarities of mixed alkali silicate glasses

International Nuclear Information System (INIS)

Bershtein, V.A.; Gorbachev, V.V.; Egorov, V.

1980-01-01

The thermal porperties and structure of alkali and mixed alkali (Li, Na, K) silicate glasses by means of differential scanning calorimetry (DSC), the positron annihilation method, X-ray fluorescence and infrared (300-30 cm -1 ) spectroscopy were studied. Introduction of different alkali cations in glass results in nonadditive change in their electron structure (bond covalence degree growth) and the thermal behaviour. The different manifestations of mixed alkali effect can be explained by the lessening of long distance Coulomb interactions and strengthening the short-range forces in the mixed alkali glasses. (orig.)

Momentum densities and Compton profiles of alkali-metal atoms

Indian Academy of Sciences (India)

Abstract. It is assumed that the dynamics of valence electrons of alkali-metal atoms can be well accounted for by a quantum-defect theoretic model while the core electrons may be supposed to move in a self-consistent field. This model is used to study the momentum properties of atoms from. 3Li to 37Rb. The numerical ...

Solution enthalpies of alkali metal halides in water and heavy water mixtures with dimethyl sulfoxide

International Nuclear Information System (INIS)

Egorov, G.I.

1994-01-01

Solution enthalpies of CsF, LiCl, NaI, CsI and some other halides of alkali metals and tetrabutylammonium have been measured by the method of calorimetry. Standard solution enthalpies of all alkali metals (except rubidium) halides in water and heavy water mixtures with dimethylsulfoxide at 298.15 K have been calculated. Isotopic effects in solvation enthalpy of the electrolytes mentioned in aqueous solutions of dimethylsulfoxide have been discussed. 29 refs., 2 figs., 4 tabs

Corrosion resistance of metals and alloys in molten alkalies

International Nuclear Information System (INIS)

Zarubitskij, O.G.; Dmitruk, B.F.; Minets, L.A.

1979-01-01

Literature data on the corrosion of non-ferrous and noble metals, iron and steels in the molten alkalis and mixtures of their base are presented. It is shown that zirconium, niobium and tantalum are characterized by high corrosion stability in the molten NaOH. Additions of NaOH and KOH to the alkali chloride melts result in a 1000 time decrease of zirconium corrosion rate at 850 deg. The data testify to the characteristic passivating properties of OH - ions; Mo and W do not possess an ability to selfpassivation in hydroxide melts. Corrosion resistance of carbon and chromium-nickel steels in hydroxide melts depends considerably on the temperature, electrolyte composition and atmosphere over them. At the temperatures up to 600 deg C chromium-nickel steel is corrosion resistant in the molten alkali only in the inert atmosphere. Corrosion rate of chromium-nickel alloy is the lower the less chromium and the more nickel it contains. For the small installations the 4Kh18N25S2 and Kh23N28M3D3T steels can be recommended

The Production of Polycyclic Aromatic Hydrocarbon Anions in Inert Gas Matrices Doped with Alkali Metals. Electronic Absorption Spectra of the Pentacene Anion (C22H14(-))

Science.gov (United States)

Halasinski, Thomas M.; Hudgins, Douglas M.; Salama, Farid; Allamandola, Louis J.; Mead, Susan (Technical Monitor)

1999-01-01

The absorption spectra of pentacene (C22H14) and its radical cation (C22H14(+)) and anion (C22H14(-)) isolated in inert-gas matrices of Ne, Ar, and Kr are reported from the ultraviolet to the near-infrared. The associated vibronic band systems and their spectroscopic assignments are discussed together with the physical and chemical conditions governing ion (and counterion) production in the solid matrix. In particular, the formation of isolated pentacene anions is found to be optimized in matrices doped with alkali metal (Na and K).

Higher-order Cn dispersion coefficients for the alkali-metal atoms

International Nuclear Information System (INIS)

Mitroy, J.; Bromley, M.W.J.

2005-01-01

The van der Waals coefficients, from C 11 through to C 16 resulting from second-, third-, and fourth-order perturbation theory are estimated for the alkali-metal (Li, Na, K, and Rb) atoms. The dispersion coefficients are also computed for all possible combinations of the alkali-metal atoms and hydrogen. The parameters are determined from sum rules after diagonalizing a semiempirical fixed core Hamiltonian in a large basis. Comparisons of the radial dependence of the C n /r n potentials give guidance as to the radial regions in which the various higher-order terms can be neglected. It is seen that including terms up to C 10 /r 10 results in a dispersion interaction that is accurate to better than 1% whenever the inter-nuclear spacing is larger than 20a 0 . This level of accuracy is mainly achieved due to the fortuitous cancellation between the repulsive (C 11 ,C 13 ,C 15 ) and attractive (C 12 ,C 14 ,C 16 ) dispersion forces

On solvent extraction of metals by macrocyclic polyethers

International Nuclear Information System (INIS)

Ionov, V.P.

1984-01-01

The Ksub(γ) parameter characterizing effective ion charges in ionic associates of metal salts is suggested; these charges parallel with other factors determine the metals extraction by macrocyclic polyethers (crown-ethers). The dependence of metal extraction constant on the Ksub(γ) parameter is discussed. It is shown that the less effective cation charge of alkali metal ionic associates, the more probable its entering the crown-ether cavity. The synergetic crown-ethers extraction is bound as well with Ksub(γ) of metal salts. The differences in the cation extraction constants having the same ionic radius are explained with account of different values of Ksub(γ) parameters of these salts

Development and testing of on-line analytical instrumentation for alkali and heavy metal release in pressurised conversion processes

Energy Technology Data Exchange (ETDEWEB)

Hernberg, R; Haeyrinen, V; Oikari, R [Tampere Univ. of Technology (Finland)

1997-10-01

The purpose of the project is to demonstrate in industrial conditions and further develop the continuous alkali measurement method plasma excited alkali resonance line spectroscopy (PEARLS) developed at Tampere University of Technology (TUT). The demonstration takes place in joint measuring campaigns, where two other continuous alkali measurement methods, ELIF and surface ionisation, are being simultaneously demonstrated. A modification of PEARLS will also be developed for the continuous measurement of heavy metal concentrations. A market study of continuous measuring techniques for alkali and heavy metals is further part of the project. The method will be demonstrated in two pressurised fluidised bed combustion facilities. One of these is the 10 MW PCFB of Foster Wheeler Energia Oy in Karhula. The second one is yet to be decided. The first measuring campaign is scheduled for the spring of 1997 in Karhula. In 1996 the group at TUT participated in the performance of a market study regarding continuous measuring techniques for alkali and heavy metal concentrations. A draft report was submitted to and approved by the EC. Development work on PEARLS in 1996 has centered around the construction of a calibration device for alkali measurements. The device can be used by all three measuring techniques in the project to check readings against a known alkali concentration at controlled and known conditions. In 1996 PEARLS was applied for alkali measurement at several pressurised combustion installations of laboratory and industrial pilot scale

Ultrafast electron dynamics at alkali/ice structures adsorbed on a metal surface

International Nuclear Information System (INIS)

Meyer, Michael

2011-01-01

The goal of this work is to study the interaction between excess electrons in water ice structures adsorbed on metal surfaces and other charged or neutral species, like alkali ions, or chemically reactive molecules, like chlorofluorocarbons (CFC), respectively. The excess electrons in the ice can interact with the ions directly or indirectly via the hydrogen bonded water molecules. In both cases the presence of the alkali influences the population, localization, and lifetime of electronic states of excess electrons in the ice adlayer. These properties are of great relevance when considering the highly reactive character of the excess electrons, which can mediate chemical reactions by dissociative electron attachment (DEA). The influence of alkali adsorption on electron solvation and transfer dynamics in ice structures is investigated for two types of adsorption configurations using femtosecond time-resolved two-photon photoelectron spectroscopy. In the first system alkali atoms are coadsorbed on top of a wetting amorphous ice film adsorbed on Cu(111). At temperatures between 60 and 100 K alkali adsorption leads to the formation of positively charged alkali ions at the ice/vacuum interface. The interaction between the alkali ions at the surface and the dipole moments of the surrounding water molecules results in a reorientation of the water molecules. As a consequence new electron trapping sites, i.e. at local potential minima, are formed. Photoinjection of excess electrons into these alkali-ion covered amorphous ice layers, results in the trapping of a solvated electron at an alkali-ion/water complex. In contrast to solvation in pure amorphous ice films, where the electrons are located in the bulk of the ice layer, solvated electrons at alkali-ion/water complexes are located at the ice/vacuum interface. They exhibit lifetimes of several picoseconds and show a fast energetic stabilization. With ongoing solvation, i.e. pump-probe time delay, the electron transfer is

Thermal Coefficient of Redox Potential of Alkali Metals

Science.gov (United States)

Fukuzumi, Yuya; Hinuma, Yoyo; Moritomo, Yutaka

2018-05-01

The thermal coefficient (α) of redox potential (V) is a significant physical quantity that converts the thermal energy into electric energy. In this short note, we carefully determined α of alkali metals (A = Li and Na) against electrolyte solution. The obtained α is much larger than that expected from the specific heat (CpA) of solid A and depends on electrolyte solution. These observations indicate that the solvent has significant effect on α.

Momentum densities and Compton profiles of alkali-metal atoms

Indian Academy of Sciences (India)

It is assumed that the dynamics of valence electrons of alkali-metal atoms can be well accounted for by a quantum-defect theoretic model while the core electrons may be supposed to move in a self-consistent field. This model is used to study the momentum properties of atoms from 3Li to 37Rb. The numerical results ...

Enhancing Skin Permeation of Biphenylacetic Acid (BPA) Using Salt Formation with Organic and Alkali Metal Bases.

Science.gov (United States)

Pawar, Vijay; Naik, Prashant; Giridhar, Rajani; Yadav, Mange Ram

2015-01-01

In the present study, a series of organic and alkali metal salts of biphenylacetic acid (BPA) have been prepared and evaluated in vitro for percutaneous drug delivery. The physicochemical properties of BPA salts were determined using solubility measurements, DSC, and IR. The DSC thermogram and FTIR spectra confirmed the salt formation with organic and alkali metal bases. Among the series, salts with organic amines (ethanolamine, diethanolamine, triethanolamine, and diethylamine) had lowered melting points while the alkali metal salt (sodium) had a higher melting point than BPA. The in vitro study showed that salt formation improves the physicochemical properties of BPA, leading to improved permeability through the skin. Amongst all the prepared salts, ethanolamine salt (1b) showed 7.2- and 5.4-fold higher skin permeation than the parent drug at pH 7.4 and 5.0, respectively, using rat skin.

Mechanism of selective ion flotation. 1. Selective flotation of transition metal cations

International Nuclear Information System (INIS)

Walkowiak, W.

1991-01-01

An experimental investigation is presented of the batch ion flotation of the transition metal cations Cr 3+ , Fe 3+ , Mn 2+ , Co 2+ , Zn 2+ , Ag + , Cd 2+ , and In 3+ from acidic aqueous solutions with sodium dodecylsulfonate and sodium dodecylbenzenesulfonate as anionic surfactants. The selectivity sequences Mn 2+ 2+ 2+ 3+ 3+ and Ag + 2+ 3+ are established, both from data for single and multi-ion metal cations solutions, where sublate was not formed in the bulk solution. Good agreement between the selectivity sequences and the values of ionic potential of metal cations was found. An experimental investigation was also performed on the solubility of sublates. The sublates solubility values are discussed in terms of ionic potentials of metal cations as well as of the surfactant size

Dependence of transfer number of fluorine on cation type in glasses of Ba(PO3)2-MeF2 systems (Me=Ba,Sr,Ca,Mg)

International Nuclear Information System (INIS)

Pronkin, A.A.

1978-01-01

The influence of Ba, Sr, Ca, Mg cations on transfer numbers of fluorine in glasses of Ba(PO 3 ) 2 - MeF 2 pseudobinary systems is studied. Transfer numbers are essentially different in one and the same fluorine ion concentration in glasses, containing various alkali-earth cations: increase of the cation field force brings about decrease of the transfer numbers of fluorine, and the glass-formation region in the Ba-Sr-Ca-Mg series rises. The dependence of transfer numbers of fluorine on the fluorine concentration logarithm is presented. It is established, that alkali-earth metals influence the transfer numbers of fluorine on account of selective interaction with the phosphate constituent of glass structure

Wigner Distribution Functions as a Tool for Studying Gas Phase Alkali Metal Plus Noble Gas Collisions

Science.gov (United States)

2014-03-27

WIGNER DISTRIBUTION FUNCTIONS AS A TOOL FOR STUDYING GAS PHASE ALKALI METAL PLUS NOBLE GAS COLLISIONS THESIS Keith A. Wyman, Second Lieutenant, USAF...the U.S. Government and is not subject to copyright protection in the United States. AFIT-ENP-14-M-39 WIGNER DISTRIBUTION FUNCTIONS AS A TOOL FOR...APPROVED FOR PUBLIC RELEASE; DISTRIBUTION UNLIMITED AFIT-ENP-14-M-39 WIGNER DISTRIBUTION FUNCTIONS AS A TOOL FOR STUDYING GAS PHASE ALKALI METAL PLUS

Enhancing Skin Permeation of Biphenylacetic Acid (BPA) Using Salt Formation with Organic and Alkali Metal Bases

OpenAIRE

PAWAR, Vijay; NAIK, Prashant; GIRIDHAR, Rajani; YADAV, Mange Ram

2014-01-01

In the present study, a series of organic and alkali metal salts of biphenylacetic acid (BPA) have been prepared and evaluated in vitro for percutaneous drug delivery. The physicochemical properties of BPA salts were determined using solubility measurements, DSC, and IR. The DSC thermogram and FTIR spectra confirmed the salt formation with organic and alkali metal bases. Among the series, salts with organic amines (ethanolamine, diethanolamine, triethanol-amine, and diethylamine) had lowered ...

[On-line analysis and mass concentration characters of the alkali metal ions of PM10 in Beijing].

Science.gov (United States)

Zhang, Kai; Wang, Yue-Si; Wen, Tian-Xue; Liu, Guang-Ren; Hu, Bo; Zhao, Ya-Nan

2008-01-01

The mass concentration characters and the sources of water-soluble alkali metal ions in PM10 in 2004 and 2005 in Beijing were analyzed by using the system of rapid collection of particles. The result showed that the average concentration of Na+, K+, Mg2+ and Ca2+ was 0.5-1.4, 0.5-2.5, 0.1-0.5 and 0.6-5.8 microg/m3, respectively. The highest and lowest concentration appeared in different seasons for the alkali metal ions, which was related to the quality and source. The concentration of alkali metal ions was no difference between the heating period and no heating period, which meant the heating was not the main source. Sea salt and soil were the important sources of Na+. The source of K+ came from biomass burning and vegetation. Soil was the large source of Mg2+ and Ca2+. The alkali metal ions appeared different daily variation in different seasons. Precipitation could decrease the concentration of Na+, K+, Mg2+ and Ca2+, which was 10%-70%, 20%-80%, 10%-77%, 5%-80% respectively.

Designable ultra-smooth ultra-thin solid-electrolyte interphases of three alkali metal anodes.

Science.gov (United States)

Gu, Yu; Wang, Wei-Wei; Li, Yi-Juan; Wu, Qi-Hui; Tang, Shuai; Yan, Jia-Wei; Zheng, Ming-Sen; Wu, De-Yin; Fan, Chun-Hai; Hu, Wei-Qiang; Chen, Zhao-Bin; Fang, Yuan; Zhang, Qing-Hong; Dong, Quan-Feng; Mao, Bing-Wei

2018-04-09

Dendrite growth of alkali metal anodes limited their lifetime for charge/discharge cycling. Here, we report near-perfect anodes of lithium, sodium, and potassium metals achieved by electrochemical polishing, which removes microscopic defects and creates ultra-smooth ultra-thin solid-electrolyte interphase layers at metal surfaces for providing a homogeneous environment. Precise characterizations by AFM force probing with corroborative in-depth XPS profile analysis reveal that the ultra-smooth ultra-thin solid-electrolyte interphase can be designed to have alternating inorganic-rich and organic-rich/mixed multi-layered structure, which offers mechanical property of coupled rigidity and elasticity. The polished metal anodes exhibit significantly enhanced cycling stability, specifically the lithium anodes can cycle for over 200 times at a real current density of 2 mA cm -2 with 100% depth of discharge. Our work illustrates that an ultra-smooth ultra-thin solid-electrolyte interphase may be robust enough to suppress dendrite growth and thus serve as an initial layer for further improved protection of alkali metal anodes.

Thermodynamic and kinetic analysis of solid-phase interaction of alkali metal carbonates with arsenic pentoxide

International Nuclear Information System (INIS)

Pashinkin, A.S.; Buketov, E.A.; Isabaeva, S.M.; Kasenov, B.K.

1985-01-01

The thermodynamic analysis of solid-phase reactions of alkali metal carbonates with arsenic pentoxide showing the possibility of formation of all arsenates at a higher than the room temperature is performed. Energetically most advantageous is formation of meta-arsenates. It is shown that temperature increase favours the reaction process. By Gibbs standard energy decrease the reactions form the Li>Na>K>Rb>Cs series. On the base of calculation data linear dependence of Gibbs standard energy in reactions on the atomic number of alkali metalis established. By the continuous weighing method the kinetics of interaction of alkali metal carbonates with arsenic pentoxide under isothermal conditions in the 450-500 deg C range is studied. Studies is the dependence of apparent energy of interaction of carbonates wih As 2 0 5 an atomic parameters of al

Theoretical evaluation on selective adsorption characteristics of alkali metal-based sorbents for gaseous oxidized mercury.

Science.gov (United States)

Tang, Hongjian; Duan, Yufeng; Zhu, Chun; Cai, Tianyi; Li, Chunfeng; Cai, Liang

2017-10-01

Alkali metal-based sorbents are potential for oxidized mercury (Hg 2+ ) selective adsorption but show hardly effect to elemental mercury (Hg 0 ) in flue gas. Density functional theory (DFT) was employed to investigate the Hg 0 and HgCl 2 adsorption mechanism over alkali metal-based sorbents, including calcium oxide (CaO), magnesium oxide (MgO), potassium chloride (KCl) and sodium chloride (NaCl). Hg 0 was found to weakly interact with CaO (001), MgO (001), KCl (001) and NaCl (001) surfaces while HgCl 2 was effectively adsorbed on top-O and top-Cl sites. Charge transfer and bond population were calculated to discuss the covalency and ionicity of HgCl 2 bonding with the adsorption sites. The partial density of states (PDOS) analysis manifests that HgCl 2 strongly interacts with surface sites through the orbital hybridizations between Hg and top O or Cl. Frontier molecular orbital (FMO) energy and Mulliken electronegativity are introduced as the quantitative criteria to evaluate the reactivity of mercury species and alkali metal-based sorbents. HgCl 2 is identified as a Lewis acid and more reactive than Hg 0 . The Lewis basicity of the four alkali metal-based sorbents is predicted as the increasing order: NaCl < MgO < KCl < CaO, in consistence with the trend of HgCl 2 adsorption energies. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

Science.gov (United States)

Joshi, Ashok V [Salt Lake City, UT; Balagopal, Shekar [Sandy, UT; Pendelton, Justin [Salt Lake City, UT

2011-12-13

Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

A numerical study of spin-dependent organization of alkali-metal atomic clusters using density-functional method

International Nuclear Information System (INIS)

Liu Xuan; Ito, Haruhiko; Torikai, Eiko

2012-01-01

We calculate the different geometric isomers of spin clusters composed of a small number of alkali-metal atoms using the UB3LYP density-functional method. The electron density distribution of clusters changes according to the value of total spin. Steric structures as well as planar structures arise when the number of atoms increases. The lowest spin state is the most stable and Li n , Na n , K n , Rb n , and Cs n with n = 2–8 can be formed in higher spin states. In the highest spin state, the preparation of clusters depends on the kind and the number of constituent atoms. The interaction energy between alkali-metal atoms and rare-gas atoms is smaller than the binding energy of spin clusters. Consequently, it is possible to self-organize the alkali-metal-atom clusters on a non-wetting substrate coated with rare-gas atoms.

A numerical study of spin-dependent organization of alkali-metal atomic clusters using density-functional method

Energy Technology Data Exchange (ETDEWEB)

Liu Xuan, E-mail: liu.x.ad@m.titech.ac.jp; Ito, Haruhiko [Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology (Japan); Torikai, Eiko [Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi (Japan)

2012-08-15

We calculate the different geometric isomers of spin clusters composed of a small number of alkali-metal atoms using the UB3LYP density-functional method. The electron density distribution of clusters changes according to the value of total spin. Steric structures as well as planar structures arise when the number of atoms increases. The lowest spin state is the most stable and Li{sub n}, Na{sub n}, K{sub n}, Rb{sub n}, and Cs{sub n} with n = 2-8 can be formed in higher spin states. In the highest spin state, the preparation of clusters depends on the kind and the number of constituent atoms. The interaction energy between alkali-metal atoms and rare-gas atoms is smaller than the binding energy of spin clusters. Consequently, it is possible to self-organize the alkali-metal-atom clusters on a non-wetting substrate coated with rare-gas atoms.

Ab Initio Study of Chemical Reactions of Cold SrF and CaF Molecules with Alkali-Metal and Alkaline-Earth-Metal Atoms: The Implications for Sympathetic Cooling.

Science.gov (United States)

Kosicki, Maciej Bartosz; Kędziera, Dariusz; Żuchowski, Piotr Szymon

2017-06-01

We investigate the energetics of the atom exchange reaction in the SrF + alkali-metal atom and CaF + alkali-metal atom systems. Such reactions are possible only for collisions of SrF and CaF with the lithium atoms, while they are energetically forbidden for other alkali-metal atoms. Specifically, we focus on SrF interacting with Li, Rb, and Sr atoms and use ab initio methods to demonstrate that the SrF + Li and SrF + Sr reactions are barrierless. We present potential energy surfaces for the interaction of the SrF molecule with the Li, Rb, and Sr atoms in their energetically lowest-lying electronic spin states. The obtained potential energy surfaces are deep and exhibit profound interaction anisotropies. We predict that the collisions of SrF molecules in the rotational or Zeeman excited states most likely have a strong inelastic character. We discuss the prospects for the sympathetic cooling of SrF and CaF molecules using ultracold alkali-metal atoms.

Equilibrium electrode U(4)-U and redox U(4)-U(3) potentials in molten alkali metal chlorides medium

Energy Technology Data Exchange (ETDEWEB)

Smirnov, M V; Kudyakov, V Ya; Komarov, V E; Salyulev, A B [AN SSSR, Sverdlovsk. Inst. Ehlektrokhimii

1979-02-01

Conditional standard electrode potentials of uranium are determined for diluted solutions of its tetrachloride in alkali metal chloride melts (LiCl, NaCl, NaCl-KCl, KCl, RbCl and CsCl) when using U(4) ion activity coefficient values experimentally found by the tensimetric method. These potentials shift to the electronegative side at the temperature decrease and alkali cation radius increase rsub(Msup(+)) according to the empiric ratio E*U(4)-U= -3.06+6.87x10/sup -4/ T-(1.67-10/sup -4/T-0.44) 1/rsub(Msup(+)) +-0.01. The temperature dependences of formal conditional redox potentials of the U(4)-U(3) system for above melted chlorides are estimated. The E*U(4)-U(3) value also becomes more electronegative in the series LiCl, NaCl, NaCl-KCl, KCl, RbCl and CsCl. This alternation is satisfactorily described by the empiric expression E*U(4)-U(3)= -1.74+1.74x10/sup -4/T-(0.71x10/sup -4/T-0.20) 1rsub(Msup(+)) +-0.05. The calculated values Eu*(4)-U(3) are compared with those directly measured for the NaCl-KCl equimolar mixture and 3LiCl-2KCl eutectic mixture. A satisfactory confirmity has been observed.

Equilibrium electrode U(4)-U and redox U(4)-U(3) potentials in molten alkali metal chlorides medium

International Nuclear Information System (INIS)

Smirnov, M.V.; Kudyakov, V.Ya.; Komarov, V.E.; Salyulev, A.B.

1979-01-01

Conditional standard electrode potentials of uranium are determined for diluted solutions of its tetrachloride in alkali metal chloride melts (LiCl, NaCl, NaCl-KCl, KCl, RbCl and CsCl) when using U(4) ion activity coefficient values experimentally found by the tensimetric method. These potentials shift to the electronegative side at the temperature decrease and alkali cation radius increase rsub(Msup(+)) according to the empiric ratio E*U(4)-U= -3.06+6.87x10 -4 T-(1.67-10 -4 T-0.44) 1/rsub(Msup(+)) +-0.01. The temperature dependences of formal conditional redox potentials of the U(4)-U(3) system for above melted chlorides are estimated. The E*U(4)-U(3) value also becomes more electronegative in the series LiCl, NaCl, NaCl-KCl, KCl, RbCl and CsCl. This alternation is satisfactorily described by the empiric expression E*U(4)-U(3)= -1.74+1.74x10 -4 T-(0.71x10 -4 T-0.20) 1rsub(Msup(+)) +-0.05. The calculated values Eu*(4)-U(3) are compared with those directly measured for the NaCl-KCl equimolar mixture and 3LiCl-2KCl eutectic mixture. A satisfactory confirmity has been observed

3718-F Alkali Metal Treatment and Storage Facility Closure Plan

International Nuclear Information System (INIS)

1992-11-01

The Hanford Site, located northwest of the city of Richland, Washington, houses reactors, chemical-separation systems, and related facilities used for the production of special nuclear materials, as well as for activities associated with nuclear energy development. The 300 Area of the Hanford Site contains reactor fuel manufacturing facilities and several research and development laboratories. The 3718-F Alkali Metal Treatment and Storage Facility (3718-F Facility), located in the 300 Area, was used to store and treat alkali metal wastes. Therefore, it is subject to the regulatory requirements for the storage and treatment of dangerous wastes. Closure will be conducted pursuant to the requirements of the Washington Administrative Code (WAC) 173-303-610 (Ecology 1989) and 40 CFR 270.1. Closure also will satisfy the thermal treatment facility closure requirements of 40 CFR 265.381. This closure plan presents a description of the 3718-F Facility, the history of wastes managed, and the approach that will be followed to close the facility. Only hazardous constituents derived from 3718-F Facility operations will be addressed

The Study of Anti-/Pro-Oxidant, Lipophilic, Microbial and Spectroscopic Properties of New Alkali Metal Salts of 5-O-Caffeoylquinic Acid

Directory of Open Access Journals (Sweden)

Monika Kalinowska

2018-02-01

concentration, MIC = 7.06 mM and antifungal (MIC = 14.11 mM properties than its alkali metal salts (MIC values: 6.46–2.63 mM and 12.91–5.27mM, respectively. The synthesized chlorogenates possessed better antioxidant, lipophilic, antimicrobial as well as lower pro-oxidant properties than the ligand alone. Moreover, a systematic change of the activity of alkali metal salts along the series Li→Cs suggests that there are correlations between the studied biological properties. The type of metal cation in the carboxylate group of chlorogenate is crucial for the activity of studied compounds.

Cathode architectures for alkali metal / oxygen batteries

Science.gov (United States)

Visco, Steven J; Nimon, Vitaliy; De Jonghe, Lutgard C; Volfkovich, Yury; Bograchev, Daniil

2015-01-13

Electrochemical energy storage devices, such as alkali metal-oxygen battery cells (e.g., non-aqueous lithium-air cells), have a cathode architecture with a porous structure and pore composition that is tailored to improve cell performance, especially as it pertains to one or more of the discharge/charge rate, cycle life, and delivered ampere-hour capacity. A porous cathode architecture having a pore volume that is derived from pores of varying radii wherein the pore size distribution is tailored as a function of the architecture thickness is one way to achieve one or more of the aforementioned cell performance improvements.

Uranium metalla-allenes with carbene imido R{sub 2}C=U{sup IV}=NR' units (R=Ph{sub 2}PNSiMe{sub 3}; R'=CPh{sub 3}): alkali-metal-mediated push-pull effects with an amido auxiliary

Energy Technology Data Exchange (ETDEWEB)

Lu, Erli; Tuna, Floriana; Kaltsoyannis, Nikolas; Liddle, Stephen T. [School of Chemistry, The University of Manchester (United Kingdom); Lewis, William [School of Chemistry, The University of Nottingham (United Kingdom)

2016-08-08

We report uranium(IV)-carbene-imido-amide metalla-allene complexes [U(BIPM{sup TMS})(NCPh{sub 3})(NHCPh{sub 3})(M)] (BIPM{sup TMS}=C(PPh{sub 2}NSiMe{sub 3}){sub 2}; M=Li or K) that can be described as R{sub 2}C=U=NR' push-pull metalla-allene units, as organometallic counterparts of the well-known push-pull organic allenes. The solid-state structures reveal that the R{sub 2}C=U=NR' units adopt highly unusual cis-arrangements, which are also reproduced by gas-phase theoretical studies conducted without the alkali metals to remove their potential structure-directing roles. Computational studies confirm the double-bond nature of the U=NR' and U=CR{sub 2} interactions, the latter increasingly attenuated by potassium then lithium when compared to the hypothetical alkali-metal-free anion. Combined experimental and theoretical data show that the push-pull effect induced by the alkali metal cations and amide auxiliary gives a fundamental and tunable structural influence over the C=U{sup IV}=N units. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Low temperature wetting and cleanup of alkali metal-advanced electrical machine systems

International Nuclear Information System (INIS)

Gass, W.R.; Witkowski, R.E.; Burrow, G.C.

1980-01-01

Advanced homopolar electrical machines employing high electrical current density, liquid metal sliprings for current transfer utilize NaK/sub 78/ (78 w/o potassium, 22 w/o sodium) for the conducting fluid. Experiments have been performed to improve alkali metal/oxide clean-up procedures. Studies have also confirmed chemical and materials compatibility between barium doped NaK/sub 78/ and typical machine structural materials. 4 refs

Van der Waals coefficients for alkali metal clusters and their size

Indian Academy of Sciences (India)

In this paper we employ the hydrodynamic formulation of time-dependent density functional theory to obtain the van der Waals coefficients 6 and 8 of alkali metal clusters of various sizes including very large clusters. Such calculations become computationally very demanding in the orbital-based Kohn-Sham formalism, ...

The interplay between hydrogen evolution reaction and nitrate reduction on boron-doped diamond in aqueous solution: the effect of alkali cations

International Nuclear Information System (INIS)

Manzo-Robledo, A.; Lévy-Clément, C.; Alonso-Vante, N.

2014-01-01

The nitrate ion reduction was studied on boron-doped diamond (BDD) electrodes by real-time on-line differential electrochemical mass spectrometry (DEMS) coupled with chronoamperometry in K + , Na + cation-containing electrolyte solutions. It was found, via steady state voltammetry, that the hydrogen evolution reaction (HER) was affected by the presence of K + or Na + . A moderate HER occurs in K + -containing electrolyte solution favoring the reaction between NO 3 − and H 2 species, whereas in Na + -containing electrolyte solutions, the HER kinetics was more important leading to a suppression of molecular nitrogen generation. The use of isotope-labeled nitrogen and DEMS confirmed the influence of alkali cations toward the nitrate ion reduction

Conductivity Measurements of Alkali Metal Thiocyanates in Water-Methanol Mixtures; Mizu-metanoru kongoyoubai ni okeru arukari kinzoku chioshiansan`en no denki dendodo sokutei

Energy Technology Data Exchange (ETDEWEB)

Kubota, Eiji.; Horimoto, Sanaki. [Shinshu University, Nagano (Japan). Faculty of Science

1999-03-10

The counductivity of several alkali nmetal thiocyanates in water-methanol mixtures was measured at 25degreeC. the data were analyzed using Lee-Wheaton theory for symmetrical electroyers to cbtain ion association constant, K{sub A}, limiting molar sonductivity, {Lambda}{sub 0}, and limiting ionic molar conductivity, lamnda{sub 0}{+-}. In all the solvent systems, calculated{lambda}{sub 0}{sup +} values of the alkali metal ions increase in the order L{sub i}{sup +}alkali metal ions and thiocyanate ion showed a minimum when the molar fraction of methanol was ca.0.4. The changes in {lambda}{sub 0}{+-} of these alkali metal ions and thiocyanate ion with the molar fraction of methanol agree with change in the viscosity of the solvent or the heat of mixing of wateer-methanol mixtures. These alkali metal thiocyanates from little or no ion aggregated in water and water-methanol mixtures. These alkali metal thiocyanates K{sub A}=15-24 dm{sup 3} mol{sub -1} in methanol. (author)

A review of flexible lithium-sulfur and analogous alkali metal-chalcogen rechargeable batteries.

Science.gov (United States)

Peng, Hong-Jie; Huang, Jia-Qi; Zhang, Qiang

2017-08-29

Flexible energy storage systems are imperative for emerging flexible devices that are revolutionizing our life. Lithium-ion batteries, the current main power sources, are gradually approaching their theoretical limitation in terms of energy density. Therefore, alternative battery chemistries are urgently required for next-generation flexible power sources with high energy densities, low cost, and inherent safety. Flexible lithium-sulfur (Li-S) batteries and analogous flexible alkali metal-chalcogen batteries are of paramount interest owing to their high energy densities endowed by multielectron chemistry. In this review, we summarized the recent progress of flexible Li-S and analogous batteries. A brief introduction to flexible energy storage systems and general Li-S batteries has been provided first. Progress in flexible materials for flexible Li-S batteries are reviewed subsequently, with a detailed classification of flexible sulfur cathodes as those based on carbonaceous (e.g., carbon nanotubes, graphene, and carbonized polymers) and composite (polymers and inorganics) materials and an overview of flexible lithium anodes and flexible solid-state electrolytes. Advancements in other flexible alkali metal-chalcogen batteries are then introduced. In the next part, we emphasize the importance of cell packaging and flexibility evaluation, and two special flexible battery prototypes of foldable and cable-type Li-S batteries are highlighted. In the end, existing challenges and future development of flexible Li-S and analogous alkali metal-chalcogen batteries are summarized and prospected.

Molybdenum cell for x-ray diffraction measurements of fluid alkali metals at high temperatures and high pressures

Science.gov (United States)

Matsuda, Kazuhiro; Tamura, Kozaburo; Katoh, Masahiro; Inui, Masanori

2004-03-01

We have developed a sample cell for x-ray diffraction measurements of fluid alkali metals at high temperatures and high pressures. All parts of the cell are made of molybdenum which is resistant to the chemical corrosion of alkali metals. Single crystalline molybdenum disks electrolytically thinned down to 40 μm were used as the walls of the cell through which x rays pass. The crystal orientation of the disks was controlled in order to reduce the background from the cell. All parts of the cell were assembled and brazed together using a high-temperature Ru-Mo alloy. Energy dispersive x-ray diffraction measurements have been successfully carried out for fluid rubidium up to 1973 K and 16.2 MPa. The obtained S(Q) demonstrates the applicability of the molybdenum cell to x-ray diffraction measurements of fluid alkali metals at high temperatures and high pressures.

Regulation of Cation Balance in Saccharomyces cerevisiae

Science.gov (United States)

Cyert, Martha S.; Philpott, Caroline C.

2013-01-01

All living organisms require nutrient minerals for growth and have developed mechanisms to acquire, utilize, and store nutrient minerals effectively. In the aqueous cellular environment, these elements exist as charged ions that, together with protons and hydroxide ions, facilitate biochemical reactions and establish the electrochemical gradients across membranes that drive cellular processes such as transport and ATP synthesis. Metal ions serve as essential enzyme cofactors and perform both structural and signaling roles within cells. However, because these ions can also be toxic, cells have developed sophisticated homeostatic mechanisms to regulate their levels and avoid toxicity. Studies in Saccharomyces cerevisiae have characterized many of the gene products and processes responsible for acquiring, utilizing, storing, and regulating levels of these ions. Findings in this model organism have often allowed the corresponding machinery in humans to be identified and have provided insights into diseases that result from defects in ion homeostasis. This review summarizes our current understanding of how cation balance is achieved and modulated in baker’s yeast. Control of intracellular pH is discussed, as well as uptake, storage, and efflux mechanisms for the alkali metal cations, Na+ and K+, the divalent cations, Ca2+ and Mg2+, and the trace metal ions, Fe2+, Zn2+, Cu2+, and Mn2+. Signal transduction pathways that are regulated by pH and Ca2+ are reviewed, as well as the mechanisms that allow cells to maintain appropriate intracellular cation concentrations when challenged by extreme conditions, i.e., either limited availability or toxic levels in the environment. PMID:23463800

Boson peak of alkali and alkaline earth silicate glasses: influence of the nature and size of the network-modifying cation.

Science.gov (United States)

Richet, Nicolas F

2012-01-21

The influence of the size of the alkaline earth cation on the boson peak of binary metasilicate glasses, MSiO(3) (M = Mg, Ca, Sr, Ba), has been investigated from vibrational densities of states determined by inversion of low-temperature heat capacities. As given both by C(p)/T(3) and g(ω)/ω(2), the intensity of the boson peak undergoes a 7-fold increase from Mg to Ba, whereas its temperature and frequency correlatively decrease from 18 to 10 K and from 100 to 20 cm(-1), respectively. The boson peak results from a combination of librations of SiO(4) tetrahedra and localized vibrations of network-modifying cations with non-bridging oxygens whose contribution increases markedly with the ionic radius of the alkaline earth. As a function of ionic radii, the intensity for Sr and Ba varies in the same way as previously found for alkali metasilicate glasses. The localized vibrations involving alkali and heavy alkaline earth cations appear to be insensitive to the overall glass structure. Although the new data are coherent with an almost linear relationship between the temperature of the boson peak and transverse sound velocity, pure SiO(2) and SiO(2)-rich glasses make marked exceptions to this trend because of the weak transverse character of SiO(4) librations. Finally, the universality of the calorimetric boson peak is again borne out because all data for silicate glasses collapse on the same master curve when plotted in a reduced form (C(P)∕/T(3))/(C(P)/T(3))(b) vs. T/T(b). © 2012 American Institute of Physics

Investigation of electrochemical intrusion of cations by the method of contact electric resistance

International Nuclear Information System (INIS)

Marichev, V.A.

1997-01-01

Paper shows the possibility and prospects of application of contact electric resistance technique (CER) to study in-situ the initial stages of electrochemical admission of cations (ECA). ECA is shown to increase CER of metals. It enables to determine ECA potential and to investigate kinetics of this process. Using ECA in copper, silver and zinc from alkali solutions as an example one has shown that CER technique enables to obtain results that do not contradict well-known published data. Potentials of ECA cations from acid and neutral solutions in copper, platinum, iron, titanium and tungsten are determined

Cation-Inhibited Transport of Graphene Oxide Nanomaterials in Saturated Porous Media: The Hofmeister Effects.

Science.gov (United States)

Xia, Tianjiao; Qi, Yu; Liu, Jing; Qi, Zhichong; Chen, Wei; Wiesner, Mark R

2017-01-17

Transport of negatively charged nanoparticles in porous media is largely affected by cations. To date, little is known about how cations of the same valence may affect nanoparticle transport differently. We observed that the effects of cations on the transport of graphene oxide (GO) and sulfide-reduced GO (RGO) in saturated quartz sand obeyed the Hofmeister series; that is, transport-inhibition effects of alkali metal ions followed the order of Na + cations having large ionic radii (and thus being weakly hydrated) interacted with quartz sand and GO and RGO more strongly than did cations of small ionic radii. In particular, the monovalent Cs + and divalent Ca 2+ and Ba 2+ , which can form inner-sphere complexes, resulted in very significant deposition of GO and RGO via cation bridging between quartz sand and GO and RGO, and possibly via enhanced straining, due to the enhanced aggregation of GO and RGO from cation bridging. The existence of the Hofmeister effects was further corroborated with the interesting observation that cation bridging was more significant for RGO, which contained greater amounts of carboxyl and phenolic groups (i.e., metal-complexing moieties) than did GO. The findings further demonstrate that transport of nanoparticles is controlled by the complex interplay between nanoparticle surface functionalities and solution chemistry constituents.

Special features of the formation of high-conductivity phases of halides of alkali metals at superhigh pressures

International Nuclear Information System (INIS)

Babushkin, A.N.; Babushkina, G.V.

1999-01-01

The halides of alkali metals are the simplest crystals with the ionic nature of chemical bonds and are used widely as modelling materials in high-pressure physics. As a result of previous theoretical and experimental (optical, structural, electro-physical and shock-waves) investigations it was shown that these materials may be characterised by the overlapping of the valency and conduction bands and by the formation of groups of free charge carriers at pressures of the megabaric level. However, the authors know of no data on the direct investigations of the electrophysical properties of the halides of alkali metals at such high static pressures. The end of this investigation was to examine the temperature dependences of the electrical conductivity and thermal EMF of halides of alkali metals AX (A = Na, K, Rb, Cs, X = Cl, Br, I) in a wide temperature range at pressures from 10 to 50 GPa in order to reveal the general leisure since governing the change of their electronic structures, in particular, the transition to the state with the activation-type or metallic conductivity

Element specificity of ortho-positronium annihilation for alkali-metal loaded SiO2 glasses.

Science.gov (United States)

Sato, K; Hatta, T

2015-03-07

Momentum distributions associated with ortho-positronium (o-Ps) pick-off annihilation photon are often influenced by light elements, as, e.g., carbon, oxygen, and fluorine. This phenomenon, so-called element specificity of o-Ps pick-off annihilation, has been utilized for studying the elemental environment around the open spaces. To gain an insight into the element specificity of o-Ps pick-off annihilation, the chemical shift of oxygen 1s binding energy and the momentum distributions associated with o-Ps pick-off annihilation were systematically investigated for alkali-metal loaded SiO2 glasses by means of X-ray photoelectron spectroscopy and positron-age-momentum correlation spectroscopy, respectively. Alkali metals introduced into the open spaces surrounded by oxygen atoms cause charge transfer from alkali metals to oxygen atoms, leading to the lower chemical shift for the oxygen 1s binding energy. The momentum distribution of o-Ps localized into the open spaces is found to be closely correlated with the oxygen 1s chemical shift. This correlation with the deepest 1s energy level evidences that the element specificity of o-Ps originates from pick-off annihilation with orbital electrons, i.e., dominantly with oxygen 2p valence electrons and s electrons with lower probability.

Equation of state for thermodynamic properties of pure and mixtures liquid alkali metals

International Nuclear Information System (INIS)

Mousazadeh, M.H.; Faramarzi, E.; Maleki, Z.

2010-01-01

We developed an equation of state based on statistical-mechanical perturbation theory for pure and mixtures alkali metals. Thermodynamic properties were calculated by the equation of state, based on the perturbed-chain statistical associating fluid theory (PC-SAFT). The model uses two parameters for a monatomic system, segment size, σ, and segment energy, ε. In this work, we calculate the saturation and compressed liquid density, heat capacity at constant pressure and constant volume, isobaric expansion coefficient, for which accurate experimental data exist in the literatures. Results on the density of binary and ternary alkali metal alloys of Cs-K, Na-K, Na-K-Cs, at temperatures from the freezing point up to several hundred degrees above the boiling point are presented. The calculated results are in good agreement with experimental data.

The removal of alkali metals from hot gas

Energy Technology Data Exchange (ETDEWEB)

Orjala, M.; Haukka, P. (Valtion Teknillinen Tutkimuskeskus, Jyvaeskylae (Finland). Polttoaine- ja Polttotekniikan Lab.)

1990-01-01

In investigations in progress at the Fuel and Combustion Laboratory of the Technical Research Centre of Finland, we have been studying in co-operation with A. Ahlstrom Boiler Works, the removal of alkali metals from flue gases of ash-rich fuel with a dense suspension particle cooler. The applications of the particle cooler can be found in combined cycles and in industrial gas cleaning and heat recovery. We have also developed a general mathematical model of heat and mass transfer as well as chemical and physical reactions in multiphase systems.

Electric conductivity of alkali metal vapors in the region of critical point

International Nuclear Information System (INIS)

Likal'ter, A.A.

1982-01-01

A behaviour of alkali metal conductivity in the vicinity of a critical point has been analyzed on the base of deVeloped representations on a vapor state. A phenomenological conductivity theory has been developed, which is in a good agreement with experimental data obtained

Analysis of the plasma impurity influx from alkali-metal coatings for fusion-reactor applications

International Nuclear Information System (INIS)

DeWald, A.B.; Davidson, J.N.; Krauss, A.R.; Gruen, D.M.

1982-01-01

Recently, it has been proposed that alkali-metal covered surfaces be applied to magnetic fusion devices as a means of controlling plasma impurity contamination and shielding the substrate from erosion. Monolayer films of alkali metals have been shown to sputter primarily as ions under particle bombardment. Thus, it is thought that a sheath potential and/or magnetic fields encountered by a sputtered ion will return the ion to the surface without entering the plasma. In this paper, we investigate the net wall impurity influx associated with coatings which exhibit substantial secondary ion emission as compared to those which sputter only as neutral atoms. Included in the analysis are sputtered substrate atoms. These are sometimes found to be a significant fraction of the total sputtering yield for low-Z alkali monolayers and affect the overall performance of such coatings. Estimates of the impurity influx made in the neighborhood of a sheath potential show that secondary-ion emitting coatings are effective as a means of inhibiting plasma impurity contamination and wall erosion

Assessment of alkali metal coolants for the ITER blanket

International Nuclear Information System (INIS)

Natesan, K.; Reed, C.B.; Mattas, R.F.

1994-01-01

The blanket system is one of the most important components of a fusion reactor because it has a major impact on both the economics and safety of fusion energy. The primary functions of the blanket in a deuterium/tritium-fueled fusion reactor are to convert the fusion energy into sensible heat and to breed tritium for the fuel cycle. The Blanket Comparison and Selection Study, conducted earlier, described the overall comparative performance of different blanket concepts, including liquid metal, molten salt, water, and helium. This paper will discuss the ITER requirements for a self-cooled blanket concept with liquid lithium and for indirectly cooled concepts that use other alkali metals such as NaK. The paper will address the thermodynamics of interactions between the liquid metals (i.e., lithium and NaK) and structural materials (e.g., V-base alloys), together with associated corrosion/compatibility issues. Available experimental data will be used to assess the long-term performance of the first wall in a liquid metal environment

Thermochemistry of the complex oxides of uranium, vanadium, and alkali metals

International Nuclear Information System (INIS)

Karyakin, N.V.; Chernorukov, N.G.; Suleimanov, E.V.; Kharyushina, E.A.

1992-01-01

The standard enthalpies of the formation at T 298.15 K of complex oxides of uranium(VI), vanadium(V) and alkali metals with the general formula M 1 VUO 6 where M 1 = Na, K, Rb, and Cs, were calculated from the results of calorimetric experiments and from published data. 8 refs., 1 tab

The non-pair forces and phonon dispersion in heavy alkali metals

International Nuclear Information System (INIS)

Aradhana, Km.; Rathore, R.P.S.

1990-01-01

Two types of non-pair forces, one from the Born-Mayer and the other from the Morse potential, are derived to discuss the response of electrons in heavy alkali metals, i.e., rubidium and cesium. The potentials are added to the two-body potential of Morse to account also for the ion-ion interactions. The potentials so obtained are employed to predict the phonon dispersion relations in bcc metals, which are also compared with recent precise neutron scattering data. (author). 1 fig, 3 tabs., 24 refs

Effect of cationic composition of electrolyte on kinetics of lead electrolytic separation in chloride melts

International Nuclear Information System (INIS)

Yurkinskij, V.P.; Makarov, D.V.

1995-01-01

The mechanism has been studied and kinetic parameters of the process of Pb(2) ion electrochemical reduction have been ascertained for different individual melts of alkali metal chlorides and their mixtures, using methods of linear voltammetry chronopotentiometry and chronoamperometry. It has been ascertained that cations in the melts of alkali metal chlorides affect stability of [PbCl n ] 2-n ions. The data obtained suggest that the strength of the complexes increases in the series NaCl-KCl-CsCl. In the melt of sodium chloride the electrode process is limited by diffusion, whereas in the melts of KCl, CsCl, CsCl-NaCl with cesium chloride content exceeding 70 mol% lead electrochemical reduction is controlled by preceding dissociation of the complexes. 10 refs., 3 figs., 2 tabs

Complexes of natural carbohydrates with metal cations

International Nuclear Information System (INIS)

Alekseev, Yurii E; Garnovskii, Alexander D; Zhdanov, Yu A

1998-01-01

Data on the interaction of natural carbohydrates (mono-, oligo-, and poly-saccharides, amino sugars, and natural organic acids of carbohydrate origin) with metal cations are surveyed and described systematically. The structural diversity of carbohydrate metal complexes, caused by some specific features of carbohydrates as ligands, is demonstrated. The influence of complex formation on the chemical properties of carbohydrates is discussed. It is shown that the formation of metal complexes plays an important role in the configurational and conformational analysis of carbohydrates. The practical significance of the coordination interaction in the series of carbohydrate ligands is demonstrated. The bibliography includes 571 references.

An alkali ion source based on graphite intercalation compounds for ion mobility spectrometry

International Nuclear Information System (INIS)

Tabrizchi, Mahmoud; Hosseini, Zahra S

2008-01-01

A variety of alkali cation emitters were developed as the ion source for ion mobility spectrometry. The cation emitters were constructed based on alkali ion graphite intercalation compounds (GICs). The compounds were prepared by fusing alkali salts with ground graphite. In order to produce alkali ions, the compounds were loaded on a filament and heated to red. Reactant ions of the form alk + ions were observed for the alkali salts NaCl, KCl.LiCl, CsCl and SrCl. In addition to Na + ions, K + ions were observed at the beginning of thermionic emission from Na-GIC. This is due to the low ionization potential of potassium that exists in trace amounts in sodium salts. In addition to the potassium ion, Na + was observed in the case of LiCl salt. The Na + and K + peaks originating from impurities totally disappeared after about 40 min. However, the thermionic emission of the main ion of the corresponding salt lasted for several days. No negative ions were observed upon reversing the drift field. Selected organic compounds (methyl isobutyl ketone, dimethyl sulfoxide, acetone and tetrahydrofuran) were also ionized via alkali cation attachment reaction. Distinct ion mobility patterns were observed for different substances using one type of alkali reactant ion. However, the ion mobility pattern for a given substance changed when a different alkali reactant ion was used. Ammonia and amines were not ionized when this source was used

On the influence and role of alkali metals on supported and unsupported activated hydrotalcites for CO2 sorption

NARCIS (Netherlands)

Meis, N.N.A.H.; Bitter, J.H.; de Jong, K.P.

2013-01-01

To increase the CO2 capture capacity of hydrotalcites, the influence of alkali (K, Na) metal carbonate loading of activated supported and unsupported hydrotalcites (HTact) on their CO2 capture properties was investigated. The alkali-loaded supported hydrotalcites adsorb at 523 K, depending on the

THE DISTRIBUTION OF COMMERCIAL CROWN ETHER DC18C6 AND THE EXTRACTION STUDY OF ALKALI AND EARTH ALKALI METALS

Directory of Open Access Journals (Sweden)

Bambang Rusdiarso

2010-06-01

Full Text Available Distribution of A and B isomers of crown-ether DC18C6 on their organic and water phases (chloride, nitrate and sulphocyanide salts and extraction of alkali and earth alkali metals has been studied. In LiCl 0.1 M environment, lithium extraction could be ignored. The presence of extracted potassium metal may affect the crown ether DC18C6 distribution albeit only a little. In KNO3 0.1 M environment, the distribution coefficient values (d were 6.1 and 10.3 for A and B isomers, respectively ; while in KCl  0.1 M environment the values were 4.9 and 11.8, respectively. In KSCN 0.1 M, d values for A and B isomers were 40.4 and 36.6, respectively, which were higher than the value obtained from both KNO3 and KCl  0.1 M environments. Caesium metal extraction using DC18C6 occurred weakly, up to only 5%. Strontium extraction using DC18C6 achieved better yield than the caesium extraction. The percentage of extraction increased under organic solvent according to the following: toluene (4% < chloroform (28% < TBP (35%.   Keywords: distribution, crown-ether DC18C6, extraction.

New bonding configuration on Si(111) and Ge(111) surfaces induced by the adsorption of alkali metals

DEFF Research Database (Denmark)

Lottermoser, L.; Landemark, E.; Smilgies, D.M.

1998-01-01

The structure of the (3×1) reconstructions of the Si(111) and Ge(111) surfaces induced by adsorption of alkali metals has been determined on the basis of surface x-ray diffraction and low-energy electron diffraction measurements and density functional theory. The (3×1) surface results primarily f...... from the substrate reconstruction and shows a new bonding configuration consisting of consecutive fivefold and sixfold Si (Ge) rings in 〈11̅ 0〉 projection separated by channels containing the alkali metal atoms. © 1998 The American Physical Society...

Electronic and structural ground state of heavy alkali metals at high pressure

Science.gov (United States)

Fabbris, G.; Lim, J.; Veiga, L. S. I.; Haskel, D.; Schilling, J. S.

2015-02-01

Alkali metals display unexpected properties at high pressure, including emergence of low-symmetry crystal structures, which appear to occur due to enhanced electronic correlations among the otherwise nearly free conduction electrons. We investigate the high-pressure electronic and structural ground state of K, Rb, and Cs using x-ray absorption spectroscopy and x-ray diffraction measurements together with a b i n i t i o theoretical calculations. The sequence of phase transitions under pressure observed at low temperature is similar in all three heavy alkalis except for the absence of the o C 84 phase in Cs. Both the experimental and theoretical results point to pressure-enhanced localization of the valence electrons characterized by pseudogap formation near the Fermi level and strong s p d hybridization. Although the crystal structures predicted to host magnetic order in K are not observed, the localization process appears to drive these alkalis closer to a strongly correlated electron state.

Fate of alkali and trace metals in biomass gasification

International Nuclear Information System (INIS)

Salo, K.; Mojtahedi, W.

1998-01-01

The fate of alkali metals (Na, K) and eleven toxic trace elements (Hg, Cd, Be, Se, Sb, As, Pb, Zn, Cr, Co, Ni) in biomass gasification have been extensively investigated in Finland in the past ten years. The former due to the gas turbine requirements and the latter to comply with environmental regulations. In this paper the results of several experimental studies to measure Na and K in the vapor phase after the gas cooler of a simplified (air-blown) Integrated Gasification Combined-Cycle (IGCC) system are reported. Also, trace element emissions from an IGCC plant using alfalfa as the feedstock are discussed and the concentration of a few toxic trace metals in the vapor phase in the gasifier product gas are reported. (author)

The mechanism of diffusion and ionic transport of alkali metal ions in the particles of tin(IV) antimonate

International Nuclear Information System (INIS)

El-Naggar, I.M.; El-Absy, M.A.; Aly, S.I.; Atomic Energy Establishment, Cairo

1992-01-01

The kinetics of exchange Li + , Na + , K + and Cs + ions of tin(IV) antimonate with H + form was studied under particle-diffusion-control conditions at different temperatures. The value of activation energy, diffusion coefficient and entropy of activation increase with the ionic mobilities and radii, and decrease with the hydration energy of the alkali metal ions. On the basis of the kinetic parameters, the exchange of alkali metal ions occurs in the unhydrated form. (author). 29 refs.; 4 figs.; 2 tabs

Emission spectra of alkali-metal (K,Na,Li)-He exciplexes in cold helium gas

International Nuclear Information System (INIS)

Enomoto, K.; Hirano, K.; Kumakura, M.; Takahashi, Y.; Yabuzaki, T.

2004-01-01

We have observed emission spectra of excimers and exciplexes composed of a light alkali-metal atom in the first excited state and 4 He atoms [K*He n (n=1-6), Na * He n (n=1-4), and Li * He n (n=1,2)] in cryogenic He gas (the temperature 2 K -1 . Differently from exciplexes with heavier alkali-metal atoms, the spectra for the different number of He atoms were well separated, so that their assignment could be made experimentally. Comparing with the spectra of K * He n , we found that the infrared emission spectrum of the K atom excited in liquid He was from K*He 6 . To confirm the assignment, we have also carried out ab initio calculation of adiabatic potential curves and peak positions of the emission spectra of the exciplexes

X-ray Compton scattering experiments for fluid alkali metals at high temperatures and pressures

Energy Technology Data Exchange (ETDEWEB)

Matsuda, K., E-mail: kazuhiro-matsuda@scphys.kyoto-u.ac.jp; Fukumaru, T.; Kimura, K.; Yao, M. [Graduate School of Science, Kyoto University, Kyoto 606-8502 (Japan); Tamura, K. [Graduate School of Engineering, Kyoto University, Kyoto 606-8502 (Japan); Katoh, M. [A.L.M.T. Corp., Iwasekoshi-Machi 2, Toyama 931-8543 (Japan); Kajihara, Y.; Inui, M. [Graduate School of Integrated Arts and Sciences, Hiroshima University, Higashi-Hiroshima 739-8521 (Japan); Itou, M.; Sakurai, Y. [Japan Synchrotron Radiation Research Institute, SPring-8, 1-1-1 Kouto, Sayo, Hyogo 679-5198 (Japan)

2015-08-17

We have developed a high-pressure vessel and a cell for x-ray Compton scattering measurements of fluid alkali metals. Measurements have been successfully carried out for alkali metal rubidium at elevated temperatures and pressures using synchrotron radiation at SPring-8. The width of Compton profiles (CPs) of fluid rubidium becomes narrow with decreasing fluid density, which indicates that the CPs sensitively detect the effect of reduction in the valence electron density. At the request of all authors of the paper, and with the agreement of the Proceedings Editor, an updated version of this article was published on 10 September 2015. The original article supplied to AIP Publishing was not the final version and contained PDF conversion errors in Formulas (1) and (2). The errors have been corrected in the updated and re-published article.

The Metal Cation Chelating Capacity of Astaxanthin. Does This Have Any Influence on Antiradical Activity?

Directory of Open Access Journals (Sweden)

Ana Martínez

2012-01-01

Full Text Available In this Density Functional Theory study, it became apparent that astaxanthin (ASTA may form metal ion complexes with metal cations such as Ca+2, Cu+2, Pb+2, Zn+2, Cd+2 and Hg+2. The presence of metal cations induces changes in the maximum absorption bands which are red shifted in all cases. Therefore, in the case of compounds where metal ions are interacting with ASTA, they are redder in color. Moreover, the antiradical capacity of some ASTA-metal cationic complexes was studied by assessing their vertical ionization energy and vertical electron affinity, reaching the conclusion that metal complexes are slightly better electron donors and better electron acceptors than ASTA.

STUDIES ON THE FORMATION AND IONIZATION OF THE COMPOUNDS OF CASEIN WITH ALKALI

Science.gov (United States)

Greenberg, David M.; Schmidt, Carl L. A.

1924-01-01

1. The deposition of casein on a platinum anode which takes place on the passage of a direct current through solutions of alkali caseinates was quantitatively studied, and it was found that: (a) the amount of casein which is deposited is directly proportional to the current, i.e. it obeys Faraday's law; (b) the amount of casein deposited is inversely proportional (within the limits studied) to the amount of alkali which is combined with the casein. 2. A method of determining the transport numbers of proteins insoluble at their isoelectric point has been developed. 3. A titration method for determining the amount of alkali in a casein solution is given. 4. Data from the results of transference experiments on sodium caseinate, potassium caseinate, cesium caseinate, and rubidium caseinate solutions are given. It is shown that the data are best explained on the assumption that in these solutions the carriers of the current are alkali metal cations and casein anions. 5. On the basis of our transference results an explanation is given of the results which were obtained by Robertson and by Haas in their migration experiments. PMID:19872135

Nuclear alkali metal Rankine power systems for space applications

International Nuclear Information System (INIS)

Moyers, J.C.; Holcomb, R.S.

1986-08-01

Nucler power systems utilizing alkali metal Rankine power conversion cycles offer the potential for high efficiency, lightweight space power plants. Conceptual design studies are being carried out for both direct and indirect cycle systems for steady state space power applications. A computational model has been developed for calculating the performance, size, and weight of these systems over a wide range of design parameters. The model is described briefly and results from parametric design studies, with descriptions of typical point designs, are presented in this paper

Nuclear alkali metal Rankine power systems for space applications

International Nuclear Information System (INIS)

Moyers, J.C.; Holcomb, R.S.

1986-01-01

Nuclear power systems utilizing alkali metal Rankine power conversion cycles offer the potential for high efficiency, lightweight space power plants. Conceptual design studies are being carried out for both direct and indirect cycle systems for steady state space power applications. A computational model has been developed for calculating the performance, size, and weight of these systems over a wide range of design parameters. The model is described briefly and results from parametric design studies, with descriptions of typical point designs, are presented in this paper

An analysis of the plasma impurity influx from alkali-metal coatings for fusion reactor applications

International Nuclear Information System (INIS)

DeWald, A.B.; Davidson, J.N.; Krauss, A.R.; Gruen, D.M.

1982-01-01

Recently, it has been proposed that alkali-metal covered surfaces be applied to magnetic fusion devices as a means of controlling plasma impurity contamination and shielding the substrate from erosion. Monolayer films of alkali metals have been shown to sputter primarily as ions under particle bombardment. Thus, it is thought that a sheath potential and/or magnetic fields encountered by a sputtered ion will return the ion to the surface without entering the plasma. In this paper, we investigate the net wall impurity influx associated with coatings which exhibit substantial secondary ion emission compared with those which sputter only as neutral atoms. Included in the analysis are sputtered substrate atoms. These are sometimes found to be a significant fraction of the total sputtering yield for low-Z alkali monolayers and affect the overall performance of such coatings. Estimates of the impurity influx made in the neighborhood of a sheath potential show that secondary-ion emitting coatings are effective as a means of inhibiting plasma impurity contamination and wall erosion. (orig.)

ALKALI RESISTANT CATALYST

DEFF Research Database (Denmark)

2008-01-01

The present invention concerns the selective removal of nitrogen oxides (NOx) from gasses. In particular, the invention concerns a process, a catalyst and the use of a catalyst for the selective removal of nitrogen oxides in the presence of ammonia from gases containing a significant amount...... of alkali metal and/or alkali-earth compounds which process comprises using a catalyst combined of (i) a formed porous superacidic support, said superacidic support having an Hammett acidity stronger than Ho=-12, and (ii) a metal oxide catalytic component deposited on said superacidic support selected from...

Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2.

Science.gov (United States)

Maitra, Urmimala; House, Robert A; Somerville, James W; Tapia-Ruiz, Nuria; Lozano, Juan G; Guerrini, Niccoló; Hao, Rong; Luo, Kun; Jin, Liyu; Pérez-Osorio, Miguel A; Massel, Felix; Pickup, David M; Ramos, Silvia; Lu, Xingye; McNally, Daniel E; Chadwick, Alan V; Giustino, Feliciano; Schmitt, Thorsten; Duda, Laurent C; Roberts, Matthew R; Bruce, Peter G

2018-03-01

The search for improved energy-storage materials has revealed Li- and Na-rich intercalation compounds as promising high-capacity cathodes. They exhibit capacities in excess of what would be expected from alkali-ion removal/reinsertion and charge compensation by transition-metal (TM) ions. The additional capacity is provided through charge compensation by oxygen redox chemistry and some oxygen loss. It has been reported previously that oxygen redox occurs in O 2p orbitals that interact with alkali ions in the TM and alkali-ion layers (that is, oxygen redox occurs in compounds containing Li + -O(2p)-Li + interactions). Na 2/3 [Mg 0.28 Mn 0.72 ]O 2 exhibits an excess capacity and here we show that this is caused by oxygen redox, even though Mg 2+ resides in the TM layers rather than alkali-metal (AM) ions, which demonstrates that excess AM ions are not required to activate oxygen redox. We also show that, unlike the alkali-rich compounds, Na 2/3 [Mg 0.28 Mn 0.72 ]O 2 does not lose oxygen. The extraction of alkali ions from the alkali and TM layers in the alkali-rich compounds results in severely underbonded oxygen, which promotes oxygen loss, whereas Mg 2+ remains in Na 2/3 [Mg 0.28 Mn 0.72 ]O 2 , which stabilizes oxygen.

Freezing of liquid alkali metals as screened ionic plasmas

International Nuclear Information System (INIS)

Badirkhan, Z.; Rovere, M.; Tosi, M.P.

1990-08-01

The relationship between Wigner crystallization of the classical ionic plasma and the liquid-solid transition of alkali metals is examined within the density wave theory of freezing. Freezing of the classical plasma on a rigid neutralizing background into the bcc structure is first re-evaluated, in view of recent progress in the determination of its thermodynamic functions by simulation and of the known difficulties of the theory relating to the order parameter at the (200) star of reciprocal lattice vectors. Freezing into the fcc structure is also considered in this context and found to be unfavoured. On allowing for long-wavelength deformability of the background, the ensuing appearance of a volume change on freezing into the bcc structure is accompanied by reduced stability of the fluid phase and by an increase in the entropy of melting. Freezing of alkali metals into the bcc structure is next evaluated, taking their ionic pair structure as that of an ionic plasma reference fluid screened by conduction electrons and asking that the correct ionic coupling strength at liquid-solid coexistence should be approximately reproduced. The ensuring values of the volume and entropy changes across the phase transition, as estimated from the theory by two alternative routes, are in reasonable agreement with experiment. The order parameters of the phase transition, excepting the (200) one, conform rather closely to a Gaussian behaviour and yield a Lindemann ratio in reasonable agreement with the empirical value for melting of bcc crystals. It is suggested that ionic ordering at the (200) star in the metal may be (i) assisted by medium range ordering in the conduction electrons, as indicated by differences in X-ray and neutron diffraction intensities from the liquid, and/or (ii) quite small in the hot bcc solid. Such a possible premelting behaviour of bcc metals should be worth testing experimentally by diffraction. (author). 48 refs, 1 fig., 1 tab

Temperatures and enthalpies of melting of alkali-metal perrhenates

International Nuclear Information System (INIS)

Lukas, W.; Gaune-Escard, M.

1982-01-01

Melting temperatures and enthalpies of melting were determined for alkali-metal perrhenates by differential enthalpic analysis using a high-temperature Calvet microcalorimeter. The following values were obtained: for LiReO 4 : 692 K and 24.9 kJ.mol -1 ; for NaReO 4 : 693 K and 33 kJ.mol -1 ; for KReO 4 : 828 K and 36 kJ.mol -1 ; for RbReO 4 : 878 K and 34 kJ.mol -1 ; for CsReO 4 : 893 K and 34 kJ.mol -1 . (author)

Integrated oil production and upgrading using molten alkali metal

Science.gov (United States)

Gordon, John Howard

2016-10-04

A method that combines the oil retorting process (or other process needed to obtain/extract heavy oil or bitumen) with the process for upgrading these materials using sodium or other alkali metals. Specifically, the shale gas or other gases that are obtained from the retorting/extraction process may be introduced into the upgrading reactor and used to upgrade the oil feedstock. Also, the solid materials obtained from the reactor may be used as a fuel source, thereby providing the heat necessary for the retorting/extraction process. Other forms of integration are also disclosed.

3718-F Alkali Metal Treatment and Storage Facility Closure Plan. Revision 1

Energy Technology Data Exchange (ETDEWEB)

None

1992-11-01

The Hanford Site, located northwest of the city of Richland, Washington, houses reactors, chemical-separation systems, and related facilities used for the production of special nuclear materials, as well as for activities associated with nuclear energy development. The 300 Area of the Hanford Site contains reactor fuel manufacturing facilities and several research and development laboratories. The 3718-F Alkali Metal Treatment and Storage Facility (3718-F Facility), located in the 300 Area, was used to store and treat alkali metal wastes. Therefore, it is subject to the regulatory requirements for the storage and treatment of dangerous wastes. Closure will be conducted pursuant to the requirements of the Washington Administrative Code (WAC) 173-303-610 (Ecology 1989) and 40 CFR 270.1. Closure also will satisfy the thermal treatment facility closure requirements of 40 CFR 265.381. This closure plan presents a description of the 3718-F Facility, the history of wastes managed, and the approach that will be followed to close the facility. Only hazardous constituents derived from 3718-F Facility operations will be addressed.

Heavy metal cations permeate the TRPV6 epithelial cation channel.

Science.gov (United States)

Kovacs, Gergely; Danko, Tamas; Bergeron, Marc J; Balazs, Bernadett; Suzuki, Yoshiro; Zsembery, Akos; Hediger, Matthias A

2011-01-01

TRPV6 belongs to the vanilloid family of the transient receptor potential channel (TRP) superfamily. This calcium-selective channel is highly expressed in the duodenum and the placenta, being responsible for calcium absorption in the body and fetus. Previous observations have suggested that TRPV6 is not only permeable to calcium but also to other divalent cations in epithelial tissues. In this study, we tested whether TRPV6 is indeed also permeable to cations such as zinc and cadmium. We found that the basal intracellular calcium concentration was higher in HEK293 cells transfected with hTRPV6 than in non-transfected cells, and that this difference almost disappeared in nominally calcium-free solution. Live cell imaging experiments with Fura-2 and NewPort Green DCF showed that overexpression of human TRPV6 increased the permeability for Ca(2+), Ba(2+), Sr(2+), Mn(2+), Zn(2+), Cd(2+), and interestingly also for La(3+) and Gd(3+). These results were confirmed using the patch clamp technique. (45)Ca uptake experiments showed that cadmium, lanthanum and gadolinium were also highly efficient inhibitors of TRPV6-mediated calcium influx at higher micromolar concentrations. Our results suggest that TRPV6 is not only involved in calcium transport but also in the transport of other divalent cations, including heavy metal ions, which may have toxicological implications. Copyright © 2010 Elsevier Ltd. All rights reserved.

Metal cation controls phosphate release in the myosin ATPase.

Science.gov (United States)

Ge, Jinghua; Huang, Furong; Nesmelov, Yuri E

2017-11-01

Myosin is an enzyme that utilizes ATP to produce a conformational change generating a force. The kinetics of the myosin reverse recovery stroke depends on the metal cation complexed with ATP. The reverse recovery stroke is slow for MgATP and fast for MnATP. The metal ion coordinates the γ phosphate of ATP in the myosin active site. It is accepted that the reverse recovery stroke is correlated with the phosphate release; therefore, magnesium "holds" phosphate tighter than manganese. Magnesium and manganese are similar ions in terms of their chemical properties and the shell complexation; hence, we propose to use these ions to study the mechanism of the phosphate release. Analysis of octahedral complexes of magnesium and manganese show that the partial charge of magnesium is higher than that of manganese and the slightly larger size of manganese ion makes its ionic potential smaller. We hypothesize that electrostatics play a role in keeping and releasing the abstracted γ phosphate in the active site, and the stronger electric charge of magnesium ion holds γ phosphate tighter. We used stable myosin-nucleotide analog complex and Raman spectroscopy to examine the effect of the metal cation on the relative position of γ phosphate analog in the active site. We found that in the manganese complex, the γ phosphate analog is 0.01 nm further away from ADP than in the magnesium complex. We conclude that the ionic potential of the metal cation plays a role in the retention of the abstracted phosphate. © 2017 The Protein Society.

Effects of the spaces available for cations in strongly acidic cation-exchange resins on the exchange equilibria by quaternary ammonium ions and on the hydration states of metal ions.

Science.gov (United States)

Watanabe, Yuuya; Ohnaka, Kenji; Fujita, Saki; Kishi, Midori; Yuchi, Akio

2011-10-01

The spaces (voids) available for cations in the five exchange resins with varying exchange capacities and cross-linking degrees were estimated, on the basis of the additivity of molar volumes of the constituents. Tetraalkylammonium ions (NR(4)(+); R: Me, Et, Pr) may completely exchange potassium ion on the resin having a larger void radius. In contrast, the ratio of saturated adsorption capacity to exchange capacity of the resin having a smaller void radius decreased with an increase in size of NR(4)(+) ions, due to the interionic contacts. Alkali metal ions could be exchanged quantitatively. While the hydration numbers of K(+), Rb(+), and Cs(+) were independent of the void radius, those of Li(+) and Na(+), especially Na(+), decreased with a decrease in void radius. Interionic contacts between the hydrated ions enhance the dehydration. Multivalent metal ions have the hydration numbers, comparable to or rather greater than those in water. A greater void volume available due to exchange stoichiometry released the interionic contacts and occasionally promoted the involvement of water molecules other than directly bound molecules. The close proximity between ions in the conventional ion-exchange resins having higher exchange capacities may induce varying interactions.

Oxygen production by molten alkali metal salts using multiple absorption-desorption cycles

Science.gov (United States)

Cassano, Anthony A.

1985-01-01

A continuous chemical air separation is performed wherein oxygen is recovered with a molten alkali metal salt oxygen acceptor in a series of absorption zones which are connected to a plurality of desorption zones operated in separate parallel cycles with the absorption zones. A greater recovery of high pressure oxygen is achieved at reduced power requirements and capital costs.

Effect of particle size on thermal decomposition of alkali metal picrates

International Nuclear Information System (INIS)

Liu, Rui; Zhang, Tonglai; Yang, Li; Zhou, Zunning

2014-01-01

Graphical abstract: The smaller-sized picrate has greater gas emission than do its larger counterpart. The small size effect reduces the thermal decomposition activation energy, accelerates the reaction rate, and promotes the reaction activity. - Highlights: • Picrates were prepared into three micron sizes by microemulsion synthesis. • Thermal decomposition kinetics and thermodynamics were studied by DPTA and DSC. • Smaller-sized picrate has higher activity and faster reaction rate. • Particle size effect on thermal decomposition kinetics and thermodynamics was revealed. - Abstract: Three alkali metal picrates, KPA, RbPA and CsPA, were prepared into three micron sizes by microemulsion synthesis, and their thermal decomposition behaviors were investigated by DPTA at different temperatures and by DSC at different heating rates. The smaller-sized picrate has greater gas emission and smaller kinetic and thermodynamic parameters than do its larger counterpart. It can be attributed to the decreasing particle size which leads to the high surface energy, the fast mass and heat transfer, and the increasing active sites on the reaction interface. The small size effect and surface effect cause the autocatalysis which reduces the activation energy and promotes the reaction activity. The particle size does not affect the reaction mechanism. However, the picrates with different central alkali metals exhibit different reaction mechanisms even though they are of the same size. This is because the central metal determines the bond energy and consequently affects the stability of picrate

Effect of particle size on thermal decomposition of alkali metal picrates

Energy Technology Data Exchange (ETDEWEB)

Liu, Rui; Zhang, Tonglai, E-mail: ztlbit@bit.edu.cn; Yang, Li; Zhou, Zunning

2014-05-01

Graphical abstract: The smaller-sized picrate has greater gas emission than do its larger counterpart. The small size effect reduces the thermal decomposition activation energy, accelerates the reaction rate, and promotes the reaction activity. - Highlights: • Picrates were prepared into three micron sizes by microemulsion synthesis. • Thermal decomposition kinetics and thermodynamics were studied by DPTA and DSC. • Smaller-sized picrate has higher activity and faster reaction rate. • Particle size effect on thermal decomposition kinetics and thermodynamics was revealed. - Abstract: Three alkali metal picrates, KPA, RbPA and CsPA, were prepared into three micron sizes by microemulsion synthesis, and their thermal decomposition behaviors were investigated by DPTA at different temperatures and by DSC at different heating rates. The smaller-sized picrate has greater gas emission and smaller kinetic and thermodynamic parameters than do its larger counterpart. It can be attributed to the decreasing particle size which leads to the high surface energy, the fast mass and heat transfer, and the increasing active sites on the reaction interface. The small size effect and surface effect cause the autocatalysis which reduces the activation energy and promotes the reaction activity. The particle size does not affect the reaction mechanism. However, the picrates with different central alkali metals exhibit different reaction mechanisms even though they are of the same size. This is because the central metal determines the bond energy and consequently affects the stability of picrate.

Alkali absorption and citrate excretion in calcium nephrolithiasis

Science.gov (United States)

Sakhaee, K.; Williams, R. H.; Oh, M. S.; Padalino, P.; Adams-Huet, B.; Whitson, P.; Pak, C. Y.

1993-01-01

The role of net gastrointestinal (GI) alkali absorption in the development of hypocitraturia was investigated. The net GI absorption of alkali was estimated from the difference between simple urinary cations (Ca, Mg, Na, and K) and anions (Cl and P). In 131 normal subjects, the 24 h urinary citrate was positively correlated with the net GI absorption of alkali (r = 0.49, p origin of hypocitraturia. However, the normal dependence was maintained in CDS and in idiopathic hypocitraturia, suggesting that reduced citrate excretion was largely dietary in origin as a result of low net alkali absorption (from a probable relative deficiency of vegetables and fruits or a relative excess of animal proteins).

Fixation by ion exchange of toxic materials in a glass matrix

International Nuclear Information System (INIS)

Litovitz, T.A.; Simmons, C.J.; Simmons, J.H.; Macedo, P.B.

1981-01-01

A process for disposing of toxic materials such as radioactive waste comprises reacting a porous silicate glass or silica gel, having interconnected pores and alkali metal cations. Group 1b metal cations and/or ammonium cation bonded to silicon through divalent oxygen linkages on the internal surfaces of said pores, with a toxic material containing toxic cations as well as non-cationic portions. The toxic cations are capable of displacing the alkali metal cations, Group 1b metal cations and/or ammonium cations to provide a distribution of internal silicon-bonded toxic cation oxide groups within the pores of the glass or silica gel. (author)

Effect of alkali metal content of carbon on retention of iodine at high temperatures

International Nuclear Information System (INIS)

Evans, A.G.

1975-01-01

Activated carbon for filters in reactor confinement systems is intentionally impregnated with iodine salts to enhance the removal of radioiodine from air streams containing organic iodides. When a variety of commercial impregnated carbons were evaluated for iodine retention at elevated temperatures (4 hours at 180 0 C), wide variations in iodine penetration were observed. The alkali metal and iodine content of carbon samples was determined by neutron activation analysis, and a strong correlation was shown between the atom ratio of iodine to alkali metals in the carbons and the high-temperature retention performance. Carbons containing excess alkali (especially potassium) have iodine penetration values 10 to 100 times lower than carbons containing excess iodine. Both low I/K ratios and high pH values were shown essential to high efficiency iodine retention; therefore, conversion of elemental iodine to ionic iodine is the basic reaction mechanism. The natural high K + content and high pH coconut carbons make coconut the preferred natural base material for nuclear air cleaning applications. Studies show, however, that treatment of low potassium carbons with a mixture of KOH and I 2 may produce a product equal to or better than I 2 -impregnated coconut carbons at a lower cost. (U.S.)

Metal ion attachment to the matrix meso-tetrakis(pentafluorophenyl)porphyrin, related matrices and analytes: an experimental and theoretical study.

Science.gov (United States)

van Kampen, Jeroen J A; Luider, Theo M; Ruttink, Paul J A; Burgers, Peter C

2009-11-01

In a previous study [van Kampen et al. Analytical Chemistry 2006; 78: 5403], we found that meso-tetrakis (pentafluorophenyl)porphyrin (F20TPP), in combination with lithium salts, provides an efficient matrix to cationize small molecules by Li+ attachment and that this combination can be successfully applied to the quantitative analysis of drugs, such as antiretroviral compounds using matrix-assisted laser desorption ionization in conjunction with a time-of-flight analyzer (MALDI-TOF). In the present study, we further explore the mechanism of metal ion attachment to F20TPP and analytes by MALDI-FTMS(/MS). To this end, we have studied the interaction of F20TPP and analytes with various mono-, di- and trivalent metal ions (Li+, Na+, K+, Rb+, Cs+, Co2+, Cu2+, Zn2+, Fe2+, Fe3+ and Ga3+). For the alkali cations, we find that F20TPP forms complexes only with Li+ and Na+; in addition, model analyte molecules such as poly(ethyleneglycol)s, mixed with F20TPP and the alkali cations, also only form Li+ and Na+ adducts. This contrasts sharply with the commonly used matrix 2,5-dihydroxybenzoic acid, where analytes are most efficiently cationized by Na+ or K+. Reasons for this difference are delineated. Ab initio calculations on porphyrin itself reveal that even the smallest alkali cation, Li+, does not fit in the porphyrin cavity, but lies on top of it, pushing the 21H and 23 H hydrogen atoms out of and below the plane with concomitant bending of the porphyrin skeleton in the opposite direction, i.e. toward the cation. Thus, the Li+ ion is not effectively sequestered and is in fact exposed and thus accessible for donation to analyte molecules. Interaction of F20TPP with di- and trivalent metal ions leads to protoporphyrin-metal ions, where the metal ion is captured within the protoporphyrin dianion cavity. The most intense signal is obtained when F20TPP is reacted with CuCl2 and then subjected to laser ablation. This method presents an easy general route to study the metal

Semiempirical calculation of van der Waals coefficients for alkali-metal and alkaline-earth-metal atoms

International Nuclear Information System (INIS)

Mitroy, J.; Bromley, M.W.J.

2003-01-01

The van der Waals coefficients, C 6 , C 8 , and C 10 for the alkali-metal (Li, Na, K, and Rb) and alkaline-earth-metal (Be, Mg, Ca, and Sr) atoms are estimated by a combination of ab initio and semiempirical methods. Polarizabilities and atom-wall coefficients are given as a diagnostic check, and the lowest order nonadiabatic dispersion coefficient, D 8 and the three-body coefficient, C 9 are also presented. The dispersion coefficients are in agreement with the available relativistic many-body perturbation theory calculations. The contribution from the core was included by using constrained sum rules involving the core polarizability and Hartree-Fock expectation values to estimate the f-value distribution

Impact of metal cations on the electrocatalytic properties of Pt/C nanoparticles at multiple phase interfaces.

Science.gov (United States)

Durst, Julien; Chatenet, Marian; Maillard, Frédéric

2012-10-05

Proton-exchange membrane fuel cells (PEMFCs) use carbon-supported nanoparticles based on platinum and its alloys to accelerate the rate of the sluggish oxygen-reduction reaction (ORR). The most common metals alloyed to Pt include Co, Ni and Cu, and are thermodynamically unstable in the PEMFC environment. Their dissolution yields the formation and redistribution of metal cations (M(y+)) within the membrane electrode assembly (MEA). Metal cations can also contaminate the MEA when metallic bipolar plates are used as current collectors. In each case, the electrical performance of the PEMFC severely decreases, an effect that is commonly attributed to the poisoning of the sulfonic acid groups of the perfluorosulfonated membrane (PEM) and the resulting decrease of the proton transport properties. However, the impact of metal cations on the kinetics of electrochemical reactions involving adsorption/desorption and bond-breaking processes remains poorly understood. In this paper, we use model electrodes to highlight the effect of metal cations on Pt/C nanoparticles coated or not with a perfluorosulfonated ionomer for the CO electrooxidation reaction and the oxygen reduction reaction. We show that metal cations negatively impact the ORR kinetics and the mass-transport resistance of molecular oxygen. However, the specific adsorption of sulfonate groups of the Nafion® ionomer locally modifies the double layer structure and increases the tolerance to metal cations, even in the presence of sulphate ions in the electrolyte. The survey is extended by using an ultramicroelectrode with cavity and a solid state cell (SSC) specifically developed for this study.

Oxygen production by molten alkali metal salts using multiple absorption-desorption cycles

Science.gov (United States)

Cassano, A.A.

1985-07-02

A continuous chemical air separation is performed wherein oxygen is recovered with a molten alkali metal salt oxygen acceptor in a series of absorption zones which are connected to a plurality of desorption zones operated in separate parallel cycles with the absorption zones. A greater recovery of high pressure oxygen is achieved at reduced power requirements and capital costs. 3 figs.

First-principles simulations on the new hybrid phases of germanene with alkali metal atoms coverage

Energy Technology Data Exchange (ETDEWEB)

Yuan, Jianmei [Hunan Key Laboratory for Computation and Simulation in Science and Engineering, School of Mathematics and Computational Science, Xiangtan University, Hunan 411105 (China); Tang, Chan; Zhong, Jianxin [Hunan Key Laboratory for Micro-Nano Energy Materials and Devices, School of Physics and Optoelectronic Engineering, Xiangtan University, Hunan 411105 (China); Mao, Yuliang, E-mail: ylmao@xtu.edu.cn [Hunan Key Laboratory for Micro-Nano Energy Materials and Devices, School of Physics and Optoelectronic Engineering, Xiangtan University, Hunan 411105 (China)

2016-01-01

Graphical abstract: - Highlights: • The predicted new phase of complete lithiated germanene is more favorable to form than germanane. • Besides ionic interactions, covalent component in some extent leads the complete lithiated germanene into a semiconductor. • 2D phases of Ge{sub 2}X{sub 1} (X = Li, Na, K) are metallic with weak polarization. • Half-lithiated germanene exhibits local magnetic moments on the Ge atoms neighbored with Li adatoms. - Abstract: We present first-principles calculations of a new type hybrid phases composed by buckled germanene with saturated or half-saturated alkali metal atoms adsorption. Our energetics and electronic structure analysis suggests that adsorbed alkali metal atoms (Li, Na, K) can be used as covered adatoms to synthesize germanene-based new phases in two dimensional. The predicted new phases of Ge{sub 2}X{sub 2} and Ge{sub 2}X{sub 1} (X = Li, Na, K) relative to the single germanene sheet could exist at room temperature. The formation energy of Ge{sub 2}Li{sub 2} configuration obtained from complete lithiation is even more favorable than that of germanane. Charge transfer is significant between the alkali metal atoms and Ge, indicating the ionic interactions between them. Furthermore, our charge density analysis indicates that covalent component in some extent exists in Ge{sub 2}X{sub 2} and Ge{sub 2}X{sub 1} (X = Li, Na, K) 2D phases, which even leads the complete lithiated germanene into a semiconductor with an energy gap of 0.14 eV. We report that 2D phases of Ge{sub 2}X{sub 1} (X = Li, Na, K) are metallic with weak polarization on the Fermi level and in unoccupied states. It is found that half-lithiated germanene exhibits local magnetic moments of 0.48 μ{sub B} on the Ge atoms neighbored with Li adatoms.

Separation of alkali metals by extraction chromatography using polyethers

International Nuclear Information System (INIS)

Smulek, W.; Lada, W.

1977-01-01

Separation of alkali metals by means of acyclic polyether 1,13 bis(8-chinolinyl)1, 4, 7, 10, 13 pentaoxatridecane (CPOD) and cyclic polyether dibenzo-18-crown-6 (DBC) using extraction chromatography is described. Solutions of NaSCN were used as eluting agents. The separation ability of the polyether columns strongly depends on pH and temperature. The following radioisotopes were used in the experiments: Na-22, K-42, Rb-86 and Cs-137. The radionuclide purity of the tracers was examined by γ-ray spectrometry using a Ge(Li) detector and a multichannel γ-ray spectrometer. (T.I.)

Zeolite-like metal-organic frameworks with ana topology

KAUST Repository

Eddaoudi, Mohamed

2017-04-20

Embodiments of the present disclosure describe a zeolite-like metal-organic framework composition comprising a metal-organic framework composition with ana topology characterized by the formula [MIII(4, 5-imidazole dicarboxylic acid)2X(solvent)a]n wherein MIII comprises a trivalent cation of a rare earth element, X comprises an alkali metal element or alkaline earth metal element, and solvent comprises a guest molecule occupying pores. Embodiments of the present disclosure describe a method of separating paraffins comprising contacting a zeolite-like metal-organic framework with ana topology with a flow of paraffins, and separating the paraffins by size.

Extraction process for removing metallic impurities from alkalide metals

Science.gov (United States)

Royer, Lamar T.

1988-01-01

A development is described for removing metallic impurities from alkali metals by employing an extraction process wherein the metallic impurities are extracted from a molten alkali metal into molten lithium metal due to the immiscibility of the alkali metals in lithium and the miscibility of the metallic contaminants or impurities in the lithium. The purified alkali metal may be readily separated from the contaminant-containing lithium metal by simple decanting due to the differences in densities and melting temperatures of the alkali metals as compared to lithium.

Effect of second-sphere cation nature on the character of IR spectra of molybdeum(4, 5) cyanide complexes

International Nuclear Information System (INIS)

Zubritskaya, D.I.; Semenishin, D.I.; Vretsena, N.B.; Chernyak, B.I.

1989-01-01

The effect of nature of second-sphere cations on IR spectra of molybdeum (4, 5) cyanide complexes is studied. It is found that the increase in the first ionization potential (radius decrease) brings about the increase in the frequency of valent variations ν (CN). This proves the possibility of formation of bridge bonds Mo-CN-M in the compounds (M-alkali, alkaline earth or rare earth metal, Cs, Y). The conclusion is made on a considerable effect of the nature of second-sphere cations and oxidation degree of complexing agent atoms on the nature of IR spectra of octacyanomolybdates (4, 5)

Comparison of arsenic acid with phosphoric acid in the interaction with a water molecule and an alkali/alkaline-earth metal cation.

Science.gov (United States)

Park, Sung Woo; Kim, Chang Woo; Lee, Ji Hyun; Shim, Giwoong; Kim, Kwang S

2011-10-20

Recently, Wolfe-Simon has discovered a bacterium which is able to survive using arsenic(V) rather than phosphorus(V) in its DNA. Thus it is important to investigate some important structural and chemical similarities and dissimilarities between phosphate and arsenate. We compared the monohydrated structures and the alkali/alkaline-earth metal (Na(+), K(+), Mg(2+) and Ca(2+)) complexes of the arsenic acid/anions with those of the phosphoric acid/anions [i.e., H(m)PO(4)(-(3-m)) vs H(m)AsO(4)(-(3-m)) (m = 1-3)]. We carried out geometry optimization along with harmonic frequency calculations using ab initio calculations. Despite the increased van der Waals radius of As, the hydrated structures of both P and As systems show very close similarity (within 0.25 Å in the P/As···O(water) distance and within a few kJ/mol in binding energy) because of the increased induction energies by more polar arsenic acid/anons and slightly increased dispersion energy by a larger size of the As atom. In the metal complexes, the arsenic acid has a slightly larger binding distance (by 0.07-1.0 Å) and weaker binding energy because the As(V) ion has a slightly larger radius than the P(V) ion, and the electrostatic interaction is the dominating feature in these systems.

Tetracyanidoborates with triply charged rare earth metal cations and their optical properties

International Nuclear Information System (INIS)

Hackbarth, Liisa

2015-01-01

The aim of this thesis is the description of the synthesis and characterization of a new group of tetracyanidoborates: tetracyanidoborates with trivalent rare earth metal cations. Their optical properties in the ultraviolet and visible range are also discussed. Common synthetic routes for tetracyanidoborates are adapted and applied to the preparation of the rare earth tetracyanidoborate hydrates. They are accessible with high yields and high purity through a reaction between the tetracyanidoboronic acid and rare earth hydroxides. It is shown that the rare earth tetracyanidoborates form isostructural groups, like the [LRE(H_2O)_5][B(CN)_4]_3.0.5 H_2O, where LRE"3"+ is La, Ce, Pr, Nd, Sm, Eu and Gd, the [HRE(H_2O)_7][B(CN)_4]_3 and the [HRE(H_2O)_8][B(CN)_4]_3.3 H_2O, where HRE"3"+ is Tb, Dy, Ho, Er, Tm, Yb, Lu and Y. Furthermore, the coordination number 9 is noticed to be common among the light rare earth cations, whereas the minor coordination number 8 is prevalent for the heavy rare earth cations in their tetracyanidoborates. This different construction of the coordination spheres between light and heavy rare earth cations leads to different structures depending on the energetic efficiency of the structural arrangement. Generally, the rare earth tetracyanidoborate hydrates are found to crystallize in the monoclinic crystal system. Moreover, other different crystal structures are observed depending on the crystallization temperature and the type of coordinated ligands and co-crystallized solvent molecules. The tetracyanidoborate hydrates with triply charged rare earth cations are characterized comprehensively by X-ray diffraction, vibrational spectroscopy, NMR-spectroscopy as well as by thermal analysis. Furthermore, the optical properties of some dehydrated rare earth tetracyanidoborates are investigated by UV-spectroscopy and luminescence measurements. The results of the optical measurements indicate that the tetracyanidoborates with rare earth metal cations

Alkali metals effect on the diffusion mobility of fluorine base of GaF3 and IF3

International Nuclear Information System (INIS)

Bakhvalov, S.G.; Livshits, A.I.; Shubin, A.A.; Petrova, E.M.

2000-01-01

The structure of fluoride glasses on the basis of GaF 3 and InF 3 is studied. The glass lattice bond, i.e. its uniformity or nonuniformity, was analyzed through introduction of alkali metal (LiF, NaF, RbF, CsF) into the composition of fluoride glasses. The consecutive replacement of a modification by alkali metal fluorides made it possible to establish the nonuniformity of the glass-forming lattice by studying through the NMR 19 F method. It may be confirmed by comparing the fluorine ions dynamic behavior in the glasses, based on the indium and gallium trifluorides, that the glass fluorine subsystem on the In basis is more mobile [ru

Emission Channeling Studies of the Lattice Site of Oversized Alkali Atoms Implanted in Metals

CERN Multimedia

2002-01-01

% IS340 \\\\ \\\\ As alkali atoms have the largest atomic radius of all elements, the determination of their lattice configuration following implantation into metals forms a critical test for the various models predicting the lattice site of implanted impurity atoms. The site determination of these large atoms will especially be a crucial check for the most recent model that relates the substitutional fraction of oversized elements to their solution enthalpy. Recent exploratory $^{213}$Fr and $^{221}$Fr $\\alpha$-emission channeling experiments at ISOLDE-CERN and hyperfine interaction measurements on Fr implanted in Fe gave an indication for anomalously large substitutional fractions. To investigate further the behaviour of Fr and other alkali atoms like Cs and Rb thoroughly, more on-line emission channeling experiments are needed. We propose a number of shifts for each element, where the temperature of the implanted metals will be varied between 50$^\\circ$ and 700$^\\circ$~K. Temperature dependent measurements wi...

Active-alkali metal promoted reductive desulfurization of dibenzothiophene and its hindered analogues

OpenAIRE

Pittalis, Mario; Azzena, Ugo Gavino; Carraro, Massimo; Pisano, Luisa

2013-01-01

Reductive desulfurisation of organic compounds is of importance both in organic synthesis and in industry. Benzo- and dibenzothiophenes are between the most abundant sulphur containing impurities in crude oils, and their desulfurization is a mandatory issue in the production of non polluting fuels. Following our interest in the development of efficient alkali metal-mediated synthetic procedures and alternative protocols for the chemical transformation of widespread environmental contaminants ...

Release and sorption of alkali metals in coal fired combined cycle power systems; Freisetzung und Einbindung von Alkalimetallverbindungen in kohlebefeuerten Kombikraftwerken

Energy Technology Data Exchange (ETDEWEB)

Mueller, Michael

2009-07-01

Coal fired combined cycle power systems will be a sufficient way to increase the efficiency of coal combustion. However, combined cycle power systems require a reliable hot gas cleanup. Especially alkali metals, such as sodium and potassium, can lead to hot corrosion of the gas turbine blading if they condensate as sulphates. The actual work deals with the release and sorption of alkali metals in coal fired combined cycle power systems. The influence of coal composition, temperature and pressure on the release of alkali species in coal combustion was investigated and the relevant release mechanisms identified. Alumosilicate sorbents have been found that reduce the alkali concentration in the hot flue gas of the Circulating Pressurized Fluidized Bed Combustion 2{sup nd} Generation (CPFBC 2{sup nd} Gen.) at 750 C to values sufficient for use in a gas turbine. Accordingly, alumosilicate sorbents working at 1400 C have been found for the Pressurized Pulverized Coal Combustion (PPCC). The sorption mechanisms have been identified. Thermodynamic calculations were performed to upscale the results of the laboratory experiments to conditions prevailing in power systems. According to these calculations, there is no risk of hot corrosion in both processes. Furthermore, thermodynamic calculations were performed to investigate the behaviour of alkali metals in an IGCC with integrated hot gas cleanup and H{sub 2} membrane for CO{sub 2} sequestration. (orig.)

Electron core ionization in compressed alkali metal cesium

Science.gov (United States)

Degtyareva, V. F.

2018-01-01

Elements of groups I and II in the periodic table have valence electrons of s-type and are usually considered as simple metals. Crystal structures of these elements at ambient pressure are close-packed and high-symmetry of bcc and fcc-types, defined by electrostatic (Madelung) energy. Diverse structures were found under high pressure with decrease of the coordination number, packing fraction and symmetry. Formation of complex structures can be understood within the model of Fermi sphere-Brillouin zone interactions and supported by Hume-Rothery arguments. With the volume decrease there is a gain of band structure energy accompanied by a formation of many-faced Brillouin zone polyhedra. Under compression to less than a half of the initial volume the interatomic distances become close to or smaller than the ionic radius which should lead to the electron core ionization. At strong compression it is necessary to assume that for alkali metals the valence electron band overlaps with the upper core electrons, which increases the valence electron count under compression.

Sputtering/redeposition analysis of alkali-based tungsten composites for limiter/divertor applications

International Nuclear Information System (INIS)

DeWald, A.B.; Krauss, A.R.; Gruen, D.M.; Valentine, M.G.

1986-07-01

Composites of porous tungsten infiltrated with alkali metal-bearing alloys have been projected as a means of reducing plasma impurities and sputter erosion in magnetic fusion devices. Self-sustaining alkali metal overlayers have been observed to inhibit erosion of the underlying structural substrate by 2X to 10X. The alkali metal itself, insofar as it sputters as a secondary ion, is trapped at the surface by sheath potential and tangential magnetic fields. Self-regeneration of the alkali metal coating is obtained by thermal and radiation-induced segregation from the bulk

Defect formation and desorption of metal atoms from alkali halide crystals under low energy electron bombardment studied by optical absorption and mass spectroscopy

International Nuclear Information System (INIS)

Seifert, N.R.

1993-04-01

This work presents an extensive investigation of electronically induced desorption of ground-state alkali atoms from alkali halides and for the first time correlates directly the desorption with the stability and spatial distribution of the defects formed during bombardment. The electron impact results in the formation of stable F-centers and F-center clusters in the bulk of the crystals. In striking contrast a significant metallization of the surface is observed. Even at temperatures as low as 90 deg C the metallization is achieved within the time resolution of our detection system, which can only be explained by the rapid diffusion of hot holes. Superimposed to the fast and short diffusion of hot holes is the slow F-center diffusion. Measuring the distribution of defects with low energy ion sputtering techniques indicates that at least in the case of LiF the observed diffusion constant of F-centers agrees with values derived by using methods different from that applied here. At low temperatures the formation of F-center clusters and metal on the surface dominates. Colloid formation clearly requires higher temperatures (typically around 200 deg C). This is a strong evidence that efficient F-center diffusion is necessary for the formation of metallic particles (colloids) in the bulk of the crystals. Desorption of alkali atoms from alkali halides at temperatures around room temperature is due to weakly bound alkali atoms. For elevated temperatures the stability of the metallic clusters in the bulk of the crystals (i.e. colloids) are the rate limiting process. (author)

Construction of thermionic alkali-ion sources

International Nuclear Information System (INIS)

Ul Haq, F.

1986-01-01

A simple technique is described by which singly charged alkali ions of K, Na, Li, Rb and Cs are produced by heating ultra-pure chemical salts of different alkali metals on tungsten filaments without employing a temperature measuring device. The character of alkali-ion currents at different heating powers and the remarkably constant ion emission current for prolonged periods are discussed. (author)

Thermochemical ablation therapy of VX2 tumor using a permeable oil-packed liquid alkali metal.

Directory of Open Access Journals (Sweden)

Ziyi Guo

Full Text Available Alkali metal appears to be a promising tool in thermochemical ablation, but, it requires additional data on safety is required. The objective of this study was to explore the effectiveness of permeable oil-packed liquid alkali metal in the thermochemical ablation of tumors.Permeable oil-packed sodium-potassium (NaK was prepared using ultrasonic mixing of different ratios of metal to oil. The thermal effect of the mixture during ablation of muscle tissue ex vivo was evaluated using the Fluke Ti400 Thermal Imager. The thermochemical effect of the NaK-oil mixture on VX2 tumors was evaluated by performing perfusion CT scans both before and after treatment in 10 VX2 rabbit model tumors. VX2 tumors were harvested from two rabbits immediately after treatment to assess their viability using trypan blue and hematoxylin and eosin (H.E. staining.The injection of the NaK-oil mixture resulted in significantly higher heat in the ablation areas. The permeable oil controlled the rate of heat released during the NaK reaction with water in the living tissue. Perfusion computed tomography and its parameter map confirmed that the NaK-oil mixture had curative effects on VX2 tumors. Both trypan blue and H.E. staining showed partial necrosis of the VX2 tumors.The NaK-oil mixture may be used successfully to ablate tumor tissue in vivo. With reference to the controlled thermal and chemical lethal injury to tumors, using a liquid alkali in ablation is potentially an effective and safe method to treat malignant tumors.

A DFT-D study of the interaction of methane, carbon monoxide, and nitrogen with cation-exchanged SAPO-34

Energy Technology Data Exchange (ETDEWEB)

Fischer, Michael [Bremen Univ. (Germany). Fachgebiet Kristallographie; University College London (United Kingdom). Dept. of Chemistry; Bell, Robert G. [University College London (United Kingdom). Dept. of Chemistry

2015-07-01

Density-functional theory calculations including a semi-empirical dispersion correction (DFT-D) are employed to study the interaction of small guest molecules (CH{sub 4}, CO, N{sub 2}) with the cation sites in the silicoaluminophosphate SAPO-34. Eight different cations from three different groups (alkali cations, alkaline earth cations, transition metals) are included in the study. For each case, the total interaction energy as well as the non-dispersive contribution to the interaction are analysed. Electron density difference plots are used to investigate the nature of this non-dispersive contribution in more detail. Despite a non-negligible contribution of polarisation interactions, the total interaction remains moderate in systems containing main group cations. In SAPOs exchanged with transition metals, orbital interactions between the cations and CO and N{sub 2} lead to a very strong interaction, which makes these systems attractive as adsorbents for the selective adsorption of these species. A critical comparison with experimental heats of adsorption shows reasonable quantitative agreement for CO and N{sub 2}, but a pronounced overestimation of the interaction strength for methane. While this does not affect the conclusions regarding the suitability of TM-exchanged SAPO-34 materials for gas separations, more elaborate computational approaches may be needed to improve the quantitative accuracy for this guest molecule.

A DFT-D study of the interaction of methane, carbon monoxide, and nitrogen with cation-exchanged SAPO-34

International Nuclear Information System (INIS)

Fischer, Michael; University College London; Bell, Robert G.

2015-01-01

Density-functional theory calculations including a semi-empirical dispersion correction (DFT-D) are employed to study the interaction of small guest molecules (CH 4 , CO, N 2 ) with the cation sites in the silicoaluminophosphate SAPO-34. Eight different cations from three different groups (alkali cations, alkaline earth cations, transition metals) are included in the study. For each case, the total interaction energy as well as the non-dispersive contribution to the interaction are analysed. Electron density difference plots are used to investigate the nature of this non-dispersive contribution in more detail. Despite a non-negligible contribution of polarisation interactions, the total interaction remains moderate in systems containing main group cations. In SAPOs exchanged with transition metals, orbital interactions between the cations and CO and N 2 lead to a very strong interaction, which makes these systems attractive as adsorbents for the selective adsorption of these species. A critical comparison with experimental heats of adsorption shows reasonable quantitative agreement for CO and N 2 , but a pronounced overestimation of the interaction strength for methane. While this does not affect the conclusions regarding the suitability of TM-exchanged SAPO-34 materials for gas separations, more elaborate computational approaches may be needed to improve the quantitative accuracy for this guest molecule.

Ground state of the polar alkali-metal-atom-strontium molecules: Potential energy curve and permanent dipole moment

International Nuclear Information System (INIS)

Guerout, R.; Aymar, M.; Dulieu, O.

2010-01-01

In this study, we investigate the structure of the polar alkali-metal-atom-strontium diatomic molecules as possible candidates for the realization of samples of ultracold polar molecular species not yet investigated experimentally. Using a quantum chemistry approach based on effective core potentials and core polarization potentials, we model these systems as effective three-valence-electron systems, allowing for calculation of electronic properties with full configuration interaction. The potential curve and the permanent dipole moment of the 2 Σ + ground state are determined as functions of the internuclear distance for LiSr, NaSr, KSr, RbSr, and CsSr molecules. These molecules are found to exhibit a significant permanent dipole moment, though smaller than those of the alkali-metal-atom-Rb molecules.

Cation incorporation into zirconium oxide in LiOH, NaOH, and KOH solutions

International Nuclear Information System (INIS)

Jeong, Y.H.; Kim, K.H.; Baek, J.H.

1999-01-01

To investigate the cation incorporation into zirconium oxide, SIMS analysis was performed on the specimens prepared to have an equal oxide thickness in LiOH, NaOH, and KOH solutions. Even though they have an equal oxide thickness in LiOH, NaOH, and KOH solutions, the penetration depth of cation into the oxide decreased with an increase in the ionic radius of cation. The cation is considered to control the corrosion in alkali hydroxide solutions and its effect is dependent on the concentration of alkali and the oxide thickness. The slight enhancement of the corrosion rate at a low concentration is thought to be caused by cation incorporation into oxide, while the significant acceleration at a high concentration is due to the transformation of oxide microstructures that would be also induced by cation incorporation into oxide. (orig.)

Analysis of the Alkali Metal Diatomic Spectra; Using molecular beams and ultracold molecules

Science.gov (United States)

Kim, Jin-Tae

2014-12-01

This ebook illustrates the complementarity of molecular beam (MB) spectra and ultracold molecule (UM) spectra in unraveling the complex electronic spectra of diatomic alkali metal molecules, using KRb as a prime example. Researchers interested in molecular spectroscopy, whether physicist, chemist, or engineer, may find this ebook helpful and may be able to apply similar ideas to their molecules of interest.

Post-harvest processing methods for reduction of silica and alkali metals in wheat straw.

Science.gov (United States)

Thompson, David N; Shaw, Peter G; Lacey, Jeffrey A

2003-01-01

Silica and alkali metals in wheat straw limit its use for bioenergy and gasification. Slag deposits occur via the eutectic melting of SiO2 with K2O, trapping chlorides at surfaces and causing corrosion. A minimum melting point of 950 degrees C is desirable, corresponding to an SiO2:K2O weight ratio of about 3:1. Mild chemical treatments were used to reduce Si, K, and Cl, while varying temperature, concentration, % solids, and time. Dilute acid was more effective at removing K and Cl, while dilute alkali was more effective for Si. Reduction of minerals in this manner may prove economical for increasing utilization of the straw for combustion or gasification.

Post-Harvest Processing Methods for Reduction of Silica and Alkali Metals in Wheat Straw

Energy Technology Data Exchange (ETDEWEB)

Thompson, David Neal; Lacey, Jeffrey Alan; Shaw, Peter Gordon

2002-04-01

Silica and alkali metals in wheat straw limit its use for bioenergy and gasification. Slag deposits occur via the eutectic melting of SiO2 with K2O, trapping chlorides at surfaces and causing corrosion. A minimum melting point of 950°C is desirable, corresponding to SiO2:K2O of about 3:1. Mild chemical treatments were used to reduce Si, K, and Cl, while varying temperature, concentration, %-solids, and time. Dilute acid was more effective at removing K and Cl, while dilute alkali was more effective for Si. Reduction of minerals in this manner may prove economical for increasing utilization of the straw for combustion or gasification.

Alkali metal ion-proton exchange equilibria and water sorption studies on nafon 117 membrane and dowex 50 W exchange resins: effect of long storage or aging

International Nuclear Information System (INIS)

Ramkumar, Jayshree; Venkataramani, B.

2004-09-01

Alkali metal ion -H + exchanges on Nafion 117 membrane treated differently, Dowex 50 W x 4 and Dowex 50 W x 8 resins have been studied at a total ionic strength of 0.1 mol dm -3 . The water sorption isotherms of these exchangers in different ionic forms generated over the entire range of water activity, have been analysed by the D'Arcy and Watt equation (DWE). Water sorption studies have shown that the physical structure of the exchangers have changed due to long -storage or aging, resulting in poorer water sorption and even formation of pores in the case of Dowex 50 W x 8 resin. As a result, the counter ions in the exchangers are not hydrated and the water is present in a free form, albeit structured, in the resin phase. The selectivity sequence for the alkali metal ions with reference to the H + (Li + + + ) for the exchangers used in the present study is in accordance with that reported in the literature for the ionomers having sulphonic acid as the functional group. In view of the absence of hydration of the cations in the resin phase, the driving force for the selectivity of the cation, namely, the net gain in entropy, is expected to come from the loss of structured water during the exchange process. Pre treating the Nafion 117 membrane with boiling acid solution activates the clustered region of the membrane in the H + form, while pretreatment with boiling water expands the non-ionic domain (the region connecting the clusters). These modifications influence the state of water present in the Nafion 117 membrane and the ion exchange equilibria. As a result of long storage or aging, the ion exchangers lose their elasticity or swelling characteristics. The results obtained in the present study indicate that in aged materials, the ionogenic groups are existing as isolated ion -pairs rather than in a clustered morphology. (author)

Existence of hexachlorocerates (4) of alkali metals

Energy Technology Data Exchange (ETDEWEB)

Kiselev, Yu.M.; Filatov, I.Yu.; Popov, A.I.; Goryachenkova, S.A.; Martynenko, L.I.; Spitsyn, V.I. (Moskovskij Gosudarstvennyj Univ. (USSR))

1985-01-01

A possibility has been studied to prepare alkali metal hexachlorocerates (4) of the composition M/sub 2/CeCl/sub 6/ (M=Li, Na, K, Rb) according to the reaction 2MX + fH/sub 2/CeCl/sub 6/'' ..-->.. 2HX + M/sub 2/CeCl/sub 6/ (X=Cl/sup -/, NO/sub 3//sup -/). Using X-ray phase analysis and low-temperature hTA it has been shown, that under experimental conditions (-65 deg C) the rubidium-cerium chlorocomplex is formed, in which Ce is present in the form of Ce(4). The complex is unstable at approximately 20 deg C and under the effect of moisture gets hydrolyzed with the formation of Ce(3) derivatives. Isomorphism of Rb and Cs hexachlorocerates (4) is established. According to the data of the low-temperature DTA, the authors failed to prepare Li, Na, K hexachlorocerates (4).

Structure factor of liquid alkali metals using a classical-plasma reference system

Science.gov (United States)

Pastore, G.; Tosi, M. P.

1984-06-01

This paper presents calculations of the liquid structure factor of the alkali metals near freezing, starting from the classical plasma of bare ions as reference liquid. The indirect ion-ion interaction arising from electronic screening is treated by an optimized random phase approximation (ORPA), imposing physical requirements as in the original ORPA scheme developed by Weeks, Chandler and Andersen for liquids with strongly repulsive core potentials. A comparison of the results with computer simulation data for a model of liquid rubidium shows that the present approach overcomes the well-known difficulties met in applying to these metals the standard ORPA based on a reference liquid of neutral hard spheres. The optimization scheme is also shown to be equivalent to a reduction of the range of the indirect interaction in momentum space, as proposed empirically in an earlier work. Comparison with experiment for the other alkalis shows that a good overall representation of the data can be obtained for sodium, potassium and cesium, but not for lithium, when one uses a very simple form of the electron-ion potential adjusted to the liquid compressibility. The small-angle scattering region is finally examined more carefully in the light of recent data of Waseda, with a view to possible refinements of the pseudopotential model.

Ternary Amides Containing Transition Metals for Hydrogen Storage: A Case Study with Alkali Metal Amidozincates.

Science.gov (United States)

Cao, Hujun; Richter, Theresia M M; Pistidda, Claudio; Chaudhary, Anna-Lisa; Santoru, Antonio; Gizer, Gökhan; Niewa, Rainer; Chen, Ping; Klassen, Thomas; Dornheim, Martin

2015-11-01

The alkali metal amidozincates Li4 [Zn(NH2)4](NH2)2 and K2[Zn(NH2)4] were, to the best of our knowledge, studied for the first time as hydrogen storage media. Compared with the LiNH2-2 LiH system, both Li4 [Zn(NH2)4](NH2)2-12 LiH and K2[Zn(NH2)4]-8 LiH systems showed improved rehydrogenation performance, especially K2[Zn(NH2)4]-8 LiH, which can be fully hydrogenated within 30 s at approximately 230 °C. The absorption properties are stable upon cycling. This work shows that ternary amides containing transition metals have great potential as hydrogen storage materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

C-N Bond Activation and Ring Opening of a Saturated N-Heterocyclic Carbene by Lateral Alkali-Metal-Mediated Metalation.

Science.gov (United States)

Hernán-Gómez, Alberto; Kennedy, Alan R; Hevia, Eva

2017-06-01

Combining alkali-metal-mediated metalation (AMMM) and N-heterocyclic carbene (NHC) chemistry, a novel C-N bond activation and ring-opening process is described for these increasingly important NHC molecules, which are generally considered robust ancillary ligands. Here, mechanistic investigations on reactions of saturated NHC SIMes (SIMes=[:C{N(2,4,6-Me 3 C 6 H 2 )CH 2 } 2 ]) with Group 1 alkyl bases suggest this destructive process is triggered by lateral metalation of the carbene. Exploiting co-complexation and trans-metal-trapping strategies with lower polarity organometallic reagents (Mg(CH 2 SiMe 3 ) 2 and Al(TMP)iBu 2 ), key intermediates in this process have been isolated and structurally defined. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tetracyanidoborates with triply charged rare earth metal cations and their optical properties

Energy Technology Data Exchange (ETDEWEB)

Hackbarth, Liisa

2015-11-24

The aim of this thesis is the description of the synthesis and characterization of a new group of tetracyanidoborates: tetracyanidoborates with trivalent rare earth metal cations. Their optical properties in the ultraviolet and visible range are also discussed. Common synthetic routes for tetracyanidoborates are adapted and applied to the preparation of the rare earth tetracyanidoborate hydrates. They are accessible with high yields and high purity through a reaction between the tetracyanidoboronic acid and rare earth hydroxides. It is shown that the rare earth tetracyanidoborates form isostructural groups, like the [LRE(H{sub 2}O){sub 5}][B(CN){sub 4}]{sub 3}.0.5 H{sub 2}O, where LRE{sup 3+} is La, Ce, Pr, Nd, Sm, Eu and Gd, the [HRE(H{sub 2}O){sub 7}][B(CN){sub 4}]{sub 3} and the [HRE(H{sub 2}O){sub 8}][B(CN){sub 4}]{sub 3}.3 H{sub 2}O, where HRE{sup 3+} is Tb, Dy, Ho, Er, Tm, Yb, Lu and Y. Furthermore, the coordination number 9 is noticed to be common among the light rare earth cations, whereas the minor coordination number 8 is prevalent for the heavy rare earth cations in their tetracyanidoborates. This different construction of the coordination spheres between light and heavy rare earth cations leads to different structures depending on the energetic efficiency of the structural arrangement. Generally, the rare earth tetracyanidoborate hydrates are found to crystallize in the monoclinic crystal system. Moreover, other different crystal structures are observed depending on the crystallization temperature and the type of coordinated ligands and co-crystallized solvent molecules. The tetracyanidoborate hydrates with triply charged rare earth cations are characterized comprehensively by X-ray diffraction, vibrational spectroscopy, NMR-spectroscopy as well as by thermal analysis. Furthermore, the optical properties of some dehydrated rare earth tetracyanidoborates are investigated by UV-spectroscopy and luminescence measurements. The results of the optical

Thermodynamics and structure of liquid alkali metals from the charged-hard-sphere reference fluid

International Nuclear Information System (INIS)

Lai, S.K.; Akinlade, O.; Tosi, M.P.

1989-12-01

The evaluation of thermodynamic properties of liquid alkali metals is re-examined in the approach based on the Gibbs-Bogoliubov inequality and using the fluid of charged hard spheres in the mean spherical approximation as reference system, with a view to achieving consistency with the liquid structure factor. The perturbative variational calculation of the Helmholtz free energy is based on an ab initio and highly reliable nonlocal pseudopotential. Only limited improvement is found in the calculated thermodynamic functions, even when full advantage is taken of the two variational parameters inherent in this approach. The role of thermodynamic self-consistency between the equations of state of the reference fluid derived from the routes of the internal energy and of the virial theorem is then discussed, using previous results by Hoye and Stell. An approximate evaluation of the corresponding contribution to the free energy of liquid alkali metals yields appreciable improvements in both the thermodynamic functions and the liquid structure factor. It thus appears that an accurate treatment of thermodynamic self-consistency in the charged-hard-sphere system may help to resolve some of the difficulties that are commonly met in the evaluation of thermodynamic and structural properties of liquid metals. (author). 55 refs, 4 figs, 4 tabs

Use of polysulfides of alkali and alkaline-earth metals to obtain highly dispersed sulfur

International Nuclear Information System (INIS)

Massalimov, I.A.; Vikhareva, I.N.; Kireeva, M.S.

2008-01-01

Possibilities of obtaining polysulfides of alkali and alkaline earth metals (M is Na, K, Ca, Sr, Ba) in aqueous solutions were considered. The composition of the polysulfides and their concentration in solutions were found. The efficiencies of application of highly dispersed sulfur, produced from calcium polysulfide, and colloid sulfur as a fungicide were compared [ru

An assessment of the melting, boiling, and critical point data of the alkali metals

International Nuclear Information System (INIS)

Ohse, R.W.; Babelot, J.F.; Magill, J.

1985-01-01

The measured melting, boiling and critical point data of the alkali metals are reviewed. Emphasis has been given to the assessment of the critical point data. The main experimental techniques for measurements in the critical region are described. The selected data are given. Best estimates of the critical constants of lithium are given. (author)

Enhanced PCBs sorption on biochars as affected by environmental factors: Humic acid and metal cations

International Nuclear Information System (INIS)

Wang Yu; Wang Lei; Fang Guodong; Herath, H.M.S.K.; Wang Yujun; Cang Long; Xie Zubin; Zhou Dongmei

2013-01-01

Biochar plays an important role in the behaviors of organic pollutants in the soil environment. The role of humic acid (HA) and metal cations on the adsorption affinity of polychlorinated biphenyls (PCBs) to the biochars in an aqueous medium and an extracted solution from a PCBs-contaminated soil was studied using batch experiments. Biochars were produced with pine needles and wheat straw at 350 °C and 550 °C under anaerobic condition. The results showed that the biochars had high adsorption affinity for PCBs. Pine needle chars adsorbed less nonplanar PCBs than planar ones due to dispersive interactions and separation. Coexistence of HA and metal cations increased PCBs sorption on the biochars accounted for HA adsorption and cation complexation. The results will aid in a better understanding of biochar sorption mechanism of contaminants in the environment. - Highlights: ► Application of the biochars for PCBs sorption was a new and effective way. ► The biochars had higher adsorption affinity for PCBs in the soil extracted solution. ► Pine needle chars adsorbed less nonplanar PCBs than planar ones. ► Coexisting humic acid or metal cations increased PCBs sorption on the biochars. - The biochars had higher adsorption affinity for PCBs in the extracted soil solution because coexisting humic acid and metal cations increased their sorption.

Density dependence of the diffusion coefficient of alkali metals

International Nuclear Information System (INIS)

Adebayo, G.A.; Anusionwu, B.C.; Njah, A.N.; Mathew, B.; Fabamise, O.A.T.

2004-06-01

The effect of density on transport coefficients of liquid Li, Na and K at high temperatures using the method of Molecular Dynamics simulation has been studied. Simulation of these liquid alkali metals were carried out with 800 particles in simulation boxes with periodic boundary conditions imposed. In order to test the reliability of the interatomic potential used in the calculations, experimental data on the structural properties were compared with calculated results. The calculations showed a linear relationship between the density and the diffusion coefficient in all the systems investigated except in lithium, where, due to the small size of the atom, standard molecular dynamics simulation method may not be appropriate for calculating the properties of interest. (author)

Concerted action of two cation filters in the aquaporin water channel

DEFF Research Database (Denmark)

Wu, Binghua; Steinbronn, Christina; Alsterfjord, Magnus

2009-01-01

Aquaporin (AQP) facilitated water transport is common to virtually all cell membranes and is marked by almost perfect specificity and high flux rates. Simultaneously, protons and cations are strictly excluded to maintain ionic transmembrane gradients. Yet, the AQP cation filters have not been...... identified experimentally. We report that three point mutations turned the water-specific AQP1 into a proton/alkali cation channel with reduced water permeability and the permeability sequence: H(+) >>K(+) >Rb(+) >Na(+) >Cs(+) >Li(+). Contrary to theoretical models, we found that electrostatic repulsion...... at the central asn-pro-ala (NPA) region does not suffice to exclude protons. Full proton exclusion is reached only in conjunction with the aromatic/arginine (ar/R) constriction at the pore mouth. In contrast, alkali cations are blocked by the NPA region but leak through the ar/R constriction. Expression...

Alkali-Metal-Ion-Functionalized Graphene Oxide as a Superior Anode Material for Sodium-Ion Batteries.

Science.gov (United States)

Wan, Fang; Li, Yu-Han; Liu, Dai-Huo; Guo, Jin-Zhi; Sun, Hai-Zhu; Zhang, Jing-Ping; Wu, Xing-Long

2016-06-06

Although graphene oxide (GO) has large interlayer spacing, it is still inappropriate to use it as an anode for sodium-ion batteries (SIBs) because of the existence of H-bonding between the layers and ultralow electrical conductivity which impedes the Na(+) and e(-) transformation. To solve these issues, chemical, thermal, and electrochemical procedures are traditionally employed to reduce GO nanosheets. However, these strategies are still unscalable, consume high amounts of energy, and are expensive for practical application. Here, for the first time, we describe the superior Na storage of unreduced GO by a simple and scalable alkali-metal-ion (Li(+) , Na(+) , K(+) )-functionalized process. The various alkali metals ions, connecting with the oxygen on GO, have played different effects on morphology, porosity, degree of disorder, and electrical conductivity, which are crucial for Na-storage capabilities. Electrochemical tests demonstrated that sodium-ion-functionalized GO (GNa) has shown outstanding Na-storage performance in terms of excellent rate capability and long-term cycle life (110 mAh g(-1) after 600 cycles at 1 A g(-1) ) owing to its high BET area, appropriate mesopore, high degree of disorder, and improved electrical conductivity. Theoretical calculations were performed using the generalized gradient approximation (GGA) to further study the Na-storage capabilities of functionalized GO. These calculations have indicated that the Na-O bond has the lowest binding energy, which is beneficial to insertion/extraction of the sodium ion, hence the GNa has shown the best Na-storage properties among all comparatives functionalized by other alkali metal ions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cation effect on small phosphonium based ionic liquid electrolytes with high concentrations of lithium salt

Science.gov (United States)

Chen, Fangfang; Kerr, Robert; Forsyth, Maria

2018-05-01

Ionic liquid electrolytes with high alkali salt concentrations have displayed some excellent electrochemical properties, thus opening up the field for further improvements to liquid electrolytes for lithium or sodium batteries. Fundamental computational investigations into these high concentration systems are required in order to gain a better understanding of these systems, yet they remain lacking. Small phosphonium-based ionic liquids with high concentrations of alkali metal ions have recently shown many promising results in experimental studies, thereby prompting us to conduct further theoretical exploration of these materials. Here, we conducted a molecular dynamics simulation on four small phosphonium-based ionic liquids with 50 mol. % LiFSI salt, focusing on the effect of cation structure on local structuring and ion diffusional and rotational dynamics—which are closely related to the electrochemical properties of these materials.

Manipulating the alkali metal charge compensation and tungsten oxide to continuously enhance the red fluorescence in (Li,Na,K)Ca(Mo,W)O4:Eu3+ solid solution compounds

Science.gov (United States)

Xie, Wei; Li, Jiaxin; Tian, Canxin; Wang, Zesong; Xie, Mubiao; Zou, Changwei; Sun, Guohuan; Kang, Fengwen

2018-02-01

When compared to other phosphors typically the blue and green phosphors, red phosphors, which can be used for white light-emitting diodes (wLEDs), always suffer from various problems such as higher cost, lower luminescence efficiency and bad thermal stability. And thus, great interests have been paid to how to enhance the red fluorescence intensity in the recent years. Here we report on a red-emitting solid solutions, (Li,Na,K)Ca(Mo,W)O4:Eu3+, which enable exhibiting continuous Eu3+ emission enhancement through manipulating the alkali metal ions and the relative content ratios between tungsten and molybdenum oxides. X-ray powder diffraction (XRD) has been employed to check the phase purity, and results show that all samples crystallize in a scheelite structure with space group of I41/a (No.88). A regular blue-shifting of XRD peaks, which indicates the increase of crystal plane spacing, appears as the alkali cationic radius increases from 0.92 Å (for Li), 1.18 Å (for Na) and to 1.38 Å (for K). Replacing Mo ion (0.41 Å) by W ion (0.42 Å) enables not only forming the solid solution compounds (Li,Na,K)Ca(Mo,W)O4:Eu3+, but also blue-shifting the XRD position. Similar to the XRD position shifting, our samples also exhibit the regular change in the photoluminescence (PL) spectra, in which the charge transfer (CT) band position as the alkali cationic radii increase from Li, Na and to K and further from Mo to W shows a continuous red-shifting behavior. As for the CT and Eu3+ intensity, our experimental results show that the alkali ion that corresponds to the maximum intensity is Li, and this intensity can be further enhanced by adding W. In coincidence with the change in the excitation spectral intensity, the continuous enhanced Eu3+ emission intensity can be observed up excitation at the CT band and Eu3+ lines. We have discussed the above CT band shifting and Eu3+ fluorescence enhancement and give a feasible mechanism profile that base on the energy transfer from CT

Dispersion coefficients for H and He interactions with alkali-metal and alkaline-earth-metal atoms

International Nuclear Information System (INIS)

Mitroy, J.; Bromley, M.W.J.

2003-01-01

The van der Waals coefficients C 6 , C 8 , and C 10 for H and He interactions with the alkali-metal (Li, Na, K, and Rb) and alkaline-earth-metal (Be, Mg, Ca, and Sr) atoms are determined from oscillator strength sum rules. The oscillator strengths were computed using a combination of ab initio and semiempirical methods. The dispersion parameters generally agree with close to exact variational calculations for Li-H and Li-He at the 0.1% level of accuracy. For larger systems, there is agreement with relativistic many-body perturbation theory estimates of C 6 at the 1% level. These validations for selected systems attest to the reliability of the present dispersion parameters. About half the present parameters lie within the recommended bounds of the Standard and Certain compilation [J. Chem. Phys. 83, 3002 (1985)

ESI MS/MS Study of Calix[4]arene Derivatives and their Metal Complexes

OpenAIRE

Benković, Tomislav; Tomišić, Vladislav; Frkanec, Leo; Galić, Nives

2012-01-01

The peptidocalixarenes 1–3 bearing tryptophan, phenylglycine and leucil units at the lower rim and their complexes with alkali-metal (Li+, Na+, K+, Rb+, Cs+) and selected lanthanide cations (La3+, Ce3+, Eu3+, Yb3+) were analyzed by ESI MS. The influences of the solvent (acetonitrile, methanol, addition of formic acid or sodium acetate) and the calixarene:cation molar ratio on signal intensities were investigated. Comprehensive MS/MS analyses were performed of all singly and doubly charged ion...

Use of MgO doped with a divalent or trivalent metal cation for removing arsenic from water

Science.gov (United States)

Moore, Robert C; Holt-Larese, Kathleen C; Bontchev, Ranko

2013-08-13

Systems and methods for use of magnesium hydroxide, either directly or through one or more precursors, doped with a divalent or trivalent metal cation, for removing arsenic from drinking water, including water distribution systems. In one embodiment, magnesium hydroxide, Mg(OH).sub.2 (a strong adsorbent for arsenic) doped with a divalent or trivalent metal cation is used to adsorb arsenic. The complex consisting of arsenic adsorbed on Mg(OH).sub.2 doped with a divalent or trivalent metal cation is subsequently removed from the water by conventional means, including filtration, settling, skimming, vortexing, centrifugation, magnetic separation, or other well-known separation systems. In another embodiment, magnesium oxide, MgO, is employed, which reacts with water to form Mg(OH).sub.2. The resulting Mg(OH).sub.2 doped with a divalent or trivalent metal cation, then adsorbs arsenic, as set forth above. The method can also be used to treat human or animal poisoning with arsenic.

Use of MgO doped with a divalent or trivalent metal cation for removing arsenic from water

Energy Technology Data Exchange (ETDEWEB)

Moore, Robert C.; Larese, Kathleen Caroline; Bontchev, Ranko Panayotov

2017-05-30

Systems and methods for use of magnesium hydroxide, either directly or through one or more precursors, doped with a divalent or trivalent metal cation, for removing arsenic from drinking water, including water distribution systems. In one embodiment, magnesium hydroxide, Mg(OH).sub.2 (a strong adsorbent for arsenic) doped with a divalent or trivalent metal cation is used to adsorb arsenic. The complex consisting of arsenic adsorbed on Mg(OH).sub.2 doped with a divalent or trivalent metal cation is subsequently removed from the water by conventional means, including filtration, settling, skimming, vortexing, centrifugation, magnetic separation, or other well-known separation systems. In another embodiment, magnesium oxide, MgO, is employed, which reacts with water to form Mg(OH).sub.2. The resulting Mg(OH).sub.2 doped with a divalent or trivalent metal cation, then adsorbs arsenic, as set forth above. The method can also be used to treat human or animal poisoning with arsenic.

Distributions of alkali metals, alkaline earth metals and halogens in cabbage leaves

International Nuclear Information System (INIS)

Tsukada, Hirofumi; Takeda, Akira; Hasegawa, Hidenao

2007-01-01

The distributions of stable elements in plant components provide useful information for understanding the behavior of radionuclides in plants. An entire cabbage plant sample was collected from an experimental field, and the distributions of alkali metals (K, Rb and Cs), alkaline earth metals (Ca, Sr and Ba) and halogens (Cl and I) were determined for cabbage leaves at different positions. The concentration of Cs in outer (older) cabbage leaves was higher than that in inner (younger) leaves, but the distributions of K and Rb concentrations were relatively similar in cabbage leaves, independent of leaf positions. The concentration of Sr in older cabbage leaves was one order of magnitude higher than that in younger leaves. The distributions of Ca, Ba and Sr concentrations in the plant followed a similar pattern. The concentrations of halogens were also very rich in the outer leaves. The percentage distributions of Cs, Sr, Cl and I in the inedible (extreme outer) leaves were 77, 91, 93 and 96% of the total content in the leaf part, respectively. These results show that the inedible plant components are important for understanding the transfer of the radioactive Cs, Sr Cl and I in soil-plant systems. (author)

Environmental Remediation and Sorption of Metal Cations Using Aluminum Pillared Nano-Bentonite

Science.gov (United States)

Rifai, Rifai; Abou El Safa, Magda

2015-04-01

The release of heavy metal cations into the environment is a potential threat to water and soil quality. Some clay minerals play an important role, as physical and chemical barriers, for the isolation of metal-rich wastes and to adsorb heavy metals as well as to avoid their environmental dispersion. In the present study, the bentonitic clay (southeast El-Hammam City, Egypt) was subjected to pillaring using hydroxyl-aluminum solution. The XRD patterns of the Aluminum Pillared Nano-Bentonite (APNB) showed severe alteration of the crystal structure after pillaring. Poly metal solutions with different metal concentrations of Cu, Co, Ni, Zn, Cd and Pb (0.001, 0.005 and 0.01 moles), and pH (1, 2.5, 5 and 6) were subjected to treatment by the APNB. The removal process is very rapid and spontaneous and the contact time may be short (several minutes) for most adsorption to occur. The criterion for environmental remediation of APNB is less stringent and a short contact time is sufficient. The rate of Cu2+, Zn2+, Co2+, Cd2+, Ni2+ and Pb2+sorption remained higher or equal to the CEC. The sorption of metal ions by APNB are complex and probably involve several mechanisms. In general, APNB can be used to immobilize Cu2+, Zn2+, Co2+, Cd2+, Ni2+ and Pb2+ to any extent. For each metal ion, the most effective immobilization occurs over a particular pH around 5. According to the experimental data obtained, the uptake amount of the studied cations by APNB increased with increasing solution pH, sorbent dose and contact time. The preference of the APNB adsorption for heavy metal ions that are through the cation exchange processes decreases in the order: Cu2+>Zn2+>Co2+>Cd2+ >Ni2+ >Pb2+. Keywords: Bentonitic clay, Egypt, Aluminum Pillared Nano-Bentonite, heavy metal, environmental remediation

Structural studies of Langmuir-Blodgett films containing rare-earth metal cations

DEFF Research Database (Denmark)

Khomutov, G.B.; Antipina, M.N.; Bykov, I.V.

2002-01-01

Comparative structural study of gadolinium stearate Langmuir-Blodgett (LB) films formed by monolayer deposition from either aqueous gadolinium acetate or gadolinium chloride solutions have been carried out. Structure of the films was characterized by X-ray diffraction, Fourier transform infrared...... spectroscopy, high-energy electron diffraction, atomic force microscopy and scanning electron microscopy. It was found that when subphase pH had a value at which all monolayer stearic acid molecules were ionized and bound with Gd3+ cations (pH > 5), the LB films deposited from gadolinium acetate and gadolinium....... The data obtained indicate that the control of multivalent metal cations complexes formation in the subphase and at the monolayer surface can be an instrument for optimization, the conditions to form metal-containing LB film with regulated structure and properties....

Cation-exchanged SAPO-34 for adsorption-based hydrocarbon separations: predictions from dispersion-corrected DFT calculations.

Science.gov (United States)

Fischer, Michael; Bell, Robert G

2014-10-21

The influence of the nature of the cation on the interaction of the silicoaluminophosphate SAPO-34 with small hydrocarbons (ethane, ethylene, acetylene, propane, propylene) is investigated using periodic density-functional theory calculations including a semi-empirical dispersion correction (DFT-D). Initial calculations are used to evaluate which of the guest-accessible cation sites in the chabazite-type structure is energetically preferred for a set of ten cations, which comprises four alkali metals (Li(+), Na(+), K(+), Rb(+)), three alkaline earth metals (Mg(2+), Ca(2+), Sr(2+)), and three transition metals (Cu(+), Ag(+), Fe(2+)). All eight cations that are likely to be found at the SII site (centre of a six-ring) are then included in the following investigation, which studies the interaction with the hydrocarbon guest molecules. In addition to the interaction energies, some trends and peculiarities regarding the adsorption geometries are analysed, and electron density difference plots obtained from the calculations are used to gain insights into the dominant interaction types. In addition to dispersion interactions, electrostatic and polarisation effects dominate for the main group cations, whereas significant orbital interactions are observed for unsaturated hydrocarbons interacting with transition metal (TM) cations. The differences between the interaction energies obtained for pairs of hydrocarbons of interest (such as ethylene-ethane and propylene-propane) deliver some qualitative insights: if this energy difference is large, it can be expected that the material will exhibit a high selectivity in the adsorption-based separation of alkene-alkane mixtures, which constitutes a problem of considerable industrial relevance. While the calculations show that TM-exchanged SAPO-34 materials are likely to exhibit a very high preference for alkenes over alkanes, the strong interaction may render an application in industrial processes impractical due to the large amount

Experimental (FT-IR, FT-Raman, 1H, 13C NMR) and theoretical study of alkali metal 2-aminobenzoates

Science.gov (United States)

Samsonowicz, M.; Świsłocka, R.; Regulska, E.; Lewandowski, W.

2008-09-01

The influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the 2-aminobenzoic acid was studied by the methods of molecular spectroscopy. The vibrational (FT-IR, FT-Raman) and NMR ( 1H and 13C) spectra for 2-aminobenzoic acid and its alkali metal salts were recorded. The assignment of vibrational spectra was done on the basis of literature data, theoretical calculations and our previous experience. Characteristic shifts of bands and changes in intensities of bands along the metal series were observed. The changes of chemical shifts of protons ( 1H NMR) and carbons ( 13C NMR) in the series of studied alkali metal 2-aminobenzoates were observed too. Optimized geometrical structures of studied compounds were calculated by B3LYP method using 6-311++G ∗∗ basis set. Geometric aromaticity indices, dipole moments and energies were also calculated. The theoretical wavenumbers and intensities of IR and Raman spectra were obtained. The calculated parameters were compared to experimental characteristic of studied compounds.

Studying thermal dehydration of double nickel alkali metal pyrophosphates

International Nuclear Information System (INIS)

Bykanova, T.A.; Lavrov, A.V.; AN SSSR, Moscow. Inst. Obshchej i Neorganicheskoj Khimii)

1978-01-01

The methods of thermogravimetry, paper chromatography, infrared spectroscopy and X-ray phase analysis were used in studying the process of thermal dehydration of pyrophosphates of the M 2 Ni 3 (P 2 O 7 ) 2 xnH 2 O type (where n=6, 10; M=Na, K, Rb, Cs, NH 4 ). The dehydration of Cs 2 Ni 3 (P 2 O 7 ) 2 x10H 2 O proceeds in a single stage (endothermal effect at 210 deg C). The exothermal effects at 730 and 690 deg C correspond to the crystallization of the amorphous dehydration products. It has been established that binary pyrophosphates of nickel with alkali metals decompose when heated into Ni 3 (PO 4 ) 2 +MPO 4

Enhanced brightness of organic light-emitting diodes based on Mg:Ag cathode using alkali metal chlorides as an electron injection layer

International Nuclear Information System (INIS)

Zou Ye; Deng Zhenbo; Xu Denghui; Lü Zhaoyue; Yin Yuehong; Du Hailiang; Chen Zheng; Wang Yongsheng

2012-01-01

Different thicknesses of cesium chloride (CsCl) and various alkali metal chlorides were inserted into organic light-emitting diodes (OLEDs) as electron injection layers (EILs). The basic structure of OLED is indium tin oxide (ITO)/N,N′-diphenyl-N,N′-bis(1-napthyl-phenyl)-1.1′-biphenyl-4.4′-diamine (NPB)/tris-(8-hydroxyquinoline) aluminum (Alq 3 )/Mg:Ag/Ag. The electroluminescent (EL) performance curves show that both the brightness and efficiency of the OLEDs can be obviously enhanced by using a thin alkali metal chloride layer as an EIL. The electron injection barrier height between the Alq 3 layer and Mg:Ag cathode is reduced by inserting a thin alkali metal chloride as an EIL, which results in enhanced electron injection and electron current. Therefore, a better balance of hole and electron currents at the emissive interface is achieved and consequently the brightness and efficiency of OLEDs are improved. - Highlights: ► Alkaline metal chlorides were used as electron injection layers in organic light-emitting diodes based on Mg:Ag cathode. ► Brightness and efficiency of OLEDs with alkaline metal chlorides as electron injection layers were all greatly enhanced. ► The Improved OLED performance was attributed to the possible interfacial chemical reaction. ► Electron-only devices are fabricated to demonstrate the electron injection enhancement.

Disposal of heavy metal cations in aqueous media by adsorption on coal to Ghazni

Directory of Open Access Journals (Sweden)

О.М. Заславський

2008-03-01

Full Text Available  Adsorption of Pb and Cu cations and their mixture on the surface of modified and non-modified anti-gas coal trough different time intervals have been studied. The maximum adsorption capacity of coal relative to each cations have been determined. Absence  of concurrence between cations of Pb and Cu during adsorption from mixture is explained by difference of  types of their interaction with coal surface. The high effectiveness and perspectivities of application of anti-gas coal for neutralization of heavy metal cations in aqueous solution was shown.

Hydrocolloid liquid-core capsules for the removal of heavy-metal cations from water

Energy Technology Data Exchange (ETDEWEB)

Nussinovitch, A., E-mail: amos.nussi@mail.huji.ac.il; Dagan, O.

2015-12-15

Highlights: • Novel liquid-core capsules with a non-crosslinked alginate core were produced. • Capsules demonstrated highest efficiency adsorption of ∼300 mg Pb{sup 2+}/g alginate. • Regeneration was carried out by suspending capsules in 1 M HNO{sub 3} for 24 h. • Adsorption capacities of the capsules followed the order: Pb{sup 2+} > Cu{sup 2+} > Cd{sup 2+} > Ni{sup 2+}. - Abstract: Liquid-core capsules with a non-crosslinked alginate fluidic core surrounded by a gellan membrane were produced in a single step to investigate their ability to adsorb heavy metal cations. The liquid-core gellan–alginate capsules, produced by dropping alginate solution with magnesium cations into gellan solution, were extremely efficient at adsorbing lead cations (267 mg Pb{sup 2+}/g dry alginate) at 25 °C and pH 5.5. However, these capsules were very weak and brittle, and an external strengthening capsule was added by using magnesium cations. The membrane was then thinned with the surfactant lecithin, producing capsules with better adsorption attributes (316 mg Pb{sup +2}/g dry alginate vs. 267 mg Pb{sup +2}/g dry alginate without lecithin), most likely due to the thinner membrane and enhanced mass transfer. The capsules’ ability to adsorb other heavy-metal cations – copper (Cu{sup 2+}), cadmium (Cd{sup 2+}) and nickel (Ni{sup 2+}) – was tested. Adsorption efficiencies were 219, 197 and 65 mg/g, respectively, and were correlated with the cation’s affinity to alginate. Capsules with the sorbed heavy metals were regenerated by placing in a 1 M nitric acid suspension for 24 h. Capsules could undergo three regeneration cycles before becoming damaged.

Impact of spreading olive mill waste water on agricultural soils for leaching of metal micronutrients and cations.

Science.gov (United States)

Aharonov-Nadborny, R; Tsechansky, L; Raviv, M; Graber, E R

2017-07-01

Olive mill waste water (OMWW) is an acidic (pH 4-5), saline (EC ∼ 5-10 mS cm -1 ), blackish-red aqueous byproduct of the three phase olive oil production process, with a high chemical oxygen demand (COD) of up to 220,000 mg L -1 . OMWW is conventionally disposed of by uncontrolled dumping into the environment or by semi-controlled spreading on agricultural soils. It was hypothesized that spreading such liquids on agricultural soils could result in the release and mobilization of indigenous soil metals. The effect of OMWW spreading on leaching of metal cations (Na, K, Mg, Mn, Fe, Cu, Zn) was tested in four non-contaminated agricultural soils having different textures (sand, clay loam, clay, and loam) and chemical properties. While the OMWW contributed metals to the soil solution, it also mobilized indigenous soil metals as a function of soil clay content, cation exchange capacity (CEC), and soil pH-buffer capacity. Leaching of soil-originated metals from the sandy soil was substantially greater than from the loam and clay soils, while the clay loam was enriched with metals derived from the OMWW. These trends were attributed to cation exchange and organic-metal complex formation. The organic matter fraction of OMWW forms complexes with metal cations; these complexes may be mobile or precipitate, depending on the soil chemical and physical environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Uranyl oxo activation and functionalization by metal cation coordination

International Nuclear Information System (INIS)

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

2010-01-01

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

Effective interionic pair potentials in liquid alkali metals

International Nuclear Information System (INIS)

Kumaravadivel, R.

1984-06-01

Information on the effective pair potential of liquid alkali metals is obtained from liquid structure factor data by the combination of two approximate methods in the theory of liquids. One method stems from treating the indirect ion-ion interaction in the optimised random phase approximation (ORPA) and the other uses the modified hypernetted chain (MHNC) equation. It is shown that, in the region of the main attractive well, the effective pair potential is bracketed by the results obtained from these two methods. The MHNC inversion scheme does not fare well in providing information on the potential in the region of interionic distance in the tail of the interionic potential. A cross-over from the hard-sphere bridge function to the mean spherical approximation (MSA) bridge function for the long range behaviour of the bridge term in the MHNC equation does not provide appreciable improvement. (author)

Thermal behavior of heat-pipe-assisted alkali-metal thermoelectric converters

Science.gov (United States)

Lee, Ji-Su; Lee, Wook-Hyun; Chi, Ri-Guang; Chung, Won-Sik; Lee, Kye-Bock; Rhi, Seok-Ho; Jeong, Seon-Yong; Park, Jong-Chan

2017-11-01

The alkali-metal thermal-to-electric converter (AMTEC) changes thermal energy directly into electrical energy using alkali metals, such as sodium and potassium, as the working fluid. The AMTEC system primarily consists of beta-alumina solid electrolyte (BASE) tubes, low and high-pressure chambers, an evaporator, and a condenser and work through continuous sodium circulation, similar to conventional heat pipes. When the sodium ions pass through the BASE tubes with ion conductivity, this ion transfer generates electricity. The efficiency of the AMTEC directly depends on the temperature difference between the top and bottom of the system. The optimum design of components of the AMTEC, including the condenser, evaporator, BASE tubes, and artery wick, can improve power output and efficiency. Here, a radiation shield was installed in the low-pressure chamber of the AMTEC and was investigated experimentally and numerically to determine an optimum design for preventing radiation heat loss through the condenser and the wall of AMTEC container. A computational fluid dynamics (CFD) simulation was carried out to decide the optimum size of the low-pressure chamber. The most suitable height and diameter of the chamber were 270 mm and 180 mm, respectively, with eight BASE tubes, which were 150 mm high, 25 mm in diameter, and 105 mm in concentric diameter. Increasing the temperature ratio ( T Cond /T B ) led to high power output. The minimum dimensionless value (0.4611) for temperature ( T Cond /T B ) appeared when the radiation shield was made of 500-mesh nickel. Simulation results for the best position and shape for the radiation shield, revealed that maximum power was generated when a stainless steel shield was installed in between the BASE tubes and condenser.

Surface free energy of alkali and transition metal nanoparticles

International Nuclear Information System (INIS)

Aqra, Fathi; Ayyad, Ahmed

2014-01-01

Graphical abstract: Size dependent surface free energy of spherical, cubic and disk Au nanoparticles. - Highlights: • A model to account for the surface free energy of metallic nanoparticles is described. • The model requires only the cohesive energy of the nanoparticle. • The surface free energy of a number of metallic nanoparticles has been calculated, and the obtained values agree well with existing data. • Surface energy falls down very fast when the number of atoms is less than hundred. • The model is applicable to any metallic nanoparticle. - Abstract: This paper addresses an interesting issue on the surface free energy of metallic nanoparticles as compared to the bulk material. Starting from a previously reported equation, a theoretical model, that involves a specific term for calculating the cohesive energy of nanoparticle, is established in a view to describe the behavior of surface free energy of metallic nanoparticles (using different shapes of particle: sphere, cube and disc). The results indicate that the behavior of surface energy is very appropriate for spherical nanoparticle, and thus, it is the most realistic shape of a nanoparticle. The surface energy of copper, silver, gold, platinum, tungsten, molybdenum, tantalum, paladium and alkali metallic nanoparticles is only prominent in the nanoscale size, and it decreases with the decrease of nanoparticle size. Thus, the surface free energy plays a more important role in determining the properties of nanoparticles than in bulk materials. It differs from shape to another, and falls down as the number of atoms (nanoparticle size) decreases. In the case of spherical nanoparticles, the onset of the sharp decrease in surface energy is observed at about 110 atom. A decrease of 16% and 45% in surface energy is found by moving from bulk to 110 atom and from bulk to 5 atom, respectively. The predictions are consistent with the reported data

Electron detachment energies in high-symmetry alkali halide solvated-electron anions

Science.gov (United States)

Anusiewicz, Iwona; Berdys, Joanna; Simons, Jack; Skurski, Piotr

2003-07-01

We decompose the vertical electron detachment energies (VDEs) in solvated-electron clusters of alkali halides in terms of (i) an electrostatic contribution that correlates with the dipole moment (μ) of the individual alkali halide molecule and (ii) a relaxation component that is related to the polarizability (α) of the alkali halide molecule. Detailed numerical ab initio results for twelve species (MX)n- (M=Li,Na; X=F,Cl,Br; n=2,3) are used to construct an interpolation model that relates the clusters' VDEs to their μ and α values as well as a cluster size parameter r that we show is closely related to the alkali cation's ionic radius. The interpolation formula is then tested by applying it to predict the VDEs of four systems [i.e., (KF)2-, (KF)3-, (KCl)2-, and (KCl)3-] that were not used in determining the parameters of the model. The average difference between the model's predicted VDEs and the ab initio calculated electron binding energies is less than 4% (for the twelve species studied). It is concluded that one can easily estimate the VDE of a given high-symmetry solvated electron system by employing the model put forth here if the α, μ and cation ionic radii are known. Alternatively, if VDEs are measured for an alkali halide cluster and the α and μ values are known, one can estimate the r parameter, which, in turn, determines the "size" of the cluster anion.

Tuning aromaticity in trigonal alkaline earth metal clusters and their alkali metal salts.

Science.gov (United States)

Jiménez-Halla, J Oscar C; Matito, Eduard; Blancafort, Lluís; Robles, Juvencio; Solà, Miquel

2009-12-01

In this work, we analyze the geometry and electronic structure of the [X(n)M(3)](n-2) species (M = Be, Mg, and Ca; X = Li, Na, and K; n = 0, 1, and 2), with special emphasis on the electron delocalization properties and aromaticity of the cyclo-[M(3)](2-) unit. The cyclo-[M(3)](2-) ring is held together through a three-center two-electron bond of sigma-character. Interestingly, the interaction of these small clusters with alkali metals stabilizes the cyclo-[M(3)](2-) ring and leads to a change from sigma-aromaticity in the bound state of the cyclo-[M(3)](2-) to pi-aromaticity in the XM(3) (-) and X(2)M(3) metallic clusters. Our results also show that the aromaticity of the cyclo-[M(3)](2-) unit in the X(2)M(3) metallic clusters depends on the nature of X and M. Moreover, we explored the possibility for tuning the aromaticity by simply moving X perpendicularly to the center of the M(3) ring. The Na(2)Mg(3), Li(2)Mg(3), and X(2)Ca(3) clusters undergo drastic aromaticity alterations when changing the distance from X to the center of the M(3) ring, whereas X(2)Be(3) and K(2)Mg(3) keep its aromaticity relatively constant along this process. (c) 2009 Wiley Periodicals, Inc.

Selective and low temperature transition metal intercalation in layered tellurides

Science.gov (United States)

Yajima, Takeshi; Koshiko, Masaki; Zhang, Yaoqing; Oguchi, Tamio; Yu, Wen; Kato, Daichi; Kobayashi, Yoji; Orikasa, Yuki; Yamamoto, Takafumi; Uchimoto, Yoshiharu; Green, Mark A.; Kageyama, Hiroshi

2016-01-01

Layered materials embrace rich intercalation reactions to accommodate high concentrations of foreign species within their structures, and find many applications spanning from energy storage, ion exchange to secondary batteries. Light alkali metals are generally most easily intercalated due to their light mass, high charge/volume ratio and in many cases strong reducing properties. An evolving area of materials chemistry, however, is to capture metals selectively, which is of technological and environmental significance but rather unexplored. Here we show that the layered telluride T2PTe2 (T=Ti, Zr) displays exclusive insertion of transition metals (for example, Cd, Zn) as opposed to alkali cations, with tetrahedral coordination preference to tellurium. Interestingly, the intercalation reactions proceed in solid state and at surprisingly low temperatures (for example, 80 °C for cadmium in Ti2PTe2). The current method of controlling selectivity provides opportunities in the search for new materials for various applications that used to be possible only in a liquid. PMID:27966540

3718-F Alkali Metal Treatment and Storage Facility Closure Plan

International Nuclear Information System (INIS)

1991-12-01

Since 1987, Westinghouse Hanford Company has been a major contractor to the U.S. Department of Energy-Richland Operations Office and has served as co-operator of the 3718-F Alkali Metal Treatment and Storage Facility, the waste management unit addressed in this closure plan. The closure plan consists of a Part A Dangerous waste Permit Application and a RCRA Closure Plan. An explanation of the Part A Revision (Revision 1) submitted with this document is provided at the beginning of the Part A section. The closure plan consists of 9 chapters and 5 appendices. The chapters cover: introduction; facility description; process information; waste characteristics; groundwater; closure strategy and performance standards; closure activities; postclosure; and references

3718-F Alkali Metal Treatment and Storage Facility Closure Plan

Energy Technology Data Exchange (ETDEWEB)

None

1991-12-01

Since 1987, Westinghouse Hanford Company has been a major contractor to the U.S. Department of Energy-Richland Operations Office and has served as co-operator of the 3718-F Alkali Metal Treatment and Storage Facility, the waste management unit addressed in this closure plan. The closure plan consists of a Part A Dangerous waste Permit Application and a RCRA Closure Plan. An explanation of the Part A Revision (Revision 1) submitted with this document is provided at the beginning of the Part A section. The closure plan consists of 9 chapters and 5 appendices. The chapters cover: introduction; facility description; process information; waste characteristics; groundwater; closure strategy and performance standards; closure activities; postclosure; and references.

Thermodynamic characteristics of viscous flow activation in aqueous solutions of alkali metal iodides

International Nuclear Information System (INIS)

Renskij, I.A.; Rudnitskaya, A.A.; Fialkov, Yu.A.

2003-01-01

The Gibbs activation energy of the viscous flow of the alkali metal iodides aqueous solutions MI (M = Li, Na, K, Cs) and from its temperature dependence - the enthalpy and entropy of this process are calculated by the Eyring modified equation. The kinetic compensation effects, related to the viscous flow of the unbound water and to the ion-hydrate complexes are established. The relative contribution of the enthalpy and entropy constituents for these solution components is analyzed [ru

Alkali and heavy metal emissions of the PCFB-process; Alkalipaeaestoet PCFB-prosessissa

Energy Technology Data Exchange (ETDEWEB)

Kuivalainen, R.; Eriksson, T.; Lehtonen, P. [Foster Wheeler Energia Oy, Karhula (Finland)

1996-12-01

Pressurized Circulating Fluidized Bed (PCFB) combustion technology has been developed in Karhula R and D Center since 1986. As a part of the development, 10 MW PCFB Test Facility was built in 1989. The Test Facility has been used for performance testing with different coal types through the years 1990-1995 in order to gain data for design and commercialization of the high-efficiency low-emission PCFB combustion technology. The project Y44 `Alkali and heavy metal emissions of the PCFB-process` was part of national LIEKKI 2 research program. The main object of the project was to measure vapor phase Na and K concentrations in the PCFB flue gas after hot gas filter and investigate the effects of process conditions and sorbents on alkali release. The measurements were performed using plasma assisted method by TUT Laboratory of Plasma Technology and wet absorption method of VTT Energy. The measured Na concentrations were below 30 ppb(w) in all measured data points. The results of K were below 10 ppb(w). The accuracies of the both methods are about + 50 % at this concentration range. The scatter of the data covers the effects of different process variables on the alkali emission. The measured emissions are at the same order of magnitude as the guideline emission limits estimated by gas turbine manufacturers. The measurements and development of the analyses methods are planned to be continued during PCFB test runs in spring 1996 for example within Joule II research program. (author)

Ion chromatography with the indirect ultraviolet detection of alkali metal ions and ammonium using imidazolium ionic liquid as ultraviolet absorption reagent and eluent.

Science.gov (United States)

Liu, Yong-Qiang; Yu, Hong

2016-08-01

Indirect ultraviolet detection was conducted in ultraviolet-absorption-agent-added mobile phase to complete the detection of the absence of ultraviolet absorption functional group in analytes. Compared with precolumn derivatization or postcolumn derivatization, this method can be widely used, has the advantages of simple operation and good linear relationship. Chromatographic separation of Li(+) , Na(+) , K(+) , and NH4 (+) was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid/organic solvent as the mobile phase, in which imidazolium ionic liquids acted as ultraviolet absorption reagent and eluting agent. The retention behaviors of four kinds of cations are discussed, and the mechanism of separation and detection are described. The main factors influencing the separation and detection were the background ultraviolet absorption reagent and the concentration of hydrogen ion in the ion chromatography-indirect ultraviolet detection. The successful separation and detection of Li(+) , Na(+) , K(+) , and NH4 (+) within 13 min was achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.02, 0.11, 0.30, and 0.06 mg/L, respectively. A new separation and analysis method of alkali metal ions and ammonium by ion chromatography with indirect ultraviolet detection method was developed, and the application range of ionic liquid was expanded. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Studies on the determination of trace amounts of nitrogen along with alkali and alkaline earth elements in uranium based samples by ion-chromatography (IC)

International Nuclear Information System (INIS)

Verma, Poonam; Rastogi, R.K.; Ramakumar, K.L.

2006-12-01

Present report describes an ion chromatography (IC) method with suppressed conductivity detection for the determination of traces of nitrogen along with alkali and alkaline earth elements in uranium based nuclear fuels. Method was developed to determine nitrogen as NH 4 + along with alkali and alkaline earth cations by IC using a cation exchange column. (author)

Esterification of phenyl acetic acid with p-cresol using metal cation exchanged montmorillonite nanoclay catalysts.

Science.gov (United States)

Bhaskar, M; Surekha, M; Suma, N

2018-02-01

The liquid phase esterification of phenyl acetic acid with p -cresol over different metal cation exchanged montmorillonite nanoclays yields p -cresyl phenyl acetate. Different metal cation exchanged montmorillonite nanoclays (M n +  = Al 3+ , Zn 2+ , Mn 2+ , Fe 3+ , Cu 2+ ) were prepared and the catalytic activity was studied. The esterification reaction was conducted by varying molar ratio of the reactants, reaction time and catalyst amount on the yield of the ester. Among the different metal cation exchanged catalysts used, Al 3+ -montmorillonite nanoclay was found to be more active. The characterization of the material used was studied under different techniques, namely X-ray diffraction, scanning electron microscopy and thermogravimetric analysis. The product obtained, p -cresyl phenyl acetate, was identified by thin-layer chromotography and confirmed by Fourier transform infrared, 1 H NMR and 13 C NMR. The regeneration activity of used catalyst was also investigated up to fourth generation.

Chemical effects of alkali atoms on critical temperature in superconducting alkali-doped fullerides

Science.gov (United States)

Hetfleisch, F.; Gunnarsson, O.; Srama, R.; Han, J. E.; Stepper, M.; Roeser, H.-P.; Bohr, A.; Lopez, J. S.; Mashmool, M.; Roth, S.

2018-03-01

Alkali metal doped fullerides (A3C60) are superconductors with critical temperatures, Tc, extending up to 38 K. Tc is known to depend strongly on the lattice parameter a, which can be adjusted by physical or chemical pressure. In the latter case an alkali atom is replaced by a different sized one, which changes a. We have collected an extensive data base of experimental data for Tc from very early up to recent measurements. We disentangle alkali atom chemical effects on Tc, beyond the well-known consequences of changing a. It is found that Tc, for a fixed a, is typically increased as smaller alkali atoms are replaced by larger ones, except for very large a. Possible reasons for these results are discussed. Although smaller in size than the lattice parameter contribution, the chemical effect is not negligible and should be considered in future physical model developments.

Magnetic properties of free alkali and transition metal clusters

International Nuclear Information System (INIS)

Heer, W. de; Milani, P.; Chatelain, A.

1991-01-01

The Stern-Gerlach deflections of small alkali clusters (N<6) and iron clusters (10< N<500) show that the paramagnetic alkali clusters always have a nondeflecting component, while the iron clusters always deflect in the high field direction. Both of these effects appear to be related to spin relaxation however in the case of alkali clusters it is shown that they are in fact caused by avoided level crossing in the Zeeman diagram. For alkali clusters the relatively weak couplings cause reduced magnetic moments where levels cross. For iron clusters however the total spin is strongly coupled to the molecular framework. Consequently this coupling is responsible for avoided level crossing which ultimately cause the total energy of the cluster to decrease with increasing magnetic field so that the iron clusters will deflect in one direction when introduced in an inhomogeneous magnetic field. Experiment and theory are discussed for both cases. (orig.)

Alkali-Resistant Mechanism of a Hollandite DeNOx Catalyst.

Science.gov (United States)

Hu, Pingping; Huang, Zhiwei; Gu, Xiao; Xu, Fei; Gao, Jiayi; Wang, Yue; Chen, Yaxin; Tang, Xingfu

2015-06-02

A thorough understanding of the deactivation mechanism by alkalis is of great importance for rationally designing improved alkali-resistant deNOx catalysts, but a traditional ion-exchange mechanism cannot often accurately describe the nature of the deactivation, thus hampering the development of superior catalysts. Here, we establish a new exchange-coordination mechanism on the basis of the exhaustive study on the strong alkali resistance of a hollandite manganese oxide (HMO) catalyst. A combination of isothermal adsorption measurements of ammonia with X-ray absorption near-edge structure spectra and X-ray photoelectron spectra reveals that alkali metal ions first react with protons from Brønsted acid sites of HMO via the ion exchange. Synchrotron X-ray diffraction patterns and extended X-ray absorption fine structure spectra coupled with theoretical calculations demonstrate that the exchanged alkali metal ions are subsequently stabilized at size-suitable cavities in the HMO pores via a coordination model with an energy savings. This exchange-coordination mechanism not only gives a wholly convincing explanation for the intrinsic nature of the deactivation of the reported catalysts by alkalis but also provides a strategy for rationally designing improved alkali-resistant deNOx catalysts in general.

Uranyl oxo activation and functionalization by metal cation coordination

Energy Technology Data Exchange (ETDEWEB)

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

2010-07-01

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

The effect of coal sulfur on the behavior of alkali metals during co-firing biomass and coal

Energy Technology Data Exchange (ETDEWEB)

Tianhua Yang; Xingping Kai; Yang Sun; Yeguang He; Rundong Li [Shenyang Aerospace University, Liaoning (China). Liaoning Key Laboratory of Clean Energy and Institute of Clean Energy and Environmental Engineering

2011-07-15

Biomass contains high amounts of volatile alkali metals and chlorine, which can cause deposition, corrosion and agglomeration during combustion. Meanwhile coal contains a certain amount of sulfur that produces serious environmental pollution following combustion. To investigate the effects of sulfur on the migration of alkali metals during biomass and coal co-combustion, thermodynamic equilibrium calculations were applied and experiments were performed in a laboratory scale reactor combining with a scanning electron microscope (SEM), X-ray powder diffraction (XRD) and other analytical approaches. The results indicate that inorganic sulfur FeS{sub 2} addition significantly enhanced the formation of potassium sulfate when the S/K molar ratio was less than 2. Meanwhile increasing FeS{sub 2} dosage reduced the formation of KCl(g) and KOH(g) and increased the release of HCl(g). In addition potassium sulfate can react with silica and aluminum to form potassium aluminosilicates and release HCl at the S/K molar ratio above 4. 18 refs., 9 figs., 1 tab.

Reaction of cerium dioxide with alkali metal alkoxides

International Nuclear Information System (INIS)

Sato, Nobuaki; Fujino, Takeo

1992-01-01

The gas-solid reaction process using volatile alkali metal alkoxides has many advantages in producing the uranates (plutonates) which are expected to improve the dissolution behavior of the fuel into nitric acid. In this work, the reactions of CeO 2 , which was used as a non-radioactive stand-in of PuO 2 , with MOBu t (M = Li, K) under several conditions were examined. In the case of the M y Ce 1-y O 2-x synthesized by an aqueous method, the lattice parameter was slightly increased with increasing M concentration, y, up to 0.20. When the LiOBu t vapor reacted with CeO 2 , a new fluorite phase having a = 5.4935 A, y = 0.044, x = 0.30 was formed over 973 K. A similar compound (a = 5.4797 A, y = 0.035, x = 0.22) was observed by the reaction of CeO 2 with KOBu t . (author)

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

KAUST Repository

Liang, Yin; Li, Zhikao; Nourdine, Mohamed; Shahid, Salman; Takanabe, Kazuhiro

2014-01-01

A universal reaction mechanism involved in the oxidative coupling of methane (OCM) is demonstrated under oxy-steam conditions using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH

Biochar immobilizes soil-borne arsenic but not cationic metals in the presence of low-molecular-weight organic acids.

Science.gov (United States)

Alozie, Nneka; Heaney, Natalie; Lin, Chuxia

2018-07-15

A batch experiment was conducted to examine the effects of biochar on the behaviour of soil-borne arsenic and metals that were mobilized by three low-molecular-weight organic acids. In the presence of citric acid, oxalic acid and malic acid at a molar concentration of 0.01M, the surface of biochar was protonated, which disfavours adsorption of the cationic metals released from the soil by organic acid-driven mobilization. In contrast, the oxyanionic As species were re-immobilized by the protonated biochar effectively. Biochar could also immobilize oxyanionic Cr species but not cationic Cr species. The addition of biochar increased the level of metals in the solution due to the release of the biochar-borne metals under attack by LMWOAs via cation exchange. Biochar could also have the potential to enhance reductive dissolution of iron and manganese oxides in the soil, leading to enhanced release of trace elements bound to these oxides. The findings obtained from this study have implications for evaluating the role of biochar in immobilizing trace elements in rhizosphere. Adsorption of cationic heavy metals on biochar in the presence of LMWOAs is unlikely to be a mechanism responsible for the impeded uptake of heavy metals by plants growing in heavy metal-contaminated soils. Copyright © 2018 Elsevier B.V. All rights reserved.

The role of oxygen in porous molybdenum electrodes for the alkali metal thermoelectric converter

International Nuclear Information System (INIS)

Williams, R.M.; Nagasubramanian, G.; Khanna, S.K.; Bankston, C.P.; Thakoor, A.P.; Cole, T.

1986-01-01

The alkali metal thermoelectric converter is a direct energy conversion device, utilizing a high alkali metal activity gradient to generate electrical power. Its operation is based on the unique ion conductive properties of beta''-alumina solid electrolyte. The major barrier to application of this device is identification of an electrode which can maintain optimum power densities for operation times of >10,000h. Thin, porous molybdenum electrodes have shown the best performance characteristics, but show a variety of time dependent phenomena, including eventual degradation to power densities 3-5 times lower than initial values. Several Na-Mo-O compounds, including Na/sub 2/MoO/sub 4/ and Na/sub 2/Mo/sub 3/O/sub 6/, are formed during AMTEC operation. These compounds may be responsible for enhanced Na transport through Mo electrodes via sodium ion conduction, and eventual performance degradation due to their volatilization and decomposition. No decomposition of beta''-alumina has been observed under simulated AMTEC operating conditions up to 1373 K. In this paper, we present a model for chemical reactions occurring in porous molybdenum electrodes. The model is based on thermochemical and kinetic data, known sodium-molybdenum-oxygen chemistry, x-ray diffraction analysis of molybdenum and molybdenum oxide electrodes, and the electrochemical behavior of the cell

Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

International Nuclear Information System (INIS)

Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J.; Gomes, Henrique L.; De Leeuw, Dago M.

2014-01-01

Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10 25 /m 3 . The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics

Structural diversities induced by cation sizes in a series of fluorogermanophosphates: A2[GeF2(HPO4)2] (A = Na, K, Rb, NH4, and Cs).

Science.gov (United States)

Chen, Zhang-Gai; Huang, Xia; Zhuang, Rong-Chuan; Zhang, Yu; Liu, Xin; Shi, Tao; Wang, Shuai-Hua; Wu, Shao-Fan; Mi, Jin-Xiao; Huang, Ya-Xi

2017-09-12

Germanophosphates, in comparison with other metal phosphates, have been less studied but potentially exhibit more diverse structural chemistry with wide applications. Herein we applied a hydro-/solvo-fluorothermal route to make use of both the "tailor effect" of fluoride for the formation of low dimensional anionic clusters and the presence of alkali cations of different sizes to align the anionic clusters to control the overall crystal symmetries of germanophosphates. The synergetic effects of fluoride and alkali cations led to structural changes from chain-like structures to layered structures in a series of five novel fluorogermanophosphates: A 2 [GeF 2 (HPO 4 ) 2 ] (A = Na, K, Rb, NH 4 , and Cs, denoted as Na, K, Rb, NH4, and Cs). Although these fluorogermanophosphates have stoichiometrically equivalent formulas, they feature different anionic clusters, diverse structural dimensionalities, and contrasting crystal symmetries. Chain-like structures were observed for the compounds with the smaller sized alkali ions (Na + , K + , and Rb + ), whereas layered structures were found for those containing the larger sized cations ((NH 4 ) + and Cs + ). Specifically, monoclinic space groups were observed for the Na, K, Rb, and NH4 compounds, whereas a tetragonal space group P4/mbm was found for the Cs compound. These compounds provide new insights into the effects of cation sizes on the anionic clusters built from GeO 4 F 2 octahedra and HPO 4 tetrahedra as well as their influences on the overall structural symmetries in germanophosphates. Further characterization including IR spectroscopy and thermal analyses for all five compounds is also presented.

The effect of metal ion exchange and alkali metal doping on the electrical conductivity of the Faujasite-type zeolite 13X

International Nuclear Information System (INIS)

Swart, S.

1983-12-01

Zeolite 13X was synthesized in the sodium form. Some transition metal cations were introduced into the zeolite framework by ion exchange reactions. These different cationic zeolite forms were doped or impregnated with sodium metal, utilizing the adsorptive properties of the zeolite. An A.C. technique was used to determine the electrical conductivity of the dehydrated ion exchanged zeolites and the sodium impregnated zeolite samples as a function of temperature. The conductivity value obtained was used to determine some thermodynamic parameters relating to the conduction process. For the dehydrated ion exchanged zeolites the electrical conductivity showed a general decrease with a decreasing ion exchange capacity. The sodium impregnated zeolites showed an increase in conductivity with respect to the dehydrated unimpregnated samples. This was attributed to the presence of Na 6 5 + centres in the impregnated zeolites. The reduction of some of the metal cations by the sodium on impregnation did not appear to have any significant effect on the overall ionic conductivity of the samples. The conductivity as a function of temperature and pressure for the dehydrated sodium form of zeolite 13X and its impregnated counterpart was determined. The conductivity was found to increase with increasing pressure and temperature

s-wave elastic scattering of antihydrogen off atomic alkali-metal targets

International Nuclear Information System (INIS)

Sinha, Prabal K.; Ghosh, A. S.

2006-01-01

We have investigated the s-wave elastic scattering of antihydrogen atoms off atomic alkali-metal targets (Li, Na, K, and Rb) at thermal energies (10 -16 -10 -4 a.u.) using an atomic orbital expansion technique. The elastic cross sections of these systems at thermal energies are found to be very high compared to H-H and H-He systems. The theoretical models employed in this study are so chosen to consider long-range forces dynamically in the calculation. The mechanism of cooling suggests that Li may be considered to be a good candidate as a buffer gas for enhanced cooling of antihydrogen atoms to ultracold temperature

Study of absorption spectra for alkali and alkaline earth metal salts in flameless atomic absorption spectrometry using a carbon tube atomizer

International Nuclear Information System (INIS)

Yasuda, Seiji; Kakiyama, Hitoo

1975-01-01

Absorption spectra of various salts such as alkali metal salts, alkaline earth dichlorides, and ammonium halides were investigated and absorptions of some molecular species produced in the carbon tube were identified. The aqueous solution (20 μl) containing 1.0 mg/ml of each salt was placed in the carbon tube atomizer and heated in a similar manner to usual flameless atomic absorption method. D 2 -lamp was used as a continuous light source and argon gas was employed as an inert sheath gas. The spectra were obtained over the range of wavelength 200 to 350 nm. When alkali halides were feeded, the absorption spectra agreed with those of alkali halide vapors. Therefore, in such cases vapors of the alkali halides were probably produced by the sublimation or vaporization in the atomizer. The spectra of alkali perchlorates were considered to be those of alkali chlorides produced by the pyrolysis of the perchlorates in the atomizer. The absorptions of alkaline earth chlorides below 250 nm were probably due to their gaseous states. Sulfur dioxide was found to be produced by the pyrolysis of alkali sulfates, bisulfates and sulfites in the atomizer, Alkali phosphates and pyrophosphates gave almost identical spectra below 300 nm. Gamma band spectrum of nitrogen monoxide was observed from 200 to 240 nm during ashing at bout 330 0 C for alkali nitrates and nitrites. Ammonia vapor was produced from ammonium halides during drying at about 170 0 C. Although the absorptions of alkali carbonates and hydroxides were almost undetectable, the same spectra as those of alkali halides were observed by the addition of ammonium halides to the solutions of alkali compounds. This shows that alkali halides are produced in the atomizer by the addition of halide ions. (auth.)

Electronic and atomic structures of liquid tellurium containing alkali elements

International Nuclear Information System (INIS)

Kawakita, Yukinobu; Yao, Makoto; Endo, Hirohisa.

1997-01-01

The measurements of electrical conductivity σ, density, EXAFS and neutron scattering were carried out for liquid K-Te and Rb-Te mixtures. The conductivity σ decreases rapidly with alkali concentration and a metal-semiconductor transition occurs at about 10 at.% alkali. It is found that the compositional variation of σ is nearly independent of the alkali species. The Te-Te bond length deduced from EXAFS and neutron scattering measurements is 2.8 A and changes little with alkali concentrations. The average distances from K and Rb atom to Te atoms are 3.6 A and 3.8 A, respectively. Two kinds of relaxation processes are observed in quasielastic neutron scattering for K 20 Te 80 . Upon the addition of alkali the interaction between the neighbouring Te chains, which is responsible for the metallic conduction, weaken considerably. (author)

Screen-printed electrode for alkali-metal thermoelectric converter

Energy Technology Data Exchange (ETDEWEB)

Hashimoto, T.; Shibata, K.; Tsuchida, K.; Kato, A. (Kyushu Univ., Fukuoka (Japan). Faculty of Engineering)

1992-06-01

An alkali-metal thermoelectric converter (AMTEC) is a device for the direct conversion of thermal to electric energy. An AMTEC contains sodium as working fluid and is divided into a high-temperature region (900-1300 K) and a low-temperature region (400-800 K) by [beta]''-alumina solid electrolyte. A high-performance electrode for an AMTEC must have good electrical conductivity, make a strong physical bond with low contact resistance to [beta]''-alumina, be highly permeable to sodium vapour, resist corrosion by sodium and have a low rate of evaporation at the operating temperature of the AMTEC. We have previously investigated the interaction of nitrides and carbides of some transition-metals (groups IV, V and VI) with [beta],[beta]''-alumina or liquid sodium (about 700degC) with the objective of finding a better electrode material for an AMTEC. The results showed that TiN, TiC, NbN and NbC were good candidates for AMTEC electrodes. We also showed that porous TiN film with low resistance can be prepared by the screen-printing method. In the present work the porous NbN film was prepared by the screen-printing method and the performance as the electrode of an AMTEC was examined. For comparison, the performance of TiN and Mo electrodes prepared by the screen-printing method was also examined. (author).

Development of processes for the production of solar grade silicon from halides and alkali metals

Science.gov (United States)

Dickson, C. R.; Gould, R. K.

1980-01-01

High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon in volume at low cost were studied. Experiments were performed to evaluate product separation and collection processes, measure heat release parameters for scaling purposes, determine the effects of reactants and/or products on materials of reactor construction, and make preliminary engineering and economic analyses of a scaled-up process.

Lack of cortical endoplasmic reticulum protein Ist2 alters sodium accumulation in Saccharomyces cerevisiae cells

Czech Academy of Sciences Publication Activity Database

Papoušková, Klára; Andršová, Markéta; Sychrová, Hana

2017-01-01

Roč. 17, č. 2 (2017), č. článku fox011. ISSN 1567-1356 R&D Projects: GA MŠk(CZ) LH14297 Institutional support: RVO:67985823 Keywords : Saccharomyces cerevisiae * Ist2 * alkali-metal- cation homeostasis * sodium tolerance * sodium uptake * alkali-metal- cation transporters Subject RIV: EE - Microbiology, Virology OBOR OECD: Mycology Impact factor: 3.299, year: 2016

Finite-field evaluation of the Lennard-Jones atom-wall interaction constant C3 for alkali-metal atoms

International Nuclear Information System (INIS)

Johnson, W.R.; Dzuba, V.A.; Safronova, U.I.; Safronova, M.S.

2004-01-01

A finite-field scaling method is applied to evaluate the Lennard-Jones interaction constant C 3 for alkali-metal atoms. The calculations are based on the relativistic single-double approximation in which single and double excitations of Dirac-Hartree-Fock wave functions are included to all orders in perturbation theory

Investigation of the atom-atom and structural relaxation in liquid alkali metals by means of the memory function formalism

International Nuclear Information System (INIS)

Blagoveshchenskii, N. M.; Novikov, A. G.; Savostin, V. V.

2011-01-01

An attempt is made to systematize the data on the relaxation characteristics of liquid alkali metals (Li, Na, and K), which were investigated based on neutron-scattering data with the application of the two-time memory function formalism.

Metal-mediated aminocatalysis provides mild conditions: Enantioselective Michael addition mediated by primary amino catalysts and alkali-metal ions

Directory of Open Access Journals (Sweden)

Matthias Leven

2013-01-01

Full Text Available Four catalysts based on new amides of chiral 1,2-diamines and 2-sulfobenzoic acid have been developed. The alkali-metal salts of these betaine-like amides are able to form imines with enones, which are activated by Lewis acid interaction for nucleophilic attack by 4-hydroxycoumarin. The addition of 4-hydroxycoumarin to enones gives ee’s up to 83% and almost quantitative yields in many cases. This novel type of catalysis provides an effective alternative to conventional primary amino catalysis were strong acid additives are essential components.

An Overview on Metal Cations Extraction by Azocalixarenes

Directory of Open Access Journals (Sweden)

Hasalettin Deligöz

2011-12-01

Full Text Available In this overview, our main aim is to present the design, preparation, characterization, and extraction/sorption properties of chromogenic azocalix[4]arenes (substituted with different groups toward metal cations. Azocalixarenes, which contain a conjugated chromophore, i.e. azo (-N=N- group are synthesized in “one-pot” procedures in satisfactory yields. A wide variety of applications is expected by the functionalization of the side arms. Some of them are used to complex with metal ions. These macrocycles due to their bowl-shaped geometry are indeed used as hosts allowing ionic or organic guests to coordinate onto their cavity. The azocalixarene based ionophores are generally applied in various fields such as catalyst recovery, power plant, agriculture, metals finishing, microelectonics, biotechnology processes, rare earths speciation, and potable water purification. Besides these, they find applications in the area of selective ion extractions, receptors, optical devices, chemical sensor devices, the stationary phase for capillary chromatography, ion transport membranes, and luminescence probes etc. This survey is focused to provide overview an of the versatile nature of azocalix[n]arenes as highly efficient extractants for metal ions treated as pollutants.

Infrared spectroscopy and thermal analysis of prepared cation exchangers from cellulosic materials

International Nuclear Information System (INIS)

Nada, A.M.A.; EI-Sherief, S.; Nasr, A.; Kamel, M.

2005-01-01

Different cation exchangers were prepared by incorporation of phosphate and sulfate groups into acid or alkali treated wood pulp. The molecular structure of these cation exchangers were followed by infrared spectroscopy and thermal degradation analysis technique. From infrared spectra, a new bands are seen at 1200 and 980 cm-1 in phosphorylated wood pulp due to the formation of C-O-P bond. Another bands were seen at 1400, 1200 and 980 cm-1 in phospho sulfonated wood pulp due to the formation of CO- P and C-O-S bonds. Also, it is seen from infrared spectra that the crystallinity index for acid treated wood pulp has a higher value than untreated and alkali treated wood pulp. On the other hand, the acid treated and phosphorylated acid treated wood pulp have a higher activation energy than untreated and phosphorylated alkali treated wood pulp

Hydrogen generation using silicon nanoparticles and their mixtures with alkali metal hydrides

Science.gov (United States)

Patki, Gauri Dilip

mole of Si. We compare our silicon nanoparticles (˜10nm diameter) with commercial silicon nanopowder (rate upon decreasing the particle size to 10 nm was even greater than would be expected based upon the increase in surface area. While specific surface area increased by a factor of 6 in going from rate increased by a factor of 150. However, in all cases, silicon requires a base (e.g. NaOH, KOH, hydrazine) to catalyze its reaction with water. Metal hydrides are also promising hydrogen storage materials. The optimum metal hydride would possess high hydrogen storage density at moderate temperature and pressure, release hydrogen safely and controllably, and be stable in air. Alkali metal hydrides have high hydrogen storage density, but exhibit high uncontrollable reactivity with water. In an attempt to control this explosive nature while maintaining high storage capacity, we mixed our silicon nanoparticles with the hydrides. This has dual benefits: (1) the hydride- water reaction produces the alkali hydroxide needed for base-catalyzed silicon oxidation, and (2) dilution with 10nm coating by, the silicon may temper the reactivity of the hydride, making the process more controllable. Initially, we analyzed hydrolysis of pure alkali metal hydrides and alkaline earth metal hydrides. Lithium hydride has particularly high hydrogen gravimetric density, along with faster reaction kinetics than sodium hydride or magnesium hydride. On analysis of hydrogen production we found higher hydrogen yield from the silicon nanoparticle—metal hydride mixture than from pure hydride hydrolysis. The silicon-hydride mixtures using our 10nm silicon nanoparticles produced high hydrogen yield, exceeding the theoretical yield. Some evidence of slowing of the hydride reaction rate upon addition of silicon nanoparticles was observed.

Reaction of alkali nitrates with PuO2

International Nuclear Information System (INIS)

Yamashita, T.; Ohuchi, K.; Takahashi, K.; Fujino, T.

1990-01-01

Improvement of solubility of plutonium dioxide (PuO 2 ) in acid solution is important to establish the nuclear fuel reprocessing technique for uranium-plutonium mixed oxide fuels. If insoluble PuO 2 can be converted into any soluble plutonium compounds, problems arising from the fuel dissolution process will be reduced to a great extent. Alkali metal plutonates and alkaline-earth plutonates are known to have enhanced solubility in mineral acids. However, the reaction conditions to form such plutonates and characterization thereof are not well elucidated. Then the reactivity and reaction conditions to form lithium and sodium plutonates from their nitrates and PuO 2 were studied at temperatures between 500 and 900 degree C and alkali metal to plutonium atom ratios between 0.5 and 6 by means of thermogravimetry as well as X-ray diffraction technique. The reaction behavior of alkali plutonates will be discussed in comparison with corresponding alkali uranates

On the real performance of cation exchange resins in wastewater treatment under conditions of cation competition: the case of heavy metal pollution.

Science.gov (United States)

Prelot, Benedicte; Ayed, Imen; Marchandeau, Franck; Zajac, Jerzy

2014-01-01

Sorption performance of cation-exchange resins Amberlite® IRN77 and Amberlite™ IRN9652 toward Cs(I) and Sr(II) has been tested in single-component aqueous solutions and simulated waste effluents containing other monovalent (Effluent 1) or divalent (Effluent 2) metal cations, as well as nitrate, borate, or carbonate anions. The individual sorption isotherms of each main component were measured by the solution depletion method. The differential molar enthalpy changes accompanying the ion-exchange between Cs+ or Sr2+ ions and protons at the resin surface from single-component nitrate solutions were measured by isothermal titration calorimetry and they showed a higher specificity of the two resins toward cesium. Compared to the retention limits of both resins under such idealized conditions, an important depression in the maximum adsorption capacity toward each main component was observed in multication systems. The overall effect of ion exchange process appeared to be an unpredictable outcome of the individual sorption capacities of the two resins toward various cations as a function of the cation charge, size, and concentration. The cesium retention capacity of the resins was diminished to about 25% of the "ideal" value in Effluent 1 and 50% in Effluent 2; a further decrease to about 15% was observed upon concomitant strontium addition. The uptake of strontium by the resins was found to be less sensitive to the addition of other metal components: the greatest decrease in the amount adsorbed was 60% of the ideal value in the two effluents for Amberlite® IRN77 and 75% for Amberlite™ IRN9652. It was therefore demonstrated that any performance tests carried out under idealized conditions should be exploited with much caution to predict the real performance of cation exchange resins under conditions of cation competition.

Introducing zinc cations into zeolite Y via the reduction of HY with zinc metal vapour

Science.gov (United States)

Seidel, A.; Boddenberg, B.

1996-01-01

Zeolites HY and NaY which were contacted with zinc metal vapour at 420°C were investigated by carbon monoxide and xenon adsorption as well as 129Xe NMR spectroscopy. The reaction of zeolite HY results in the incorporation of Zn 2+ cations which are shown to populate the supercage positions S II and S III to an unusually high extent. The supercage zinc cation concentration strongly decreases when the material is saturated with water and subsequently dehydrated at 400°C. The zeolite NaY turns out to be inert towards the reaction with zinc metal vapour.

Influence of alkali metal oxides and alkaline earth metal oxides on the mitigation of stress corrosion cracking in CANDU fuel sheathing

Energy Technology Data Exchange (ETDEWEB)

Metzler, J.; Ferrier, G.A.; Farahani, M.; Chan, P.K.; Corcoran, E.C., E-mail: Joseph.Metzler@rmc.ca [Royal Military College of Canada, Kingston, ON (Canada)

2015-07-01

Stress corrosion cracking (SCC)can cause failures of CANDU Zircaloy-4 fuel sheathing. The process occurs when a corrosive element (i.e.,iodine) interacts with a susceptible material that is under sufficient strain at a high temperature. Currently, there is an ongoing effort to improve SCC mitigation strategies for future iterations of CANDU reactors. A potential mechanism for SCC mitigation involves utilizing alkali metal oxides and alkaline earth metal oxides that will sequester corrosive iodine while actively repairing a protective oxide layer on the sheath. SCC tests performed with sodium oxide (Na{sub 2}O) and calcium oxide (CaO) have shown to decrease significantly the sheath degradation. (author)

James C. McGroddy Prize Talk: Superconductivity in alkali-metal doped Carbon-60

Science.gov (United States)

Hebard, Arthur

2008-03-01

Carbon sixty (C60), which was first identified in 1985 in laser desorption experiments, is unquestionably an arrestingly beautiful molecule. The high symmetry of the 12 pentagonal and 20 hexagonal faces symmetrically arrayed in a soccer-ball like structure invites special attention and continues to stimulate animated speculation. The availability in 1990 of macroscopic amounts of purified C60 derived from carbon-arc produced soot allowed the growth and characterization of both bulk and thin-film samples. Crystalline C60 is a molecular solid held together by weak van der Waals forces. The fcc structure has a 74% packing fraction thus allowing ample opportunity (26% available volume) for the intercalation of foreign atoms into the interstitial spaces of the three dimensional host. This opportunity catalyzed much of the collaborative work amongst chemists, physicists and materials scientists at Bell Laboratories, and resulted in the discovery of superconductivity in alkali-metal doped C60 with transition temperatures (Tc) in the mid-30-kelvin range. In this talk I will review how the successes of this initial team effort stimulated a worldwide collaboration between experimentalists and theorists to understand the promise and potential of an entirely new class of superconductors containing only two elements, carbon and an intercalated alkali metal. Although the cuprates still hold the record for the highest Tc, there are still open scientific questions about the mechanism that gives rise to such unexpectedly high Tc's in the non-oxide carbon-based superconductors. The doped fullerenes have unusual attributes (e.g., narrow electronic bands, high disorder, anomalous energy scales, and a tantalizing proximity to a metal-insulator Mott transition), which challenge conventional thinking and at the same time provide useful insights into new directions for finding even higher Tc materials. The final chapter of the `soot to superconductivity' story has yet to be written.

Chlorination of uranium oxides in melts of alkali metal chlorides and their mixtures

International Nuclear Information System (INIS)

Vorobej, M.P.; Bevz, A.S.; Skiba, O.V.

1978-01-01

Chlorination of UO 2 , U 3 O 8 , and UO 3 in melts of chlorides of alkali metals and of their mixtures has been studied by thermogravimetric, X-ray phase, and spectrophotometric methods. The thermogravimetric method has been proposed for evaluating the state of uranylcation in the melt; the effect of the composition of the oxide being chlorinated and of the salt-solvent on the composition of the chlorination products has been studied. The effect of the composition of the chlorination products on the stoichiometry of the electrolytic uranium dioxide has been shown

A study of fluid alkali metals in the critical region

International Nuclear Information System (INIS)

Balasubramanian, R.

2006-01-01

On the basis of the generalised van der Waals equation of state, Riedel's thermodynamic similarity parameter, a measure of the temperature dependence of vapour pressure in the critical region is determined for caesium, rubidium and potassium. This generalised equation differs from the known van der Waals equation of state by the modified expression for molecular pressure. The results of determination of Riedel's thermodynamic similarity parameter of caesium, rubidium and potassium are in good agreement with experimental data. Moreover, the given generalised van der Waals equation of state yields a better fit with experimental data on Riedel's thermodynamic similarity parameter for fluid alkali metals when compared with other correlations such as Van Ness and Abbott equation, Pitzer expansion, Pitzer acentric factor correlation, modified Rackett technique, Lee-Kesler vapour pressure relation and Clausius-Clayperon equation

An Active Alkali-Exchanged Faujasite Catalyst for p-Xylene Production via the One-Pot Diels-Alder Cycloaddition/Dehydration Reaction of 2,5-Dimethylfuran with Ethylene.

Science.gov (United States)

Rohling, Roderigh Y; Uslamin, Evgeny; Zijlstra, Bart; Tranca, Ionut C; Filot, Ivo A W; Hensen, Emiel J M; Pidko, Evgeny A

2018-02-02

The one-pot Diels-Alder cycloaddition (DAC)/dehydration (D) tandem reaction between 2,5-dimethylfuran and ethylene is a potent pathway toward biomass-derived p -xylene. In this work, we present a cheap and active low-silica potassium-exchanged faujasite (KY, Si/Al = 2.6) catalyst. Catalyst optimization was guided by a computational study of the DAC/D reaction mechanism over different alkali-exchanged faujasites using periodic density functional theory calculations complemented by microkinetic modeling. Two types of faujasite models were compared, i.e., a high-silica alkali-exchanged faujasite model representing isolated active cation sites and a low-silica alkali-exchanged faujasite in which the reaction involves several cations in the proximity. The mechanistic study points to a significant synergetic cooperative effect of the ensemble of cations in the faujasite supercage on the DAC/D reaction. Alignment of the reactants by their interactions with the cationic sites and stabilization of reaction intermediates contribute to the high catalytic performance. Experiments confirmed the prediction that KY is the most active catalyst among low-silica alkali-exchanged faujasites. This work is an example of how the catalytic reactivity of zeolites depends on multiple interactions between the zeolite and reagents.

A Quantitative Tunneling/Desorption Model for the Exchange Current at the Porous Electrode/Beta - Alumina/Alkali Metal Gas Three Phase Zone at 700-1300K

Science.gov (United States)

Williams, R. M.; Ryan, M. A.; Saipetch, C.; LeDuc, H. G.

1996-01-01

The exchange current observed at porous metal electrodes on sodium or potassium beta -alumina solid electrolytes in alkali metal vapor is quantitatively modeled with a multi-step process with good agreement with experimental results.

Toxic effect of metal cation binary mixtures to the seaweed Gracilaria domingensis (Gracilariales, Rhodophyta).

Science.gov (United States)

Mendes, Luiz Fernando; Stevani, Cassius Vinicius; Zambotti-Villela, Leonardo; Yokoya, Nair Sumie; Colepicolo, Pio

2014-01-01

The macroalga Gracilaria domingensis is an important resource for the food, pharmaceutical, cosmetic, and biotechnology industries. G. domingensis is at a part of the food web foundation, providing nutrients and microelements to upper levels. As seaweed storage metals in the vacuoles, they are considered the main vectors to magnify these toxic elements. This work describes the evaluation of the toxicity of binary mixtures of available metal cations based on the growth rates of G. domingensis over a 48-h exposure. The interactive effects of each binary mixture were determined using a toxic unit (TU) concept that was the sum of the relative contribution of each toxicant and calculated using the ratio between the toxicant concentration and its endpoint. Mixtures of Cd(II)/Cu(II) and Zn(II)/Ca(II) demonstrated to be additive; Cu(II)/Zn(II), Cu(II)/Mg(II), Cu(II)/Ca(II), Zn(II)/Mg(II), and Ca(II)/Mg(II) mixtures were synergistic, and all interactions studied with Cd(II) were antagonistic. Hypotheses that explain the toxicity of binary mixtures at the molecular level are also suggested. These results represent the first effort to characterize the combined effect of available metal cations, based on the TU concept on seaweed in a total controlled medium. The results presented here are invaluable to the understanding of seaweed metal cation toxicity in the marine environment, the mechanism of toxicity action and how the tolerance of the organism.

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

KAUST Repository

Liang, Yin

2014-03-24

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

A Novel Method for the Determination of Membrane Hydration Numbers of Cations in Conducting Polymers

DEFF Research Database (Denmark)

Jafeen, M.J.M.; Careem, M.A.; Skaarup, Steen

2012-01-01

Polypyrrole polymer films doped with the large, immobile dodecy lbenzene sulfonate anions operating in alkali halide aqueous electroly tes has beenused as a novel physico-chemical environment to develop a more direct way of obtaining reliable values for the hydration numbers of cations. Simultane......Polypyrrole polymer films doped with the large, immobile dodecy lbenzene sulfonate anions operating in alkali halide aqueous electroly tes has beenused as a novel physico-chemical environment to develop a more direct way of obtaining reliable values for the hydration numbers of cations....... The number of water moleculesentering the polymer during the initial part of the first reduction was found to be constant and independent of the concentration of the electrolyte below ∼1 M. This well-defined value can be considered as the primarymembrane hydration number of the cation involved...... in the reduction process. The goal was to investigate both the effects of cation size and of cation charge. The membrane hydration number values obtained by this simple and direct method for a number of cations are: The hydration number for all of these cations seems to follow the same simple relation....

Immobilized poly-L-histidine for chelation of metal cations and metal oxyanions

International Nuclear Information System (INIS)

Malachowski, Lisa; Holcombe, James A.

2003-01-01

The biohomopolymer poly-L-histidine (PLHis) was immobilized onto controlled pore glass (CPG) and its metal binding capabilities evaluated through the use of a flow injection-flame atomic absorption system. The metal binding capability of PLHis-CPG was determined through the analysis of the generated breakthrough curves. The polymer likely coordinates cationic metals through the imidazole side chain (pK a ∼6) present on each histidine residue with both strong and weak binding sites for Cu 2+ , Cd 2+ , Co 2+ , and Ni 2+ . Weak to minimal binding was observed for Mn 2+ , Ca 2+ , Mg 2+ , Na + , and Cr 3+ . The bound metals are quantitatively released from the column with an acid strip. It has also been shown that the protonated imidazole side chain present in acidic solutions is capable of binding metal oxyanions such as chromates, arsenates, and selenites; although oxyanion binding currently exhibits interferences from competing anions in solution, such as sulfate and nitrate. The interference in oxyanion binding is less severe in the presence of chloride, phosphate, and acetate. PLHis-CPG exhibits a capacity of ∼30 μmol Cu 2+ /g CPG in neutral to basic conditions, and a capacity of ∼70 μmol Cr(VI)/g CPG, ∼4 μmol As(V)/g CPG, and ∼4 μmol Se(IV)/g CPG in acidic conditions

Effect of charging on silicene with alkali metal atom adsorption

Science.gov (United States)

Li, Manman; Li, Zhongyao; Gong, Shi-Jing

2018-02-01

Based on first-principles calculations, we studied the effects of charging on the structure, binding energy and electronic properties of silicene with alkali metal (AM) atom (Li, Na or K) adsorption. In AMSi2, electron doping enlarges the lattice constant of silicene, while the influence of hole doping is non-monotonic. In AMSi8, the lattice constant increases/decreases almost linearly with the increase in electron/hole doping. In addition, the AM-Si vertical distance can be greatly enlarged by excessive hole doping in both AMSi2 and AMSi8 systems. When the hole doping is as large as  +e per unit cell, both AMSi2 and AMSi8 can be transformed from metal to semiconductor. However, the binding energy would be negative in the AM+ Si2 semiconductor. It suggests AM+ Si2 is unstable in this case. In addition, the electron doping and the AM-Si vertical distance would greatly influence the band gap of silicene in LiSi8 and NaSi8, while the band gap in KSi8 is relatively stable. Therefore, KSi8 may be a more practicable material in nanotechnology.

Mechanical filter for alkali atoms

CERN Document Server

Toporkov, D K

2000-01-01

A device for separating gases of different mass is discussed. Such a device could be used in a laser-driven spin exchange source of polarized hydrogen atoms to reduce the contamination of alkali atoms. A Monte Carlo simulation has shown that the suggested apparatus based on a commercial turbo pump could reduce by a factor of 10-15 the concentration of the alkali-metal atoms in the hydrogen flow from a laser driven polarized source. This would greatly enhance the effective polarization in hydrogen targets.

(e, 2e) triple differential cross sections of alkali and alkali earth atoms: Na, K and Mg, Ca

International Nuclear Information System (INIS)

Hitawala, U; Purohit, G; Sud, K K

2008-01-01

Recently low-energy measurements have been reported for alkali targets Na and K and alkali earth targets Mg and Ca in coplanar symmetric geometry. We report the results of our calculation of triple differential cross section (TDCS) for electron impact single ionization (i.e. (e, 2e) processes) of alkali atoms Na, K and alkali earth atoms Mg, Ca in coplanar symmetric geometry. We have performed the present calculations using the distorted-wave Born approximation (DWBA) formalism at intermediate incident electron energies used in the recently performed experiments. Ionization takes place from the valence shell for all the targets investigated and the outgoing electrons share the excess energy equally. We have also considered the effect of target polarization in our DWBA calculations which may be an important quantity at incident electron energies used in the present investigation. We find that the DWBA formalism is able to reproduce most of the trend of experimental data and may provide a future direction for further investigation of ionization process on alkali and alkali earth metals. It is also observed that the second-order effects are more important to understand the collision dynamics of (e, 2e) processes on alkali earth targets

γ-radiation effect on dicyclohexano-18-crown-6 aqueous solution in the presence of metal cations

Energy Technology Data Exchange (ETDEWEB)

Yu, Chuhong; Peng, Jing; Li, Jiuqiang; Zhai, Maolina [Peking Univ. (China). Beijing National Laboratory for Molecular Sciences (BNLMS)

2014-04-01

γ-radiation effect on dicyclohexano-18-crown-6 (DCH18C6) aqueous solution in the presence of metal cations, such as K{sup +} and Sr{sup 2+}, was investigated, and some pale yellow precipitates were obtained at doses above 100 kGy. It was found that the complexation interaction of metal cations could accelerate the conversion of DCH18C6 into oligomers and the formation of precipitates, but it did not affect the formation mechanism of precipitates. Furthermore, the salting-out effect of metal cations played an important role in the precipitation. In order to inhibit the radiation-induced precipitation of DCH18C6 in water phase, nitric acid with a concentration of more than 1 M could be added to the system. The methods and results for analyzing radiation-induced products reported in this work are useful to understand the radiation chemistry behavior of DCH18C6 which is used as the extractant in the separation of long half-life radionuclides from spent nuclear fuel. (orig.)

Structural and energetic characteristics of alkali metal hexachlorouranates (5)

International Nuclear Information System (INIS)

Kudryashov, V.L.; Suglobova, I.G.; Chirkst, D.Eh.

1978-01-01

Structure types and lattice parameters of alkali metal hexachlorouranates (5) have been determined by indicating the X-ray diffraction patterns of polycrystals. α-NaVCl 6 has a cubic structure of the Csub(s)PFsub(6) type; β-NaVCl 6 -trigonal lattice of the LiSbF 6 type; KVCl 6 and RbVCl 6 crystallize in the RbPaF 6 structure type; CsVCl 6 is isomorphous to CsPF 6 . Enthalpy values of hexachlorouranates (5) dissolution in 0.5% FeCl 3 solution and in 2% HCl have been measured and the standard enthalpy values of their formation have been calculated. The energies of crystal lattices and of the uranium-uranium-chlorine bonds have been calculated. When uranium coordination number is 6 the energy of the uranium-chlorine bond is 99.6+-0.5; when this number is 8 the energy equals 101.9+-0.5 kcal/mol

Dual Carbon-Confined SnO2 Hollow Nanospheres Enabling High Performance for the Reversible Storage of Alkali Metal Ions.

Science.gov (United States)

Wu, Qiong; Shao, Qi; Li, Qiang; Duan, Qian; Li, Yanhui; Wang, Heng-Guo

2018-04-25

To explore a universal electrode material for the high-performance electrochemical storage of Li + , Na + , and K + ions remains a big challenge. Herein, we propose a "trinity" strategy to coat the SnO 2 hollow nanospheres using the dual carbon layer from the polydopamine-derived nitrogen-doped carbon and graphene. Thereinto, hollow structures with sufficient void space could buffer the volume expansion, whereas dual carbon-confined strategy could not only elastically prevent the aggregation of nanoparticle and ensure the structural integrity but also immensely improve the conductivity and endow high rate properties. Benefiting from the effective strategy and specific structure, the dual carbon-confined SnO 2 hollow nanosphere (denoted as G@C@SnO 2 ) can serve as the universal host material for alkali metal ions and enable their rapid and reversible storage. As expected, the resulting G@C@SnO 2 as a universal anode material shows reversible alkali-metal-ion storage with high performance. We believe this that strategy could pave the way for constructing other metal-oxide-based dual carbon-confined high-performance materials for the future energy storage applications.

A study of fluid alkali metals in the critical region

Energy Technology Data Exchange (ETDEWEB)

Balasubramanian, R. [Department of Physics, Kongu Engineering College, Perundurai, Erode 638 052, Tamil Nadu (India)]. E-mail: drrbala@yahoo.com

2006-05-31

On the basis of the generalised van der Waals equation of state, Riedel's thermodynamic similarity parameter, a measure of the temperature dependence of vapour pressure in the critical region is determined for caesium, rubidium and potassium. This generalised equation differs from the known van der Waals equation of state by the modified expression for molecular pressure. The results of determination of Riedel's thermodynamic similarity parameter of caesium, rubidium and potassium are in good agreement with experimental data. Moreover, the given generalised van der Waals equation of state yields a better fit with experimental data on Riedel's thermodynamic similarity parameter for fluid alkali metals when compared with other correlations such as Van Ness and Abbott equation, Pitzer expansion, Pitzer acentric factor correlation, modified Rackett technique, Lee-Kesler vapour pressure relation and Clausius-Clayperon equation.

Removal of toxic and alkali/alkaline earth metals during co-thermal treatment of two types of MSWI fly ashes in China.

Science.gov (United States)

Yu, Jie; Qiao, Yu; Jin, Limei; Ma, Chuan; Paterson, Nigel; Sun, Lushi

2015-12-01

This study aims to vaporize heavy metals and alkali/alkaline earth metals from two different types of fly ashes by thermal treatment method. Fly ash from a fluidized bed incinerator (HK fly ash) was mixed with one from a grate incinerator (HS fly ash) in various proportions and thermally treated under different temperatures. The melting of HS fly ash was avoided when treated with HK fly ash. Alkali/alkaline earth metals in HS fly ash served as Cl-donors to promote the vaporization of heavy metals during thermal treatment. With temperature increasing from 800 to 900°C, significant amounts of Cl, Na and K were vaporized. Up to 1000°C in air, less than 3% of Cl and Na and less than 5% of K were retained in ash. Under all conditions, Cd can be vaporized effectively. The vaporization of Pb was mildly improved when treated with HS fly ash, while the effect became less pronounced above 900°C. Alkali/alkaline earth metals can promote Cu vaporization by forming copper chlorides. Comparatively, Zn vaporization was low and only slightly improved by HS fly ash. The low vaporization of Zn could be caused by the formation of Zn2SiO4, ZnFe2O4 and ZnAl2O4. Under all conditions, less than 20% of Cr was vaporized. In a reductive atmosphere, the vaporization of Cd and Pb were as high as that in oxidative atmosphere. However, the vaporization of Zn was accelerated and that of Cu was hindered because the formation of Zn2SiO4, ZnFe2O4 and ZnAl2O4 and copper chloride was depressed in reductive atmosphere. Copyright © 2015. Published by Elsevier Ltd.

Carbonation of metal silicates for long-term CO2 sequestration

Science.gov (United States)

Blencoe, James G; Palmer, Donald A; Anovitz, Lawrence M; Beard, James S

2014-03-18

In a preferred embodiment, the invention relates to a process of sequestering carbon dioxide. The process comprises the steps of: (a) reacting a metal silicate with a caustic alkali-metal hydroxide to produce a hydroxide of the metal formerly contained in the silicate; (b) reacting carbon dioxide with at least one of a caustic alkali-metal hydroxide and an alkali-metal silicate to produce at least one of an alkali-metal carbonate and an alkali-metal bicarbonate; and (c) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to produce a carbonate of the metal formerly contained in the metal silicate of step (a).