Methods of recovering alkali metals

DOEpatents

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

DOEpatents

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.

EXTINGUISHMENT OF ALKALI METAL FIRES

DTIC Science & Technology

Contents: Effect of inert gas nket and ow O2 partial pressures on alkali metal fires Extinguishment of small scale fires Extinguishment of alkali... metal fires using inorganic salt foam Alkali metal jet stream ignition at various pressure conditions

Alkali metal for ultraviolet band-pass filter

NASA Technical Reports Server (NTRS)

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.

Purification of alkali metal nitrates

DOEpatents

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.

Ultrafast selective transport of alkali metal ions in metal organic frameworks with subnanometer pores

PubMed Central

Zhang, Huacheng; Hou, Jue; Hu, Yaoxin; Wang, Peiyao; Ou, Ranwen; Jiang, Lei; Liu, Jefferson Zhe; Freeman, Benny D.; Hill, Anita J.; Wang, Huanting

2018-01-01

Porous membranes with ultrafast ion permeation and high ion selectivity are highly desirable for efficient mineral separation, water purification, and energy conversion, but it is still a huge challenge to efficiently separate monatomic ions of the same valence and similar sizes using synthetic membranes. We report metal organic framework (MOF) membranes, including ZIF-8 and UiO-66 membranes with uniform subnanometer pores consisting of angstrom-sized windows and nanometer-sized cavities for ultrafast selective transport of alkali metal ions. The angstrom-sized windows acted as ion selectivity filters for selection of alkali metal ions, whereas the nanometer-sized cavities functioned as ion conductive pores for ultrafast ion transport. The ZIF-8 and UiO-66 membranes showed a LiCl/RbCl selectivity of ~4.6 and ~1.8, respectively, which are much greater than the LiCl/RbCl selectivity of 0.6 to 0.8 measured in traditional porous membranes. Molecular dynamics simulations suggested that ultrafast and selective ion transport in ZIF-8 was associated with partial dehydration effects. This study reveals ultrafast and selective transport of monovalent ions in subnanometer MOF pores and opens up a new avenue to develop unique MOF platforms for efficient ion separations in the future. PMID:29487910

Ultrafast selective transport of alkali metal ions in metal organic frameworks with subnanometer pores.

PubMed

Zhang, Huacheng; Hou, Jue; Hu, Yaoxin; Wang, Peiyao; Ou, Ranwen; Jiang, Lei; Liu, Jefferson Zhe; Freeman, Benny D; Hill, Anita J; Wang, Huanting

2018-02-01

Porous membranes with ultrafast ion permeation and high ion selectivity are highly desirable for efficient mineral separation, water purification, and energy conversion, but it is still a huge challenge to efficiently separate monatomic ions of the same valence and similar sizes using synthetic membranes. We report metal organic framework (MOF) membranes, including ZIF-8 and UiO-66 membranes with uniform subnanometer pores consisting of angstrom-sized windows and nanometer-sized cavities for ultrafast selective transport of alkali metal ions. The angstrom-sized windows acted as ion selectivity filters for selection of alkali metal ions, whereas the nanometer-sized cavities functioned as ion conductive pores for ultrafast ion transport. The ZIF-8 and UiO-66 membranes showed a LiCl/RbCl selectivity of ~4.6 and ~1.8, respectively, which are much greater than the LiCl/RbCl selectivity of 0.6 to 0.8 measured in traditional porous membranes. Molecular dynamics simulations suggested that ultrafast and selective ion transport in ZIF-8 was associated with partial dehydration effects. This study reveals ultrafast and selective transport of monovalent ions in subnanometer MOF pores and opens up a new avenue to develop unique MOF platforms for efficient ion separations in the future.

Alkali metal ionization detector

DOEpatents

Bauerle, James E.; Reed, William H.; Berkey, Edgar

1978-01-01

Variations in the conventional filament and collector electrodes of an alkali metal ionization detector, including the substitution of helical electrode configurations for either the conventional wire filament or flat plate collector; or, the substitution of a plurality of discrete filament electrodes providing an in situ capability for transferring from an operationally defective filament electrode to a previously unused filament electrode without removing the alkali metal ionization detector from the monitored environment. In particular, the helical collector arrangement which is coaxially disposed about the filament electrode, i.e. the thermal ionizer, provides an improved collection of positive ions developed by the filament electrode. The helical filament design, on the other hand, provides the advantage of an increased surface area for ionization of alkali metal-bearing species in a monitored gas environment as well as providing a relatively strong electric field for collecting the ions at the collector electrode about which the helical filament electrode is coaxially positioned. Alternatively, both the filament and collector electrodes can be helical. Furthermore, the operation of the conventional alkali metal ionization detector as a leak detector can be simplified as to cost and complexity, by operating the detector at a reduced collector potential while maintaining the sensitivity of the alkali metal ionization detector adequate for the relatively low concentration of alkali vapor and aerosol typically encountered in leak detection applications.

Alkali metal hafnium oxide scintillators

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

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

The present invention provides for a composition comprising an inorganic scintillator comprising an alkali metal hafnate, optionally cerium-doped, having the formula A 2HfO 3: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.

Thermal Coefficient of Redox Potential of Alkali Metals

NASA Astrophysics Data System (ADS)

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.

Alkali metal recovery from carbonaceous material conversion process

DOEpatents

Sharp, David W.; Clavenna, LeRoy R.; Gorbaty, Martin L.; Tsou, Joe M.

1980-01-01

In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced in the gasifier or similar reaction zone, alkali metal constitutents are recovered from the particles by withdrawing and passing the particles from the reaction zone to an alkali metal recovery zone in the substantial absence of molecular oxygen and treating the particles in the recovery zone with water or an aqueous solution in the substantial absence of molecular oxygen. The solution formed by treating the particles in the recovery zone will contain water-soluble alkali metal constituents and is recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preventing contact of the particles with oxygen as they are withdrawn from the reaction zone and during treatment in the recovery zone avoids the formation of undesirable alkali metal constituents in the aqueous solution produced in the recovery zone and insures maximum recovery of water-soluble alkali metal constituents from the alkali metal residues.

Neuropsychiatric manifestations of alkali metal deficiency and excess

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

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 investigatedmore » 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.« less

Method for the safe disposal of alkali metal

DOEpatents

Johnson, Terry 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.sub.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.

Apparatus enables accurate determination of alkali oxides in alkali metals

NASA Technical Reports Server (NTRS)

Dupraw, W. A.; Gahn, R. F.; Graab, J. W.; Maple, W. E.; Rosenblum, L.

1966-01-01

Evacuated apparatus determines the alkali oxide content of an alkali metal by separating the metal from the oxide by amalgamation with mercury. The apparatus prevents oxygen and moisture from inadvertently entering the system during the sampling and analytical procedure.

Method of handling radioactive alkali metal waste

DOEpatents

Wolson, Raymond D.; McPheeters, Charles C.

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.

Method of handling radioactive alkali metal waste

DOEpatents

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.

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

PubMed

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

Upgrading platform using alkali metals

DOEpatents

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.

Controlled in-situ dissolution of an alkali metal

DOEpatents

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.

Electrochemical devices utilizing molten alkali metal electrode-reactant

DOEpatents

Hitchcock, David C.; Mailhe, Catherine C.; De Jonghe, Lutgard C.

1986-01-01

Electrochemical cells are provided with a reactive metal to reduce the oxide of the alkali metal electrode-reactant. Cells employing a molten alkali metal electrode, e.g., sodium, in contact with a ceramic electrolyte, which is a conductor of the ions of the alkali metal forming the electrode, exhibit a lower resistance when a reactive metal, e.g., vanadium, is allowed to react with and reduce the alkali metal oxide. Such cells exhibit less degradation of the electrolyte and of the glass seals often used to joining the electrolyte to the other components of the cell under cycling conditions.

Electrochemical devices utilizing molten alkali metal electrode-reactant

DOEpatents

Hitchcock, D.C.; Mailhe, C.C.; De Jonghe, L.C.

1985-07-10

Electrochemical cells are provided with a reactive metal to reduce the oxide of the alkali metal electrode-reactant. Cells employing a molten alkali metal electrode, e.g., sodium, in contact with a ceramic electrolyte, which is a conductor of the ions of the alkali metal forming the electrode, exhibit a lower resistance when a reactive metal, e.g., vanadium, is allowed to react with and reduce the alkali metal oxide. Such cells exhibit less degradation of the electrolyte and of the glass seals often used to joining the electrolyte to the other components of the cell under cycling conditions.

Upgrading of petroleum oil feedstocks using alkali metals and hydrocarbons

DOEpatents

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.

Spill-Resistant Alkali-Metal-Vapor Dispenser

NASA Technical Reports Server (NTRS)

Klipstein, William

2005-01-01

A spill-resistant vessel has been developed for dispensing an alkali-metal vapor. Vapors of alkali metals (most commonly, cesium or rubidium, both of which melt at temperatures slightly above room temperature) are needed for atomic frequency standards, experiments in spectroscopy, and experiments in laser cooling. Although the present spill-resistant alkali-metal dispenser was originally intended for use in the low-gravity environment of outer space, it can also be used in normal Earth gravitation: indeed, its utility as a vapor source was confirmed by use of cesium in a ground apparatus. The vessel is made of copper. It consists of an assembly of cylinders and flanges, shown in the figure. The uppermost cylinder is a fill tube. Initially, the vessel is evacuated, the alkali metal charge is distilled into the bottom of the vessel, and then the fill tube is pinched closed to form a vacuum seal. The innermost cylinder serves as the outlet for the vapor, yet prevents spilling by protruding above the surface of the alkali metal, no matter which way or how far the vessel is tilted. In the event (unlikely in normal Earth gravitation) that any drops of molten alkali metal have been shaken loose by vibration and are floating freely, a mesh cap on top of the inner cylinder prevents the drops from drifting out with the vapor. Liquid containment of the equivalent of 1.2 grams of cesium was confirmed for all orientations with rubbing alcohol in one of the prototypes later used with cesium.

Alkali Metal Handling Practices at NASA MSFC

NASA Technical Reports Server (NTRS)

Salvail, Patrick G.; Carter, Robert R.

2002-01-01

NASA Marshall Space Flight Center (MSFC) is NASA s principle propulsion development center. Research and development is coordinated and carried out on not only the existing transportation systems, but also those that may be flown in the near future. Heat pipe cooled fast fission cores are among several concepts being considered for the Nuclear Systems Initiative. Marshall Space Flight Center has developed a capability to handle high-purity alkali metals for use in heat pipes or liquid metal heat transfer loops. This capability is a low budget prototype of an alkali metal handling system that would allow the production of flight qualified heat pipe modules or alkali metal loops. The processing approach used to introduce pure alkali metal into heat pipe modules and other test articles are described in this paper.

40 CFR 721.4660 - Alcohol, alkali metal salt.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151) is...

Low-temperature fabrication of alkali metal-organic charge transfer complexes on cotton textile for optoelectronics and gas sensing.

PubMed

Ramanathan, Rajesh; Walia, Sumeet; Kandjani, Ahmad Esmaielzadeh; Balendran, Sivacarendran; Mohammadtaheri, Mahsa; Bhargava, Suresh Kumar; Kalantar-zadeh, Kourosh; Bansal, Vipul

2015-02-03

A generalized low-temperature approach for fabricating high aspect ratio nanorod arrays of alkali metal-TCNQ (7,7,8,8-tetracyanoquinodimethane) charge transfer complexes at 140 °C is demonstrated. This facile approach overcomes the current limitation associated with fabrication of alkali metal-TCNQ complexes that are based on physical vapor deposition processes and typically require an excess of 800 °C. The compatibility of soft substrates with the proposed low-temperature route allows direct fabrication of NaTCNQ and LiTCNQ nanoarrays on individual cotton threads interwoven within the 3D matrix of textiles. The applicability of these textile-supported TCNQ-based organic charge transfer complexes toward optoelectronics and gas sensing applications is established.

Recovery of alkali metal constituents from catalytic coal conversion residues

DOEpatents

Soung, W.Y.

In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide to precipitate silicon constituents, the pH of the resultant solution is increased, preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

Recovery of alkali metal constituents from catalytic coal conversion residues

DOEpatents

Soung, Wen Y.

1984-01-01

In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them (46, 53, 61, 69) with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide (63) to precipitate silicon constituents, the pH of the resultant solution is increased (81), preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated (84) to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process (86, 18, 17) where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

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

DOEpatents

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).

Code of Federal Regulations, 2010 CFR

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...

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

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 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...

Electrochemical cell utilizing molten alkali metal electrode-reactant

DOEpatents

Virkar, Anil V.; Miller, Gerald R.

1983-11-04

An improved electrochemical cell comprising an additive-modified molten alkali metal electrode-reactant and/or electrolyte is disclosed. Various electrochemical cells employing a molten alkali metal, e.g., sodium, electrode in contact with a cationically conductive ceramic membrane experience a lower resistance and a lower temperature coefficient of resistance whenever small amounts of selenium are present at the interface of the electrolyte and the molten alkali metal. Further, cells having small amounts of selenium present at the electrolyte-molten metal interface exhibit less degradation of the electrolyte under long term cycling conditions.

Process for the disposal of alkali metals

DOEpatents

Lewis, Leroy 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.

Organic solvent soluble oxide supported hydrogenation catalyst precursors

DOEpatents

Edlund, David J.; Finke, Richard G.; Saxton, Robert J.

1992-01-01

The present invention discloses two polyoxoanion supported metal complexes found to be useful in olefin hydrogenation. The complexes are novel compositions of matter which are soluble in organic solvents. In particular, the compositions of matter comprise A.sub.x [L.sub.n Ir.sup.(I) .multidot.X.sub.2 M.sub.15 M'.sub.3 O.sub.62 ].sup.x- and A.sub.y [L.sub.n Ir.sup.(I) .multidot.X.sub.2 M.sub.9 M'.sub.3 O.sub.40 ].sup.y- where L is a ligand preferably chosen from 1,5-cyclooctadiene (COD), ethylene, cyclooctene, norbornadiene and other olefinic ligands; n=1 or 2 depending upon the number of double bonds present in the ligand L; X is a "hetero" atom chosen from B, Si, Ge, P, As, Se, Te, I, Co, Mn and Cu; M is either W or Mo; M' is preferably Nb or V but Ti, Zr, Ta, Hf are also useful; and A is a countercation preferably selected from tetrabutyl ammonium and alkali metal ions.

The effects of the macrotetralide actin antibiotics on the equilibrium extraction of alkali metal salts into organic solvents.

PubMed

Eisenman, G; Ciani, S; Szabo, G

1969-12-01

In order to clarify the mechanism by which neutral molecules such as the macrotetralide actin antibiotics make phospholipid bilayer membranes selectively permeable to cations, we have studied, both theoretically and experimentally, the extraction by these antibiotics of cations from aqueous solutions into organic solvents. The experiments involve merely shaking an organic solvent phase containing the antibiotic with aqueous solutions containing various cationic salts of a lipid-soluble colored anion. The intensity of color of the organic phase is then measured spectrophotometrically to indicate how much salt has been extracted. From such measurements of the equilibrium extraction of picrate and dinitrophenolate salts of Li, Na, K, Rb, Cs, and NH4 into n-hexane, dichloromethane, and hexane-dichloromethane mixtures, we have verified that the chemical reactions are as simple as previously postulated, at least for nonactin, monactin, dinactin, and trinactin. The equilibrium constant for the extraction of each cation by a given macrotetralide actin antibiotic was also found to be measurable with sufficient precision for meaningful differences among the members of this series of antibiotics to be detected. It is noteworthy that the ratios of selectivities among the various cations were discovered to be characteristic of a given antibiotic and to be completely independent of the solvent used. This finding and others reported here indicate that the size and shape of the complex formed between the macrotetralide and a given cation is the same, regardless of the species of cation bound. For such "isosteric" complexes, notable simplifications of the theory become possible which enable us to predict not only the electrical properties of a membrane made of the same solvent and having the thinness of the phospholipid bilayer but also, and more importantly, the electrical properties of the phospholipid bilayer membrane itself. These predictions will be compared with experimental

Alkali metal intercalates of molybdenum disulfide.

NASA Technical Reports Server (NTRS)

Somoano, R. B.; Hadek, V.; Rembaum, A.

1973-01-01

Study of some of the physicochemical properties of compounds obtained by subjecting natural molybdenite and single crystals of molybdenum disulfide grown by chemical vapor transport to intercalation with the alkali group of metals (Li, Na, K, Rb, and Cs) by means of the liquid ammonia technique. Reported data and results include: (1) the intercalation of the entire alkali metal group, (2) stoichiometries and X-ray data on all of the compounds, and (3) superconductivity data for all the intercalation compounds.

Alkali Metal/Salt Thermal-Energy-Storage Systems

NASA Technical Reports Server (NTRS)

Phillips, Wayne W.; Stearns, John W.

1987-01-01

Proposed thermal-energy-storage system based on mixture of alkali metal and one of its halide salts; metal and salt form slurry of two immiscible melts. Use of slurry expected to prevent incrustations of solidified salts on heat-transfer surfaces that occur where salts alone used. Since incrustations impede heat transfer, system performance improved. In system, charging heat-exchanger surface immersed in lower liquid, rich in halide-salt, phase-charge material. Discharging heat exchanger surface immersed in upper liquid, rich in alkali metal.

COMPLEX FLUORIDES OF PLUTONIUM AND AN ALKALI METAL

DOEpatents

Seaborg, G.T.

1960-08-01

A method is given for precipitating alkali metal plutonium fluorides. such as KPuF/sub 5/, KPu/sub 2/F/sub 9/, NaPuF/sub 5/, and RbPuF/sub 5/, from an aqueous plutonium(IV) solution by adding hydrogen fluoride and alkali-metal- fluoride.

A comprehensive study of the complexation of alkali metal cations by lower rim calix[4]arene amide derivatives.

PubMed

Horvat, Gordan; Frkanec, Leo; Cindro, Nikola; Tomišić, Vladislav

2017-09-13

The complexation of alkali metal cations by lower rim N,N-dihexylacetamide (L1) and newly synthesized N-hexyl-N-methylacetamide (L2) calix[4]arene tertiary-amide derivatives was thoroughly studied at 25 °C in acetonitrile (MeCN), benzonitrile (PhCN), and methanol (MeOH) by means of direct and competitive microcalorimetric titrations, and UV and 1 H NMR spectroscopies. In addition, by measuring the ligands' solubilities, the solution (transfer) Gibbs energies of the ligands and their alkali metal complexes were obtained. The inclusion of solvent molecules in the free and complexed calixarene hydrophobic cavities was also investigated. Computational (classical molecular dynamics) investigations of the studied systems were also carried out. The obtained results were compared with those previously obtained by studying the complexation ability of an N-hexylacetamidecalix[4]arene secondary-amide derivative (L3). The stability constants of 1 : 1 complexes were determined in all solvents used (the values obtained by different methods being in excellent agreement), as were the corresponding complexation enthalpies and entropies. Almost all of the examined reactions were enthalpically controlled. The most striking exceptions were reactions of Li + with both ligands in methanol, for which the entropic contribution to the reaction Gibbs energy was substantial due the entropically favourable desolvation of the smallest lithium cation. The thermodynamic stabilities of the complexes were quite solvent dependent (the stability decreased in the solvent order: MeCN > PhCN ≫ MeOH), which could be accounted for by considering the differences in the solvation of the ligand and free and complexed alkali metal cations in the solvents used. Comparison of the stability constants of the ligand L1 and L2 complexes clearly revealed that the higher electron-donating ability of the hexyl with respect to the methyl group is of considerable importance in determining the equilibria of the

Electronic structure of semiconducting alkali-metal silicides and germanides

NASA Astrophysics Data System (ADS)

Tegze, M.; Hafner, J.

1989-11-01

We present self-consistent linearized-muffin-tin-orbital calculations of the electronic structure of three alkali-metal germanides and silicides (KGe, NaGe, and NaSi). Like the alkali-metal-lead compounds investigated in our earlier work [M. Tegze and J. Hafner, Phys. Rev. B 39, 8263 (1989)] the Ge and Si compounds of the alkali metals form complex structures based on the packing of tetrahedral Ge4 and Si4 clusters. Our calculations show that all three compounds are narrow-gap semiconductors. The width of the energy gap depends on two main factors: the ratio of the intracluster to the intercluster interactions between the group-IV elements (which increases from Pb to Si) and the strength of the interactions between the alkali-metal atoms (which varies with the size ratio).

Spectroscopic studies of transition-metal ions in molten alkali-metal carboxylates

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

Maroni, V.A.; Maciejewski, M.L.

This paper presents the results of electronic absorption and /sup 13/C-NMR measurements on molten alkali metal formates and acetates and on solutions of selected 3d transition metal ions therein. These studies provide a unique opportunity to explore (1) the highly ordered nature of alkali carboxylates, (2) the ligand field properties of acetate and formate ions, and (3) the coordination chemistry of the 3d transition metals in molten carboxylates. 1 figure, 2 tables.

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

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 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 721.5452 - Alkali metal salt of halogenated organoborate (generic).

Code of Federal Regulations, 2010 CFR

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.

Code of Federal Regulations, 2010 CFR

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

Code of Federal Regulations, 2010 CFR

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...

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

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 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...

Crown Ether Complexes of Alkali-Metal Chlorides from SO2.

PubMed

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.

40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

Code of Federal Regulations, 2011 CFR

2011-07-01

... metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... 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...

A fluorescent paramagnetic Mn metal-organic framework based on semi-rigid pyrene tetra-carboxylic acid: sensing of solvent polarity and explosive nitroaromatics.

PubMed

Bajpai, Alankriti; Mukhopadhyay, Arindam; Krishna, Manchugondanahalli Shivakumar; Govardhan, Savitha; Moorthy, Jarugu Narasimha

2015-09-01

An Mn metal-organic framework (Mn-MOF), Mn-L, based on a pyrene-tetraacid linker (H4 L), displays a respectable fluorescence quantum yield of 8.3% in spite of the presence of the paramagnetic metal ions, due presumably to fixation of the metal ions in geometries that do not allow complete energy/charge-transfer quenching. Remarkably, the porous Mn-L MOF with ∼25% solvent-accessible volume exhibits a heretofore unprecedented solvent-dependent fluorescence emission maximum, permitting its use as a probe of solvent polarity; the emission maxima in different solvents correlate excellently with Reichardt's solvent polarity parameter (E T (N)). Further, the applicability of Mn-L to the sensing of nitroaromatics via fluorescence quenching is demonstrated; the detection limit for TNT is shown to be 125 p.p.m. The results bring out the fact that MOFs based on paramagnetic metal ions can indeed find application when the quenching mechanisms are attenuated by certain geometries of the organic linkers of the MOF.

IUPAC-NIST Solubility Data Series. 75. Nonmetals in Liquid Alkali Metals

NASA Astrophysics Data System (ADS)

Borgstedt, Hans Ulrich; Guminski, Cezary; Borgstedt, Hans Ulrich; Guminski, Cezary

2001-07-01

Liquid alkali metals have several physical properties which favor their use in a number of important applications. For example, their large liquidus temperature range and their excellent heat transfer properties are important for use as heat transfer media. They are used in large nuclear reactors in which hundreds of tons of sodium are circulating, and in small parts of engines for cooling of valves. Since these metals are among the most electropositive elements, several of them (Li, Na) can be used in high specific capacity and high energy density batteries at moderately elevated temperatures. The compatibility of metallic constructional materials which are used to contain the liquid metals is strongly influenced by nonmetals present in the liquids. The physical properties of the liquid metals are also influenced by dissolved substances. Several nonmetals dissolved in alkali metals are able to form ternary compounds with components of the constructional materials. Thus, corrosion and compatibility studies have been accompanied by extensive chemical work related to the solutions of non-metallic substances in liquid alkali metals. All available solubility data of nonmetallic elements and some of their compounds in the five liquid alkali metal solvents (Li, Na, K, Rb, and Cs) are collected and compiled. Original publications with reliable data and information on the methods used to generate them are reported in individual Compilations. When numerical data are not given in a publication, the data are often read out from figures and converted into numerical data by the compilers. The precision of this procedure is indicated in the Compilations under Estimated Error. Evaluated solubility data are tabulated at the end of the Critical Evaluations: if there is agreement of at least two independent studies within the experimental error, the solubility values are assigned to the "recommended" category. Values are assigned as "tentative," if only one reliable result was

Electrochemical cell having an alkali-metal-nitrate electrode

DOEpatents

Roche, M.F.; Preto, S.K.

1982-06-04

A power-producing secondary electrochemical cell includes a molten alkali metal as the negative-electrode material and a molten-nitrate salt as the positive-electrode material. The molten material in the respective electrodes are separated by a solid barrier of alkali-metal-ion conducting material. A typical cell includes active materials of molten sodium separated from molten sodium nitrate and other nitrates in mixture by a layer of sodium ..beta..'' alumina.

Purification and Characterization of Haloalkaline, Organic Solvent Stable Xylanase from Newly Isolated Halophilic Bacterium-OKH

PubMed Central

Sanghvi, Gaurav; Jivrajani, Mehul; Patel, Nirav; Jivrajani, Heta; Bhaskara, Govinal Badiger; Patel, Shivani

2014-01-01

A novel, alkali-tolerant halophilic bacterium-OKH with an ability to produce extracellular halophilic, alkali-tolerant, organic solvent stable, and moderately thermostable xylanase was isolated from salt salterns of Mithapur region, Gujarat, India. Identification of the bacterium was done based upon biochemical tests and 16S rRNA sequence. Maximum xylanase production was achieved at pH 9.0 and 37°C temperature in the medium containing 15% NaCl and 1% (w/v) corn cobs. Sugarcane bagasse and wheat straw also induce xylanase production when used as carbon source. The enzyme was active over a range of 0–25% sodium chloride examined in culture broth. The optimum xylanase activity was observed at 5% sodium chloride. Xylanase was purified with 25.81%-fold purification and 17.1% yield. Kinetic properties such as Km and Vmax were 4.2 mg/mL and 0.31 μmol/min/mL, respectively. The enzyme was stable at pH 6.0 and 50°C with 60% activity after 8 hours of incubation. Enzyme activity was enhanced by Ca2+, Mn2+, and Mg2+ but strongly inhibited by heavy metals such as Hg2+, Fe3+, Ni2+, and Zn2+. Xylanase was found to be stable in organic solvents like glutaraldehyde and isopropanol. The purified enzyme hydrolysed lignocellulosic substrates. Xylanase, purified from the halophilic bacterium-OKH, has potential biotechnological applications. PMID:27350996

Alkali metal vapors - Laser spectroscopy and applications

NASA Technical Reports Server (NTRS)

Stwalley, W. C.; Koch, M. E.

1980-01-01

The paper examines the rapidly expanding use of lasers for spectroscopic studies of alkali metal vapors. Since the alkali metals (lithium, sodium, potassium, rubidium and cesium) are theoretically simple ('visible hydrogen'), readily ionized, and strongly interacting with laser light, they represent ideal systems for quantitative understanding of microscopic interconversion mechanisms between photon (e.g., solar or laser), chemical, electrical and thermal energy. The possible implications of such understanding for a wide variety of practical applications (sodium lamps, thermionic converters, magnetohydrodynamic devices, new lasers, 'lithium waterfall' inertial confinement fusion reactors, etc.) are also discussed.

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

Code of Federal Regulations, 2010 CFR

2010-07-01

..., alkali metal salt (generic). 721.10097 Section 721.10097 Protection of Environment ENVIRONMENTAL... metal salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted benzenesulfonic acid, alkali metal salt (PMN P...

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

Code of Federal Regulations, 2011 CFR

2011-07-01

..., alkali metal salt (generic). 721.10097 Section 721.10097 Protection of Environment ENVIRONMENTAL... metal salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted benzenesulfonic acid, alkali metal salt (PMN P...

Metal-doped organic foam

DOEpatents

Rinde, James A.

1982-01-01

Organic foams having a low density and very small cell size and method for producing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

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

Code of Federal Regulations, 2010 CFR

2010-07-01

... metal salt (generic). 721.10098 Section 721.10098 Protection of Environment ENVIRONMENTAL PROTECTION... 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 CFR 721.10098 - Disubstituted benzoic acid, alkali metal salt (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... metal salt (generic). 721.10098 Section 721.10098 Protection of Environment ENVIRONMENTAL PROTECTION... 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...

Effects of pH on frog gustatory responses to chloride salts of alkali-metal and alkali-earth-metal.

PubMed

Kumai, T; Nomura, H

1980-01-01

The pH effects on frog gustatory responses to alkali-metal and alkali-earth-metal chloride salts were examined using single fungi-form papilla preparations. Responses to 0.1-0.5 M NaCl were clearly dependent upon the pH of the stimulating solutions. The responses increased as the pH decreased from 6.5 to 4.5 and were almost completely suppressed at pH's above 6.5. There was no significant difference in the pH dependency of the response among alkali-metal chlorides. HCl solutions elicited only a poor response under conditions in which the water response was suppressed by the simultaneous presence of a low NaCl concentration. Responses to alkali-earth-metal chlorides varied in their pH dependency. Response to CaCl2 was slightly affected by pH changes from 4.5 to 9.0, response to SrCl2 was considerably suppressed in the alkaline region, and responses to BaCl2 and MgCl2 were strongly suppressed at pH's above 6.5. BeCl2 solutions showed less marked stimulating effects over the pH range tested. The differences in pH dependency described above suggest the existence of two kinds of receptor sites, one being pH-insensitive sites responsible for the calcium response and the other pH-sensitive sites responsible for the sodium response. A cross-adaptation test appeared to support this possibility. Assuming that the pH effect mentioned is related to changes in the state of ionization of the receptor molecule, the pKa of the ionizable group responsible for the sodium response was determined to be approximately 5.5.

Thermodynamics of solvent interaction with the metal-organic framework MOF-5.

PubMed

Akimbekov, Zamirbek; Wu, Di; Brozek, Carl K; Dincă, Mircea; Navrotsky, Alexandra

2016-01-14

The inclusion of solvent in metal-organic framework (MOF) materials is a highly specific form of guest-host interaction. In this work, the energetics of solvent MOF-5 interactions has been investigated by solution calorimetry in 5 M sodium hydroxide (NaOH) at room temperature. Solution calorimetric measurement of enthalpy of formation (ΔH(f)) of Zn4O(C8H4O4)3·C3H7NO (MOF-5·DMF) and Zn4O(C8H4O4)3·0.60C5H11NO (MOF-5·0.60DEF) from the dense components zinc oxide (ZnO), 1,4-benzenedicarboxylic acid (H2BDC), N,N-dimethylformamide (DMF) and N,N-diethylformamide (DEF) gives values of 16.69 ± 1.21 and 45.90 ± 1.46 kJ (mol Zn4O)(-1), respectively. The enthalpies of interaction (ΔH(int)) for DMF and DEF with MOF-5 are -82.78 ± 4.84 kJ (mol DMF)(-1) and -89.28 ± 3.05 kJ (mol DEF)(-1), respectively. These exothermic interaction energies suggest that, at low guest loading, Lewis base solvents interact more strongly with electron accepting Zn4O clusters in the MOF than at high solvent loading. These data provide a quantitative thermodynamic basis to investigate transmetallation and solvent assisted linker exchange (SALE) methods and to synthesize new MOFs.

Role of solvent in metal-on-metal surface diffusion: A case for rational solvent selection for materials synthesis

NASA Astrophysics Data System (ADS)

Imandi, Venkataramana; Jagannath, Mantha Sai Pavan; Chatterjee, Abhijit

2018-09-01

The effect of solvent on diffusion at metal surfaces is poorly understood despite its importance to morphological evolution during materials processing, corrosion and catalysis. In this article, we probe the metal-solvent interfacial structure, effective nature of interactions and dynamics when a solvent is in contact with a metal using a novel accelerated molecular dynamics simulation technique called temperature programmed molecular dynamics (TPMD). TPMD simulations reveal that surface diffusion of metal-on-metal can be made to vary over orders-of-magnitude by tuning the metal-solvent interaction. Ultimately, the solvent can have an indirect effect on diffusion. As the solvent tugs at the metal surface the separation between the adsorbed metal atom (adatom) and the surface layer can be modulated via metal-solvent interactions. The resulting adatom-surface separation can cause stronger/weaker binding of the adatom to the metal surface, which in turn results in the observed slower/enhanced diffusion in the presence of solvent. We believe this effect is ubiquitous in pure metal and metal alloys and in principle one could rationally select solvent to control the material structural evolution. Implications on materials synthesis are discussed in the context of formation of nanoporous materials.

Method of assembling and sealing an alkali metal battery

DOEpatents

Elkins, Perry E.; Bell, Jerry E.; Harlow, Richard A.; Chase, Gordon G.

1983-01-01

A method of initially assembling and then subsequently hermetically sealing a container portion of an alkali metal battery to a ceramic portion of such a battery is disclosed. Sealing surfaces are formed respectively on a container portion and a ceramic portion of an alkali metal battery. These sealing surfaces are brought into juxtaposition and a material is interposed therebetween. This interposed material is one which will diffuse into sealing relationship with both the container portion and the ceramic portion of the alkali metal battery at operational temperatures of such a battery. A pressure is applied between these sealing surfaces to cause the interposed material to be brought into intimate physical contact with such juxtaposed surfaces. A temporary sealing material which will provide a seal against a flow of alkali metal battery reactants therethrough at room temperatures and is applied over the juxtaposed sealing surfaces and material interposed therebetween. The entire assembly is heated to an operational temperature so that the interposed material diffuses into the container portion and the ceramic portion to form a hermetic seal therebetween. The pressure applied to the juxtaposed sealing surfaces is maintained in order to ensure the continuation of the hermetic seal.

Fluorescent probes and bioimaging: alkali metals, alkaline earth metals and pH.

PubMed

Yin, Jun; Hu, Ying; Yoon, Juyoung

2015-07-21

All living species and life forms have an absolute requirement for bio-functional metals and acid-base equilibrium chemistry owing to the critical roles they play in biological processes. Hence, a great need exists for efficient methods to detect and monitor biometals and acids. In the last few years, great attention has been paid to the development of organic molecule based fluorescent chemosensors. The availability of new synthetic fluorescent probes has made fluorescence microscopy an indispensable tool for tracing biologically important molecules and in the area of clinical diagnostics. This review highlights the recent advances that have been made in the design and bioimaging applications of fluorescent probes for alkali metals and alkaline earth metal cations, including lithium, sodium and potassium, magnesium and calcium, and for pH determination within biological systems.

Method of assembling and sealing an alkali metal battery

DOEpatents

Elkins, P.E.; Bell, J.E.; Harlow, R.A.; Chase, G.G.

1983-03-01

A method of initially assembling and then subsequently hermetically sealing a container portion of an alkali metal battery to a ceramic portion of such a battery is disclosed. Sealing surfaces are formed respectively on a container portion and a ceramic portion of an alkali metal battery. These sealing surfaces are brought into juxtaposition and a material is interposed there between. This interposed material is one which will diffuse into sealing relationship with both the container portion and the ceramic portion of the alkali metal battery at operational temperatures of such a battery. A pressure is applied between these sealing surfaces to cause the interposed material to be brought into intimate physical contact with such juxtaposed surfaces. A temporary sealing material which will provide a seal against a flow of alkali metal battery reactants there through at room temperatures and is applied over the juxtaposed sealing surfaces and material interposed there between. The entire assembly is heated to an operational temperature so that the interposed material diffuses into the container portion and the ceramic portion to form a hermetic seal there between. The pressure applied to the juxtaposed sealing surfaces is maintained in order to ensure the continuation of the hermetic seal. 4 figs.

The interactions of sorbates with gallosilicates and alkali-metal exchanged gallosilicates

NASA Astrophysics Data System (ADS)

Limtrakul, J.; Kuno, M.; Treesukol, P.

1999-11-01

Structures, energetics and vibrational frequencies of the interaction of adsorbates with H-aluminosilicates (H-AlZ), H-gallosilicates (H-GaZ), alkali-metal exchanged aluminosilicates (X-AlZ) and alkali-metal exchanged gallosilicates (X-GaZ), where X being Li, Na, or K, have been carried out at B3LYP and HF levels of theory with 6-31G(d) as the basis set. The charge compensating alkali-metal ions can affect the catalytically active site (Si-O-T where T=Al or Ga) by weakening the Si-O, Al-O, and Ga-O bonds as compared to their anionic frameworks. Comparing the net stabilization energies, Δ ENSE, of the naked alkali-metal/H 2O adducts with those of the alkali-metal exchanged zeolite/H 2O systems, the latter amounts only to about 50% of the former, which is partly due to the destabilizing role of the negative zeolitic oxygen frameworks surrounding the cations. The interaction of sorbates with the alkali-metal exchanged gallosilicates can be employed to probe the field strength inside the catalytic frameworks as indicated by the plot of the binding energy, Δ E, versus 1/ RX-O w2, with R(X-O w) being the distance between the cationic nucleus and the oxygen atom of the adsorbate. The IR spectra of H 2O adsorbed on Na-AlZ are calculated to be 3584, 3651, and 1686 cm -1. The obtained results are in excellent agreement with the very recent experimental IR spectra of water adsorbed on Na-ZSM-5 of Zecchina et al. (J. Phys. Chem., 100 (1996) 16 484). Other important features, i.e. the correlation between Δ νOH and, Δ E, R(X-O w) , and 1/ RX-O w2, cationic size, demonstrate that the interactions of sorbates with alkali-metal exchanged gallosilicates are well approximated by electrostatic contribution.

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

PubMed

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.

Role of crystal field in mixed alkali metal effect: electron paramagnetic resonance study of mixed alkali metal oxyfluoro vanadate glasses.

PubMed

Honnavar, Gajanan V; Ramesh, K P; Bhat, S V

2014-01-23

The mixed alkali metal effect is a long-standing problem in glasses. Electron paramagnetic resonance (EPR) is used by several researchers to study the mixed alkali metal effect, but a detailed analysis of the nearest neighbor environment of the glass former using spin-Hamiltonian parameters was elusive. In this study we have prepared a series of vanadate glasses having general formula (mol %) 40 V2O5-30BaF2-(30 - x)LiF-xRbF with x = 5, 10, 15, 20, 25, and 30. Spin-Hamiltonian parameters of V(4+) ions were extracted by simulating and fitting to the experimental spectra using EasySpin. From the analysis of these parameters it is observed that the replacement of lithium ions by rubidium ions follows a "preferential substitution model". Using this proposed model, we were able to account for the observed variation in the ratio of the g parameter, which goes through a maximum. This reflects an asymmetric to symmetric changeover of the alkali metal ion environment around the vanadium site. Further, this model also accounts for the variation in oxidation state of vanadium ion, which was confirmed from the variation in signal intensity of EPR spectra.

Alkali metal cation complexation by 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds

DOE PAGES

Surowiec, Malgorzata A.; Custelcean, Radu; Surowiec, Kazimierz; ...

2014-04-23

Alkali metal cation extraction behavior for two series of 1,3-alternate, mono-ionizable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionizable group is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the proton-ionizable group is attached to one para position in the calixarene framework, thus positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs+ efficiency and selectivity. Single-species extraction pH profiles of Cs+ for Series 1 and 2 ligands with the same proton-ionizable groupmore » are very similar. Thus, association of Cs+ with the calixcrown ring is more important than the the proton-ionizable group’s position in relation to the crown ether cavity. Solid-state structures are presented for two unionized ligands from Series 2, as is a crystal containing two different ionized ligand–Cs+ complexes.« less

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

PubMed

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.

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

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

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

2011-11-18

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

Alkali metal/sulfur battery

DOEpatents

Anand, Joginder N.

1978-01-01

Alkali metal/sulfur batteries in which the electrolyte-separator is a relatively fragile membrane are improved by providing means for separating the molten sulfur/sulfide catholyte from contact with the membrane prior to cooling the cell to temperatures at which the catholyte will solidify. If the catholyte is permitted to solidify while in contact with the membrane, the latter may be damaged. The improvement permits such batteries to be prefilled with catholyte and shipped, at ordinary temperatures.

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

NASA Astrophysics Data System (ADS)

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.

Alkali metal yttrium neo-pentoxide double alkoxide precursors to alkali metal yttrium oxide nanomaterials

DOE PAGES

Boyle, Timothy J.; Neville, Michael L.; Sears, Jeremiah Matthew; ...

2016-03-15

In this study, a series of alkali metal yttrium neo-pentoxide ([AY(ONep) 4]) compounds were developed as precursors to alkali yttrium oxide (AYO 2) nanomaterials. The reaction of yttrium amide ([Y(NR 2) 3] where R=Si(CH 3) 3) with four equivalents of H-ONep followed by addition of [A(NR 2)] (A=Li, Na, K) or A o (A o=Rb, Cs) led to the formation of a complex series of A nY(ONep) 3+n species, crystallographically identified as [Y 2Li 3(μ 3-ONep)(μ 3-HONep)(μ-ONep) 5(ONep) 3(HONep) 2] (1), [YNa 2(μ 3-ONep) 4(ONep)] 2 (2), {[Y 2K 3(μ 3-ONep) 3(μ-ONep) 4(ONep) 2(ηξ-tol) 2][Y 4K 2(μ 4-O)(μ 3-ONep) 8(ONep)more » 4]•η x-tol]} (3), [Y 4K 2(μ 4-O)(μ 3-ONep) 8(ONep) 4] (3a), [Y 2Rb 3(μ 4-ONep) 3(μ-ONep) 6] (4), and [Y 2Cs 4(μ 6-O)(μ 3-ONep) 6(μ 3-HONep) 2(ONep) 2(η x-tol) 4]•tol (5). Compounds 1–5 were investigated as single source precursors to AYOx nanomaterials following solvothermal routes (pyridine, 185 °C for 24h). The final products after thermal processing were found by powder X-ray diffraction experiments to be Y 2O 3 with variable sized particles based on transmission electron diffraction. Energy dispersive X-ray spectroscopy studies indicated that the heavier alkali metal species were present in the isolated nanomaterials.« less

Process for carbonaceous material conversion and recovery of alkali metal catalyst constituents held by ion exchange sites in conversion residue

DOEpatents

Sharp, David W.

1980-01-01

In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered for the particles by contacting or washing them with an aqueous solution containing calcium or magnesium ions in an alkali metal recovery zone at a low temperature, preferably below about 249.degree. F. During the washing or leaching process, the calcium or magnesium ions displace alkali metal ions held by ion exchange sites in the particles thereby liberating the ions and producing an aqueous effluent containing alkali metal constituents. The aqueous effluent from the alkali metal recovery zone is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

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

PubMed

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

2011-11-18

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

Observation of Raman self-focusing in an alkali-metal vapor cell

NASA Astrophysics Data System (ADS)

Proite, N. A.; Unks, B. E.; Green, J. T.; Yavuz, D. D.

2008-02-01

We report an experimental demonstration of Raman self-focusing and self-defocusing in a far-off resonant alkali-metal atomic system. The key idea is to drive a hyperfine transition in an alkali-metal atom to a maximally coherent state with two laser beams. In this regime, the two-photon detuning from the Raman resonance controls the nonlinear index of the medium.

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

DOEpatents

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

NASA Astrophysics Data System (ADS)

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.

Advances in high temperature components for AMTEC (alkali metal thermal-to-electric converter)

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

Williams, R.M.; Jeffries-Nakamura, B.; Underwood, M.L.

1991-12-31

Long lifetimes are required for AMTEC (or sodium heat engine) components for aerospace and terrestrial applications, and the high heat input temperature as well as the alkali metal liquid and vapor environment places unusual demands on the materials used to construct AMTEC devices. In addition, it is important to maximize device efficiency and power density, while maintaining a long life capability. In addition to the electrode, which must provide both efficient electrode kinetics, transport of the alkali metal, and low electrical resistance, other high temperature components of the cell face equally demanding requirements. The beta{double_prime} alumina solid electrolyte (BASE), themore » seal between the BASE ceramic and its metallic transition to the hot alkali metal (liquid or vapor) source, and metallic components of the device are exposed to hot liquid alkali metal. Modification of AMTEC components may also be useful in optimizing the device for particular operating conditions. In particular, a potassium AMTEC may be expected to operate more efficiently at lower temperatures.« less

Advances in high temperature components for AMTEC (alkali metal thermal-to-electric converter)

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

Williams, R.M.; Jeffries-Nakamura, B.; Underwood, M.L.

1991-01-01

Long lifetimes are required for AMTEC (or sodium heat engine) components for aerospace and terrestrial applications, and the high heat input temperature as well as the alkali metal liquid and vapor environment places unusual demands on the materials used to construct AMTEC devices. In addition, it is important to maximize device efficiency and power density, while maintaining a long life capability. In addition to the electrode, which must provide both efficient electrode kinetics, transport of the alkali metal, and low electrical resistance, other high temperature components of the cell face equally demanding requirements. The beta{double prime} alumina solid electrolyte (BASE),more » the seal between the BASE ceramic and its metallic transition to the hot alkali metal (liquid or vapor) source, and metallic components of the device are exposed to hot liquid alkali metal. Modification of AMTEC components may also be useful in optimizing the device for particular operating conditions. In particular, a potassium AMTEC may be expected to operate more efficiently at lower temperatures.« less

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

DOEpatents

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.

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

DOEpatents

Doeff, M.M.; Peng, M.Y.; Ma, Y.; Visco, S.J.; DeJonghe, L.C.

1996-09-24

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{minus}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. 11 figs.

Alkali metal-refractory metal biphase electrode for AMTEC

NASA Technical Reports Server (NTRS)

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.

Development of operationally stable inverted organic light-emitting diode prepared without using alkali metals (Presentation Recording)

NASA Astrophysics Data System (ADS)

Fukagawa, Hirohiko; Morii, Katsuyuki; Hasegawa, Munehiro; Gouda, Shun; Tsuzuki, Toshimitsu; Shimizu, Takahisa; Yamamoto, Toshihiro

2015-10-01

The OLED is one of the key devices for realizing future flexible displays and lightings. One of the biggest challenges left for the OLED fabricated on a flexible substrate is the improvement of its resistance to oxygen and moisture. A high barrier layer [a water vapor transmission rate (WVTR) of about 10-6 g/m2/day] is proposed to be necessary for the encapsulation of conventional OLEDs. Some flexible high barrier layers have recently been demonstrated; however, such high barrier layers require a complex process, which makes flexible OLEDs expensive. If an OLED is prepared without using air-sensitive materials such as alkali metals, no stringent encapsulation is necessary for such an OLED. In this presentation, we will discuss our continuing efforts to develop an inverted OLED (iOLED) prepared without using alkali metals. iOLEDs with a bottom cathode are considered to be effective for realizing air-stable OLEDs since the electron injection layer (EIL) can be prepared by fabrication processes that might damage the organic layers, resulting in the enhanced range of materials suitable for EILs. We have demonstrated that a highly efficient and relatively air-stable iOLED can be realized by employing poly(ethyleneimine) as an EIL. Dark spot formation was not observed after 250 days in the poly(ethyleneimine)-based iOLED encapsulated by a barrier film with a WVTR of 10-4 g/m2/day. In addition, we have demonstrated the fabrication of a highly operational stable iOLED utilizing a newly developed EIL. The iOLED exhibits an expected half-lifetime of over 10,000 h from an initial luminance of 1,000 cd/m2.

Measurement of dielectric constant of organic solvents by indigenously developed dielectric probe

NASA Astrophysics Data System (ADS)

Keshari, Ajay Kumar; Rao, J. Prabhakar; Rao, C. V. S. Brahmmananda; Ramakrishnan, R.; Ramanarayanan, R. R.

2018-04-01

The extraction, separation and purification of actinides (uranium and plutonium) from various matrices are an important step in nuclear fuel cycle. One of the separation process adopted in an industrial scale is the liquid-liquid extraction or solvent extraction. Liquid-liquid extraction uses a specific ligand/extractant in conjunction with suitable diluent. Solvent extraction or liquid-liquid extraction, involves the partitioning of the solute between two immiscible phases. In most cases, one of the phases is aqueous, and the other one is an organic solvent. The solvent used in solvent extraction should be selective for the metal of interest, it should have optimum distribution ratio, and the loaded metal from the organic phase should be easily stripped under suitable experimental conditions. Some of the important physical properties which are important for the solvent are density, viscosity, phase separation time, interfacial surface tension and the polarity of the extractant.

Hall Determination of Atomic Radii of Alkali Metals

ERIC Educational Resources Information Center

Houari, Ahmed

2008-01-01

I will propose here an alternative method for determining atomic radii of alkali metals based on the Hall measurements of their free electron densities and the knowledge of their crystal structure. (Contains 2 figures.)

Alkali Metal Doping for Improved CH3NH3PbI3 Perovskite Solar Cells.

PubMed

Zhao, Wangen; Yao, Zhun; Yu, Fengyang; Yang, Dong; Liu, Shengzhong Frank

2018-02-01

Organic-inorganic hybrid halide perovskites are proven to be a promising semiconductor material as the absorber layer of solar cells. However, the perovskite films always suffer from nonuniform coverage or high trap state density due to the polycrystalline characteristics, which degrade the photoelectric properties of thin films. Herein, the alkali metal ions which are stable against oxidation and reduction are used in the perovskite precursor solution to induce the process of crystallization and nucleation, then affect the properties of the perovskite film. It is found that the addition of the alkali metal ions clearly improves the quality of perovskite film: enlarges the grain sizes, reduces the defect state density, passivates the grain boundaries, increases the built-in potential ( V bi ), resulting to the enhancement in the power conversion efficiency of perovskite thin film solar cell.

Process for preparing higher oxides of the alkali and alkaline earth metals

NASA Technical Reports Server (NTRS)

Sadhukhan, P.; Bell, A. (Inventor)

1978-01-01

High purity inorganic higher oxides of the alkali and alkaline earth metals are prepared by subjecting the hydroxide of the alkali and alkaline earth metal to a radio frequency discharge sustained in oxygen. The process is particulary adaptable to the production of high purity potassium superoxide by subjecting potassium hydroxide to glow discharge sustained in oxygen under the pressure of about 0.75 to 1.00 torr.

Stabilized Alkali-Metal Ultraviolet-Band-Pass Filters

NASA Technical Reports Server (NTRS)

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

1995-01-01

Layers of bismuth 5 to 10 angstrom thick incorporated into alkali-metal ultraviolet-band-pass optical filters by use of advanced fabrication techniques. In new filters layer of bismuth helps to reduce surface migration of sodium. Sodium layer made more stable and decreased tendency to form pinholes by migration.

Method for inhibiting alkali metal corrosion of nickel-containing alloys

DOEpatents

DeVan, Jackson H.; Selle, James E.

1983-01-01

Structural components of nickel-containing alloys within molten alkali metal systems are protected against corrosion during the course of service by dissolving therein sufficient aluminum, silicon, or manganese to cause the formation and maintenance of a corrosion-resistant intermetallic reaction layer created by the interaction of the molten metal, selected metal, and alloy.

Method of making metal-doped organic foam products

DOEpatents

Rinde, James A.

1981-01-01

Organic foams having a low density and very small cell size and method for roducing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

Alkali Metal Heat Pipe Life Issues

NASA Technical Reports Server (NTRS)

Reid, Robert S.

2004-01-01

One approach to space fission power system design is predicated on the use of alkali metal heat pipes, either as radiator elements, thermal management components, or as part of the core primary heat-transfer system. This synopsis characterizes long-life core heat pipes. References are included where more detailed information can be found. Specifics shown here are for demonstrational purposes and do not necessarily reflect current Project Prometheus point designs.

SOLVENT EXTRACTION PROCESS

DOEpatents

Jonke, A.A.

1957-10-01

In improved solvent extraction process is described for the extraction of metal values from highly dilute aqueous solutions. The process comprises contacting an aqueous solution with an organic substantially water-immiscible solvent, whereby metal values are taken up by a solvent extract phase; scrubbing the solvent extract phase with an aqueous scrubbing solution; separating an aqueous solution from the scrubbed solvent extract phase; and contacting the scrubbed solvent phase with an aqueous medium whereby the extracted metal values are removed from the solvent phase and taken up by said medium to form a strip solution containing said metal values, the aqueous scrubbing solution being a mixture of strip solution and an aqueous solution which contains mineral acids anions and is free of the metal values. The process is particularly effective for purifying uranium, where one starts with impure aqueous uranyl nitrate, extracts with tributyl phosphate dissolved in carbon tetrachloride, scrubs with aqueous nitric acid and employs water to strip the uranium from the scrubbed organic phase.

Absorption Spectroscopy of Rubidium in an Alkali Metal Dispenser Cell and Bleached Wave Analysis

DTIC Science & Technology

2015-03-26

Department of Engineering Physics Graduate School of Engineering and Management Air Force Institute of Technology Air University Air Education and...at atmospheric temperatures and pressures, so none of the safety measures needed with pure solid alkali metal would be required. AMDs can also be...Institute of Technology Graduate School of Engineering and Management (AFIT/ENP) 2950 Hobson Way WPAFB OH 45433-7765 8. PERFORMING ORGANIZATION

Characterization of microwave-induced electric discharge phenomena in metal-solvent mixtures.

PubMed

Chen, Wen; Gutmann, Bernhard; Kappe, C Oliver

2012-02-01

Electric discharge phenomena in metal-solvent mixtures are investigated utilizing a high field density, sealed-vessel, single-mode 2.45 GHz microwave reactor with a built-in camera. Particular emphasis is placed on studying the discharges exhibited by different metals (Mg, Zn, Cu, Fe, Ni) of varying particle sizes and morphologies in organic solvents (e.g., benzene) at different electric field strengths. Discharge phenomena for diamagnetic and paramagnetic metals (Mg, Zn, Cu) depend strongly on the size of the used particles. With small particles, short-lived corona discharges are observed that do not lead to a complete breakdown. Under high microwave power conditions or with large particles, however, bright sparks and arcs are experienced, often accompanied by solvent decomposition and formation of considerable amounts of graphitized material. Small ferromagnetic Fe and Ni powders (<40 μm) are heated very rapidly in benzene suspensions and start to glow in the microwave field, whereas larger particles exhibit extremely strong discharges. Electric discharges were also observed when Cu metal or other conductive materials such as silicon carbide were exposed to the microwave field in the absence of a solvent in an argon or nitrogen atmosphere.

SOLVENT EXTRACTION OF RUTHENIUM

DOEpatents

Hyman, H.H.; Leader, G.R.

1959-07-14

The separation of rathenium from aqueous solutions by solvent extraction is described. According to the invention, a nitrite selected from the group consisting of alkali nitrite and alkaline earth nitrite in an equimolecular quantity with regard to the quantity of rathenium present is added to an aqueous solution containing ruthenium tetrantrate to form a ruthenium complex. Adding an organic solvent such as ethyl ether to the resulting mixture selectively extracts the rathenium complex.

Metal-doped organic gels and method thereof

DOEpatents

Satcher, Jr., Joe H.; Baumann, Theodore F.

2003-09-02

Disclosed herein is a sol-gel polymerization process for synthesizing metal-doped organic gels. The process polymerizes metal salts of hydroxylated benzenes or hydroxylated benzene derivatives with alkyl or aryl aldehydes to form metal-doped, wet, organic gels. The gels can then be dried by supercritical solvent extraction to form metal-doped aerogels or by evaporation to form metal-doped xerogels. The aerogels and xerogels can then be pyrolyzed.

Metal-doped organic gels and method thereof

DOEpatents

Satcher, Jr., Joe H.; Baumann, Theodore F.

2007-10-23

Disclosed herein is a sol-gel polymerization process for synthesizing metal-doped organic gels. The process polymerizes metal salts of hydroxylated benzenes or hydroxylated benzene derivatives with alkyl or aryl aldehydes to form metal-doped, wet, organic gels. The gels can then be dried by supercritical solvent extraction to form metal-doped aerogels or by evaporation to form metal-doped xerogels. The aerogels and xerogels can then be pyrolyzed.

Method for intercalating alkali metal ions into carbon electrodes

DOEpatents

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.

Method for intercalating alkali metal ions into carbon electrodes

DOEpatents

Doeff, M.M.; Ma, Y.; Visco, S.J.; DeJonghe, L.

1995-08-22

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.

A simple model for metal cation-phosphate interactions in nucleic acids in the gas phase: alkali metal cations and trimethyl phosphate.

PubMed

Ruan, Chunhai; Huang, Hai; Rodgers, M T

2008-02-01

Threshold collision-induced dissociation techniques are employed to determine the bond dissociation energies (BDEs) of complexes of alkali metal cations to trimethyl phosphate, TMP. Endothermic loss of the intact TMP ligand is the only dissociation pathway observed for all complexes. Theoretical calculations at the B3LYP/6-31G* level of theory are used to determine the structures, vibrational frequencies, and rotational constants of neutral TMP and the M+(TMP) complexes. Theoretical BDEs are determined from single point energy calculations at the B3LYP/6-311+G(2d,2p) level using the B3LYP/6-31G* optimized geometries. The agreement between theory and experiment is reasonably good for all complexes except Li+(TMP). The absolute M+-(TMP) BDEs are found to decrease monotonically as the size of the alkali metal cation increases. No activated dissociation was observed for alkali metal cation binding to TMP. The binding of alkali metal cations to TMP is compared with that to acetone and methanol.

Solvent and process for recovery of hydroxide from aqueous mixtures

DOEpatents

Moyer, Bruce A.; Chambliss, C. Kevin; Bonnesen, Peter V.; Keever, Tamara J.

2001-01-01

Hydroxide values and associated alkali metal may be recovered from alkaline aqueous solutions using classes of fluorinated alcohols in a water immiscible solvent. The alcohols are characterized by fluorine substituents which are proximal to the acidic alcohol protons and are located to adjust the acidity of the extractant and the solubility of the extractant in the solvent. A method for stripping the extractant and solvent to regenerate the extractant and purified aqueous hydroxide solution is described.

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

DOEpatents

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.

Device and method for upgrading petroleum feedstocks and petroleum refinery streams using an alkali metal conductive membrane

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

Gordon, John Howard; Alvare, Javier

A reactor has two chambers, namely an oil feedstock chamber and a source chamber. An ion separator separates the oil feedstock chamber from the source chamber, wherein the ion separator allows alkali metal ions to pass from the source chamber, through the ion separator, and into the oil feedstock chamber. A cathode is at least partially housed within the oil feedstock chamber and an anode is at least partially housed within the source chamber. A quantity of an oil feedstock is within the oil feedstock chamber, the oil feedstock comprising at least one carbon atom and a heteroatom and/or onemore » or more heavy metals, the oil feedstock further comprising naphthenic acid. When the alkali metal ion enters the oil feedstock chamber, the alkali metal reacts with the heteroatom, the heavy metals and/or the naphthenic acid, wherein the reaction with the alkali metal forms inorganic products.« less

Investigation of Anti-Relaxation Coatings for Alkali-Metal Vapor Cells using Surface Science Techniques

DTIC Science & Technology

2011-02-01

worldwide. Lawrence Berkeley National Laboratory Peer Reviewed Title: Investigation of anti-Relaxation coatings for alkali-metal vapor cells using ...2010 Abstract: Many technologies based on cells containing alkali-metal atomic vapor benefit from the use of antirelaxation surface coatings in order to...preserve atomic spin polarization. In particular, paraffin has been used for this purpose for several decades and has been demonstrated to allow an

Alkali metal protective garment and composite material

DOEpatents

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.

Elliptical polarization of near-resonant linearly polarized probe light in optically pumped alkali metal vapor

PubMed Central

Li, Yingying; Wang, Zhiguo; Jin, Shilong; Yuan, Jie; Luo, Hui

2017-01-01

Optically pumped alkali metal atoms currently provide a sensitive solution for magnetic microscopic measurements. As the most practicable plan, Faraday rotation of linearly polarized light is extensively used in spin polarization measurements of alkali metal atoms. In some cases, near-resonant Faraday rotation is applied to improve the sensitivity. However, the near-resonant linearly polarized probe light is elliptically polarized after passing through optically pumped alkali metal vapor. The ellipticity of transmitted near-resonant probe light is numerically calculated and experimentally measured. In addition, we also analyze the negative impact of elliptical polarization on Faraday rotation measurements. From our theoretical estimate and experimental results, the elliptical polarization forms an inevitable error in spin polarization measurements. PMID:28216649

Molecular origin of high free energy barriers for alkali metal ion transfer through ionic liquid-graphene electrode interfaces.

PubMed

Ivaništšev, Vladislav; Méndez-Morales, Trinidad; Lynden-Bell, Ruth M; Cabeza, Oscar; Gallego, Luis J; Varela, Luis M; Fedorov, Maxim V

2016-01-14

In this work we study mechanisms of solvent-mediated ion interactions with charged surfaces in ionic liquids by molecular dynamics simulations, in an attempt to reveal the main trends that determine ion-electrode interactions in ionic liquids. We compare the interfacial behaviour of Li(+) and K(+) at a charged graphene sheet in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, and its mixtures with lithium and potassium tetrafluoroborate salts. Our results show that there are dense interfacial solvation structures in these electrolytes that lead to the formation of high free energy barriers for these alkali metal cations between the bulk and direct contact with the negatively charged surface. We show that the stronger solvation of Li(+) in the ionic liquid leads to the formation of significantly higher interfacial free energy barriers for Li(+) than for K(+). The high free energy barriers observed in our simulations can explain the generally high interfacial resistance in electrochemical storage devices that use ionic liquid-based electrolytes. Overcoming these barriers is the rate-limiting step in the interfacial transport of alkali metal ions and, hence, appears to be a major drawback for a generalised application of ionic liquids in electrochemistry. Some plausible strategies for future theoretical and experimental work for tuning them are suggested.

Selective Metal Cation Capture by Soft Anionic Metal-Organic Frameworks via Drastic Single-Crystal-to-Single-Crystal Transformations

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

Tian, Jian; Saraf, Laxmikant V.; Schwenzer, Birgit

2012-05-25

Flexible anionic metal-organic frameworks transform to neutral heterobimetallic systems via single-crystal-to-single-crystal processes invoked by cation insertion. These transformations are directed by cooperative bond breakage and formation, resulting in expansion or contraction of the 3D framework by up to 33% due to the flexible nature of the organic linker. These MOFs displays highly selective uptake of divalent transition metal cations (Co2+ and Ni2+ for example) over alkali metal cations (Li+ and Na+).

Alkali-metal induced band structure deformation investigated by angle-resolved photoemission spectroscopy and first-principles calculations

NASA Astrophysics Data System (ADS)

Ito, S.; Feng, B.; Arita, M.; Someya, T.; Chen, W.-C.; Takayama, A.; Iimori, T.; Namatame, H.; Taniguchi, M.; Cheng, C.-M.; Tang, S.-J.; Komori, F.; Matsuda, I.

2018-04-01

Alkali-metal adsorption on the surface of materials is widely used for in situ surface electron doping, particularly for observing unoccupied band structures by angle-resolved photoemission spectroscopy (ARPES). However, the effects of alkali-metal atoms on the resulting band structures have yet to be fully investigated, owing to difficulties in both experiments and calculations. Here, we combine ARPES measurements on cesium-adsorbed ultrathin bismuth films with first-principles calculations of the electronic charge densities and demonstrate a simple method to evaluate alkali-metal induced band deformation. We reveal that deformation of bismuth surface bands is directly correlated with vertical charge-density profiles at each electronic state of bismuth. In contrast, a change in the quantized bulk bands is well described by a conventional rigid-band-shift picture. We discuss these two aspects of the band deformation holistically, considering spatial distributions of the electronic states and cesium-bismuth hybridization, and provide a prescription for applying alkali-metal adsorption to a wide range of materials.

Ionic Transport Through Metal-Rich Organic Coatings

DTIC Science & Technology

2016-08-19

COVERED October 2013-Septermber 2015 4. TITLE AND SUBTITLE Ionic Transport Through Metal-Rich Organic Coatings 5a. CONTRACT NUMBER 5b. GRANT...NOTES 14. ABSTRACT Organic coatings are commonly used on aircraft and in the automotive industry to protect against corrosive environments. Although...volume (MPV) percent, solvent polarity, and resin molecular weight impact corrosion protection of metal-rich organic (MRO) coatings. Following design

Ionic Transport Through Metal-Rich Organic Coatings

DTIC Science & Technology

2016-08-19

COVERED October 2013-Septermber 2015 4. TITLE AND SUBTITLE Ionic Transport Through Metal-Rich Organic Coatings 5a. CONTRACT NUMBER 5b. GRANT...14. ABSTRACT Organic coatings are commonly used on aircraft and in the automotive industry to protect against corrosive environments. Although...volume (MPV) percent, solvent polarity, and resin molecular weight impact corrosion protection of metal-rich organic (MRO) coatings. Following design of

First-principles study on interlayer state in alkali and alkaline earth metal atoms intercalated bilayer graphene

NASA Astrophysics Data System (ADS)

Kaneko, Tomoaki; Saito, Riichiro

2017-11-01

Energetics and electronic structures of alkali metal (Li, Na, K, Rb, and Cs) and alkaline earth metal (Be, Mg, Ca, Sr, and Ba) atoms intercalated bilayer graphene are systematically investigated using first-principles calculations based on density functional theory. Formation of alkali and alkaline earth metal atoms intercalated bilayer graphene is exothermic except for Be and Mg. The interlayer state between two graphene layers is occupied for K, Rb, Cs, Ca, Sr, and Ba. We find that the energetic position of the interlayer states between bilayer graphene monotonically shifts downward with increasing of interlayer distance. The interlayer distances of more than 4.5 Å and 4.0 Å, respectively, are necessary for the occupation of the interlayer state in bilayer graphene for alkali and alkaline earth metal atoms, which is almost independent of the intercalant metal species. We discuss the relevance to occurrence of superconductivity for the metal intercalated bilayer graphene in terms of the occupation of the interlayer state and the phonon frequency of metal ions.

The roles of the solute and solvent cavities in charge-transfer-to-solvent dynamics: Ultrafast studies of potasside and sodide in diethyl ether

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

Cavanagh, Molly C.; Young, Ryan M.; Schwartz, Benjamin J.

2008-10-07

alkali metal anions essentially instantaneously produces a gas-phase-like neutral alkali metal atom, which then spontaneously undergoes partial ejection of the remaining valence electron to form a neutral alkali metal cation:solvated electron tight-contact pair.« less

SOLVENT EXTRACTION PROCESS FOR SEPARATING ACTINIDE AND LANTHANIDE METAL VALUES

DOEpatents

Hildebrandt, R.A.; Hyman, H.H.; Vogler, S.

1962-08-14

A process of countercurrently extracting an aqueous mineral acid feed solution for the separation of actinides from lanthanides dissolved therern is described. The feed solution is made acid-defrcient with alkali metal hydroxide prior to.contact with acid extractant; during extraction, however, acid is transferred from organic to aqueous solution and the aqueous solution gradually becomes acid. The acid-deficient phase ' of the process promotes the extraction of the actinides, while the latter acid phase'' of the process improves retention of the lanthanides in the aqueous solution. This provides for an improved separation. (AEC)

Alkali metal intercalated fullerene-like MS(2) (M = W, Mo) nanoparticles and their properties.

PubMed

Zak, Alla; Feldman, Yishay; Lyakhovitskaya, Vera; Leitus, Gregory; Popovitz-Biro, Ronit; Wachtel, Ellen; Cohen, Hagai; Reich, Shimon; Tenne, Reshef

2002-05-01

Layered metal disulfides-MS(2) (M = Mo, W) in the form of fullerene-like nanoparticles and in the form of platelets (crystallites of the 2H polytype) have been intercalated by exposure to alkali metal (potassium and sodium) vapor using a two-zone transport method. The composition of the intercalated systems was established using X-ray energy dispersive spectrometer and X-ray photoelectron spectroscopy (XPS). The alkali metal concentration in the host lattice was found to depend on the kind of sample and the experimental conditions. Furthermore, an inhomogeneity of the intercalated samples was observed. The product consisted of both nonintercalated and intercalated phases. X-ray diffraction analysis and transmission electron microscopy of the samples, which were not exposed to the ambient atmosphere, showed that they suffered little change in their lattice parameters. On the other hand, after exposure to ambient atmosphere, substantial increase in the interplanar spacing (3-5 A) was observed for the intercalated phases. Insertion of one to two water molecules per intercalated metal atom was suggested as a possible explanation for this large expansion along the c-axis. Deintercalation of the hydrated alkali atoms and restacking of the MS(2) layers was observed in all the samples after prolonged exposure to the atmosphere. Electric field induced deintercalation of the alkali metal atoms from the host lattice was also observed by means of the XPS technique. Magnetic moment measurements for all the samples indicate a diamagnetic to paramagnetic transition after intercalation. Measurements of the transport properties reveal a semiconductor to metal transition for the heavily K intercalated 2H-MoS(2). Other samples show several orders of magnitude decrease in resistivity and two- to five-fold decrease in activation energies upon intercalation. These modifications are believed to occur via charge transfer from the alkali metal to the conduction band of the host lattice

Aqueous alkali metal hydroxide insoluble cellulose ether membrane

NASA Technical Reports Server (NTRS)

Hoyt, H. E.; Pfluger, H. L. (Inventor)

1969-01-01

A membrane that is insoluble in an aqueous alkali metal hydroxide medium is described. The membrane is a resin which is a water-soluble C2-C4 hydroxyalkyl cellulose ether polymer and an insolubilizing agent for controlled water sorption, a dialytic and electrodialytic membrane. It is particularly useful as a separator between electrodes or plates in an alkaline storage battery.

Inorganic Metal Oxide/Organic Polymer Nanocomposites And Method Thereof

DOEpatents

Gash, Alexander E.; Satcher, Joe H.; Simpson, Randy

2004-11-16

A synthetic method for preparation of hybrid inorganic/organic energetic nanocomposites is disclosed herein. The method employs the use of stable metal in organic salts and organic solvents as well as an organic polymer with good solubility in the solvent system to produce novel nanocomposite energetic materials. In addition, fuel metal powders (particularly those that are oxophilic) can be incorporated into composition. This material has been characterized by thermal methods, energy-filtered transmission electron microscopy (EFTEM), N.sub.2 adsoprtion/desorption methods, and Fourier-Transform (FT-IR) spectroscopy. According to these characterization methods the organic polymer phase fills the nanopores of the material, providing superb mixing of the component phases in the energetic nanocomposite.

Thermodynamics of Liquid Alkali Metals and Their Binary Alloys

NASA Astrophysics Data System (ADS)

Thakor, P. B.; Patel, Minal H.; Gajjar, P. N.; Jani, A. R.

2009-07-01

The theoretical investigation of thermodynamic properties like internal energy, entropy, Helmholtz free energy, heat of mixing (ΔE) and entropy of mixing (ΔS) of liquid alkali metals and their binary alloys are reported in the present paper. The effect of concentration on the thermodynamic properties of Ac1Bc2 alloy of the alkali-alkali elements is investigated and reported for the first time using our well established local pseudopotential. To investigate influence of exchange and correlation effects, we have used five different local field correction functions viz; Hartree(H), Taylor(T), Ichimaru and Utsumi(IU), Farid et al. (F) and Sarkar et al. (S). The increase of concentration C2, increases the internal energy and Helmholtz free energy of liquid alloy Ac1Bc2. The behavior of present computation is not showing any abnormality in the outcome and hence confirms the applicability of our model potential in explaining the thermodynamics of liquid binary alloys.

High capacity nickel battery material doped with alkali metal cations

DOEpatents

Jackovitz, John F.; Pantier, Earl A.

1982-05-18

A high capacity battery material is made, consisting essentially of hydrated Ni(II) hydroxide, and about 5 wt. % to about 40 wt. % of Ni(IV) hydrated oxide interlayer doped with alkali metal cations selected from potassium, sodium and lithium cations.

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

PubMed Central

Boughlala, Zakaria; Fonseca Guerra, Célia

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 of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn–Sham molecular orbital (KS‐MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities. PMID:27551660

Tube radial distribution phenomenon with a two-phase separation solution of a fluorocarbon and hydrocarbon organic solvent mixture in a capillary tube and metal compounds separation.

PubMed

Kitaguchi, Koichi; Hanamura, Naoya; Murata, Masaharu; Hashimoto, Masahiko; Tsukagoshi, Kazuhiko

2014-01-01

A fluorocarbon and hydrocarbon organic solvent mixture is known as a temperature-induced phase-separation solution. When a mixed solution of tetradecafluorohexane as a fluorocarbon organic solvent and hexane as a hydrocarbon organic solvent (e.g., 71:29 volume ratio) was delivered in a capillary tube that was controlled at 10°C, the tube radial distribution phenomenon (TRDP) of the solvents was clearly observed through fluorescence images of the dye, perylene, dissolved in the mixed solution. The homogeneous mixed solution (single phase) changed to a heterogeneous solution (two phases) with inner tetradecafluorohexane and outer hexane phases in the tube under laminar flow conditions, generating the dynamic liquid-liquid interface. We also tried to apply TRDP to a separation technique for metal compounds. A model analyte mixture, copper(II) and hematin, was separated through the capillary tube, and detected with a chemiluminescence detector in this order within 4 min.

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

NASA Astrophysics Data System (ADS)

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)Se 2 solar cells on glass substrate

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

Kamikawa, Yukiko; Nishinaga, Jiro; Ishizuka, Shogo

The precise control of alkali-metal concentrations in Cu(In,Ga)Se 2 (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 frommore » 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.« less

Effect of thermal annealing on the redistribution of alkali metals in Cu(In,Ga)Se 2 solar cells on glass substrate

DOE PAGES

Kamikawa, Yukiko; Nishinaga, Jiro; Ishizuka, Shogo; ...

2018-03-07

The precise control of alkali-metal concentrations in Cu(In,Ga)Se 2 (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 frommore » 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.« less

Transversely diode-pumped alkali metal vapour laser

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

Parkhomenko, A I; Shalagin, A M

2015-09-30

We have studied theoretically the operation of a transversely diode-pumped alkali metal vapour laser. For the case of high-intensity laser radiation, we have obtained an analytical solution to a complex system of differential equations describing the laser. This solution allows one to exhaustively determine all the energy characteristics of the laser and to find optimal parameters of the working medium and pump radiation (temperature, buffer gas pressure, and intensity and width of the pump spectrum). (lasers)

Solvent induced rapid modulation of micro/nano structures of metal carboxylates coordination polymers: mechanism and morphology dependent magnetism.

PubMed

Liu, Kun; Shen, Zhu-Rui; Li, Yue; Han, Song-De; Hu, Tong-Liang; Zhang, Da-Shuai; Bu, Xian-He; Ruan, Wen-Juan

2014-08-12

Rational modulation of morphology is very important for functional coordination polymers (CPs) micro/nanostructures, and new strategies are still desired to achieve this challenging target. Herein, organic solvents have been established as the capping agents for rapid modulating the growth of metal-carboxylates CPs in organic solvent/water mixtures at ambient conditions. Co-3,5-pyridinedicarboxylate (pydc) CPs was studied here as the example. During the reaction, the organic solvents exhibited three types of modulation effect: anisotropic growth, anisotropic growth/formation of new crystalline phase and the formation of new crystalline phase solely, which was due to the variation of their binding ability with metal cations. The following study revealed that the binding ability was critically affected by their functional groups and molecular size. Moreover, their modulation effect could be finely tuned by changing volume ratios of solvent mixtures. Furthermore, they could be applied for modulating other metal-carboxylates CPs: Co-1,3,5-benzenetricarboxylic (BTC), Zn-pydc and Eu-pydc etc. Additionally, the as-prepared Co-pydc CPs showed a fascinating morphology-dependent antiferromagnetic behavior.

Solvent induced rapid modulation of micro/nano structures of metal carboxylates coordination polymers: mechanism and morphology dependent magnetism

NASA Astrophysics Data System (ADS)

Liu, Kun; Shen, Zhu-Rui; Li, Yue; Han, Song-De; Hu, Tong-Liang; Zhang, Da-Shuai; Bu, Xian-He; Ruan, Wen-Juan

2014-08-01

Rational modulation of morphology is very important for functional coordination polymers (CPs) micro/nanostructures, and new strategies are still desired to achieve this challenging target. Herein, organic solvents have been established as the capping agents for rapid modulating the growth of metal-carboxylates CPs in organic solvent/water mixtures at ambient conditions. Co-3,5-pyridinedicarboxylate (pydc) CPs was studied here as the example. During the reaction, the organic solvents exhibited three types of modulation effect: anisotropic growth, anisotropic growth/formation of new crystalline phase and the formation of new crystalline phase solely, which was due to the variation of their binding ability with metal cations. The following study revealed that the binding ability was critically affected by their functional groups and molecular size. Moreover, their modulation effect could be finely tuned by changing volume ratios of solvent mixtures. Furthermore, they could be applied for modulating other metal-carboxylates CPs: Co-1,3,5-benzenetricarboxylic (BTC), Zn-pydc and Eu-pydc etc. Additionally, the as-prepared Co-pydc CPs showed a fascinating morphology-dependent antiferromagnetic behavior.

Solvent induced rapid modulation of micro/nano structures of metal carboxylates coordination polymers: mechanism and morphology dependent magnetism

PubMed Central

Liu, Kun; Shen, Zhu-Rui; Li, Yue; Han, Song-De; Hu, Tong-Liang; Zhang, Da-Shuai; Bu, Xian-He; Ruan, Wen-Juan

2014-01-01

Rational modulation of morphology is very important for functional coordination polymers (CPs) micro/nanostructures, and new strategies are still desired to achieve this challenging target. Herein, organic solvents have been established as the capping agents for rapid modulating the growth of metal-carboxylates CPs in organic solvent/water mixtures at ambient conditions. Co-3,5-pyridinedicarboxylate (pydc) CPs was studied here as the example. During the reaction, the organic solvents exhibited three types of modulation effect: anisotropic growth, anisotropic growth/formation of new crystalline phase and the formation of new crystalline phase solely, which was due to the variation of their binding ability with metal cations. The following study revealed that the binding ability was critically affected by their functional groups and molecular size. Moreover, their modulation effect could be finely tuned by changing volume ratios of solvent mixtures. Furthermore, they could be applied for modulating other metal-carboxylates CPs: Co-1,3,5-benzenetricarboxylic (BTC), Zn-pydc and Eu-pydc etc. Additionally, the as-prepared Co-pydc CPs showed a fascinating morphology-dependent antiferromagnetic behavior. PMID:25113225

Metal-doped organic foam and method of making same. [Patent application

DOEpatents

Rinde, J.A.

Organic foams having a low density and very small cell size and method for producing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

Inorganic metal oxide/organic polymer nanocomposites and method thereof

DOEpatents

Gash, Alexander E.; Satcher, Joe H.; Simpson, Randy

2004-03-30

A synthetic method for preparation of hybrid inorganic/organic energetic nanocomposites is disclosed herein. The method employs the use of stable metal inorganic salts and organic solvents as well as an organic polymer with good solubility in the solvent system to produce novel nanocomposite energetic materials. In addition, fuel metal powders (particularly those that are oxophillic) can be incorporated into composition. This material has been characterized by thermal methods, energy-filtered transmission electron microscopy (EFTEM), N.sub.2 adsoprtion/desorption methods, and Fourier-Transform (FT-IR) spectroscopy. According to these characterization methods the organic polymer phase fills the nanopores of the composite material, providing superb mixing of the component phases in the energetic nanocomposite.

Theory of metal atom-water interactions and alkali halide dimers

NASA Technical Reports Server (NTRS)

Jordan, K. D.; Kurtz, H. A.

1982-01-01

Theoretical studies of the interactions of metal atoms with water and some of its isoelectronic analogs, and of the properties of alkali halides and their aggregates are discussed. Results are presented of ab initio calculations of the heats of reaction of the metal-water adducts and hydroxyhydrides of Li, Be, B, Na, Mg, and Al, and of the bond lengths and angles an; the heats of reaction for the insertion of Al into HF, H2O, NH3, H2S and CH3OH, and Be and Mg into H2O. Calculations of the electron affinities and dipole moments and polarizabilities of selected gas phase alkali halide monomers and dimers are discussed, with particular attention given to results of calculations of the polarizability of LiF taking into account electron correlation effects, and the polarizability of the dimer (LiF)2.

Organic solvents in the pharmaceutical industry.

PubMed

Grodowska, Katarzyna; Parczewski, Andrzej

2010-01-01

Organic solvents are commonly used in the pharmaceutical industry as reaction media, in separation and purification of synthesis products and also for cleaning of equipment. This paper presents some aspects of organic solvents utilization in an active pharmaceutical ingredient and a drug product manufacturing process. As residual solvents are not desirable substances in a final product, different methods for their removal may be used, provided they fulfill safety criteria. After the drying process, analyses need to be performed to check if amounts of solvents used at any step of the production do not exceed acceptable limits (taken from ICH Guideline or from pharmacopoeias). Also new solvents like supercritical fluids or ionic liquids are developed to replace "traditional" organic solvents in the pharmaceutical production processes.

Solvent-induced controllable synthesis, single-crystal to single-crystal transformation and encapsulation of Alq3 for modulated luminescence in (4,8)-connected metal-organic frameworks.

PubMed

Lan, Ya-Qian; Jiang, Hai-Long; Li, Shun-Li; Xu, Qiang

2012-07-16

In this work, for the first time, we have systematically demonstrated that solvent plays crucial roles in both controllable synthesis of metal-organic frameworks (MOFs) and their structural transformation process. With solvent as the only variable, five new MOFs with different structures have been constructed, in which one MOF undergoes solvent-induced single-crystal to single-crystal (SCSC) transformation that involves not only solvent exchange but also the cleavage and formation of coordination bonds. Particularly, a significant crystallographic change has been realized through an unprecedented three-step SCSC transformation process. Furthermore, we have demonstrated that the obtained MOF could be an excellent host for chromophores such as Alq3 for modulated luminescent properties.

Immobilizing Highly Catalytically Active Pt Nanoparticles inside the Pores of Metal-Organic Framework: A Double Solvents Approach

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

Aijaz, Arshad; Karkamkar, Abhijeet J.; Choi, Young Joon

2012-08-29

Ultrafine Pt nanoparticles were successfully immobilized inside the pores of a metal-organic framework MIL-101 without deposition of Pt nanoparticles on the external surfaces of framework by using a 'double solvents' method. The resulting Pt@MIL-101 composites with different Pt loadings represent the first highly active MOF-immobilized metal nanocatalysts for catalytic reactions in all three phases: liquid-phase ammonia borane hydrolysis; solid-phase ammonia borane thermal dehy-drogenation and gas-phase CO oxidation. The observed excellent catalytic performances are at-tributed to the small Pt nanoparticles within the pores of MIL-101. 'We are thankful to AIST and METI for financial support. TA & AK are thankful formore » support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. PNNL is operated by Battelle.'« less

Effects of industrial effluents, heavy metals, and organic solvents on mallard embryo development.

PubMed

Hoffman, D J; Eastin, W C

1981-09-01

Mallard eggs were externally exposed at 3 and 8 days of incubation to 7 different industrial effluents and to 7 different heavy metal, organic solvent, and petroleum solutions to screen for potential embryo-toxic effects. This route of exposure was chosen in order to simulate the transfer of pollutant from the plumage of aquatic birds to their eggs. Five of the effluents including mineral pigment, scouring effluent, sludge, and tannery effluent resulted in small but significant reductions in embryonic growth. Treatment with methyl mercury chloride solution of 50 ppm (Hg) impaired embryonic growth but much higher concentrations were required to affect survival and cause teratogenic effects. Oil used to suppress road dust was the most toxic of the pollutants tested and only 0.5 microliter/egg caused 60% mortality by 18 days of development. These findings, in combination with other studies suggest that petroleum pollutants, or effluents in combination with petroleum, may pose a hazard to birds' eggs when exposure is by this route.

Effects of industrial effluents, heavy metals, and organic solvents on mallard embryo development

USGS Publications Warehouse

Hoffman, D.J.; Eastin, W.C.

1981-01-01

Mallard eggs were externally exposed at 3 and 8 days of incubation to 7 different industrial effluents and to 7 different heavy metal, organic solvent, and petroleum solutions to screen for potential embryo-toxic effects. This route of exposure was chosen in order to simulate the transfer of pollutant from the plumage of aquatic birds to their eggs. Five of the effluents including mineral pigment, scouring effluent, sludge, and tannery effluent resulted in small but significant reductions in embryonic growth. Treatment with methyl mercury chloride solution of 50 ppm (Hg) impaired embryonic growth but much higher concentrations were required to affect survival and cause teratogenic effects. Oil used to suppress road dust was the most toxic of the pollutants tested and only 0.5 microliter/egg caused 60% mortality by 18 days of development. These findings, in combination with other studies suggest that petroleum pollutants, or effluents in combination with petroleum, may pose a hazard to birds' eggs when exposure is by this route.

[Evaluation of exposure of auto painters to organic solvents in the city of Bogota].

PubMed

Palma, Marien; Briceño, Leonardo; Idrovo, Álvaro J; Varona, Marcela

2015-08-01

Painters of automobiles are exposed to pure and mixed solvents that have been associated with neurological effects and carcinogenic mutations. To characterize the health and work conditions of individuals who are occupationally exposed to organic solvents used in sheet metal and auto body shops in Bogota. Descriptive, cross-sectional study that characterizes the health and work conditions of individuals exposed to organic solvents in sheet metal and auto body shops in Bogota. A group exposed to the solvents was compared to an unexposed group. Air concentrations of benzene, toluene and xylene (BTX) were determined, individual questionnaires were administered and phenylmercapturic, hippuric and ortho- and para-methylhippuric acids were measured in urine. The results of the measurements and the questionnaires were correlated to determine the exposure panorama. For the three BTX metabolites, statistically significant differences (p<0.001) were found between the population exposed to the solvents and the unexposed population. For the exposed population, positive correlations were found between toluene in air and hippuric acid in urine (rho=0.82) and between xylene in air and o-methylhippuric acid in urine (rho=0.76). Hippuric acid values exceeded permissible levels in 11 workers and p-methylhippuric acid exceeded permissible levels in 8 workers. None of the phenylmercapturic values exceeded the limit. Auto painters are exposed to high levels of organic solvents at the workplace and do not have adequate industrial health and safety conditions to perform their jobs.

Alkali metal carbon dioxide electrochemical system for energy storage and/or conversion of carbon dioxide to oxygen

NASA Technical Reports Server (NTRS)

Hagedorn, Norman H. (Inventor)

1993-01-01

An alkali metal, such as lithium, is the anodic reactant; carbon dioxide or a mixture of carbon dioxide and carbon monoxide is the cathodic reactant; and carbonate of the alkali metal is the electrolyte in an electrochemical cell for the storage and delivery of electrical energy. Additionally, alkali metal-carbon dioxide battery systems include a plurality of such electrochemical cells. Gold is a preferred catalyst for reducing the carbon dioxide at the cathode. The fuel cell of the invention produces electrochemical energy through the use of an anodic reactant which is extremely energetic and light, and a cathodic reactant which can be extracted from its environment and therefore exacts no transportation penalty. The invention is, therefore, especially useful in extraterrestrial environments.

Coordination effect-regulated CO2 capture with an alkali metal onium salts/crown ether system

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

Yang, Zhen-Zhen; Jiang, Deen; Zhu, Xiang

2014-01-01

A coordination effect was employed to realize equimolar CO2 absorption, adopting easily synthesized amino group containing absorbents (alkali metal onium salts). The essence of our strategy was to increase the steric hindrance of cations so as to enhance a carbamic acid pathway for CO2 capture. Our easily synthesized alkali metal amino acid salts or phenolates were coordinated with crown ethers, in which highly sterically hindered cations were obtained through a strong coordination effect of crown ethers with alkali metal cations. For example, a CO2 capacity of 0.99 was attained by potassium prolinate/18-crown-6, being characterized by NMR, FT-IR, and quantum chemistrymore » calculations to go through a carbamic acid formation pathway. The captured CO2 can be stripped under very mild conditions (50 degrees C, N-2). Thus, this protocol offers an alternative for the development of technological innovation towards efficient and low energy processes for carbon capture and sequestration.« less

40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fluorinated carboxylic acid alkali metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4663...

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

PubMed

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.

Anionic Gallium-Based Metal;#8722;Organic Framework and Its Sorption and Ion-Exchange Properties

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

Banerjee, Debasis; Kim, Sun Jin; Wu, Haohan

2012-04-30

A gallium-based metal-organic framework Ga{sub 6}(C{sub 9}H{sub 3}O{sub 6}){sub 8} {center_dot} (C{sub 2}H{sub 8}N){sub 6}(C{sub 3}H{sub 7}NO){sub 3}(H{sub 2}O){sub 26} [1, Ga{sub 6}(1,3,5-BTC){sub 8} {center_dot} 6DMA {center_dot} 3DMF {center_dot} 26H{sub 2}O], GaMOF-1; BTC = benzenetricarboxylate/trimesic acid and DMA = dimethylamine, with space group I{bar 4}3d, a = 19.611(1) {angstrom}, and V = 7953.4(6) {angstrom}{sup 3}, was synthesized using solvothermal techniques and characterized by synchrotron-based X-ray microcrystal diffraction. Compound 1 contains isolated gallium tetrahedra connected by the organic linker (BTC) forming a 3,4-connected anionic porous network. Disordered positively charged ions and solvent molecules are present in the pore, compensating for themore » negative charge of the framework. These positively charged molecules could be exchanged with alkali-metal ions, as is evident by an ICP-MS study. The H{sub 2} storage capacity of the parent framework is moderate with a H{sub 2} storage capacity of {approx}0.5 wt % at 77 K and 1 atm.« less

Compressed air-assisted solvent extraction (CASX) for metal removal.

PubMed

Li, Chi-Wang; Chen, Yi-Ming; Hsiao, Shin-Tien

2008-03-01

A novel process, compressed air-assisted solvent extraction (CASX), was developed to generate micro-sized solvent-coated air bubbles (MSAB) for metal extraction. Through pressurization of solvent with compressed air followed by releasing air-oversaturated solvent into metal-containing wastewater, MSAB were generated instantaneously. The enormous surface area of MSAB makes extraction process extremely fast and achieves very high aqueous/solvent weight ratio (A/S ratio). CASX process completely removed Cr(VI) from acidic electroplating wastewater under A/S ratio of 115 and extraction time of less than 10s. When synthetic wastewater containing Cd(II) of 50mgl(-1) was treated, A/S ratios of higher than 714 and 1190 could be achieved using solvent with extractant/diluent weight ratio of 1:1 and 5:1, respectively. Also, MSAB have very different physical properties, such as size and density, compared to the emulsified solvent droplets, making separation and recovery of solvent from treated effluent very easy.

Production, Optimization, and Characterization of Organic Solvent Tolerant Cellulases from a Lignocellulosic Waste-Degrading Actinobacterium, Promicromonospora sp. VP111.

PubMed

Thomas, Lebin; Ram, Hari; Kumar, Alok; Singh, Ved Pal

2016-07-01

High costs of natural cellulose utilization and cellulase production are an industrial challenge. In view of this, an isolated soil actinobacterium identified as Promicromonospora sp. VP111 showed potential for production of major cellulases (CMCase, FPase, and β-glucosidase) utilizing untreated agricultural lignocellulosic wastes. Extensive disintegration of microcrystalline cellulose and adherence on it during fermentation divulged true cellulolytic efficiency of the strain. Conventional optimization resulted in increased cellulase yield in a cost-effective medium, and the central composite design (CCD) analysis revealed cellulase production to be limited by cellulose and ammonium sulfate. Cellulase activities were enhanced by Co(+2) (1 mM) and retained up to 60 °C and pH 9.0, indicating thermo-alkaline tolerance. Cellulases showed stability in organic solvents (25 % v/v) with log P ow  ≥ 1.24. Untreated wheat straw during submerged fermentation was particularly degraded and yielded about twofold higher levels of cellulases than with commercial cellulose (Na-CMC and avicel) which is especially economical. Thus, this is the first detailed report on cellulases from an efficient strain of Promicromonospora that was non-hemolytic, alkali-halotolerant, antibiotic (erythromycin, kanamycin, rifampicin, cefaclor, ceftazidime) resistant, multiple heavy metal (Mo(+6) = W(+6) > Pb(+2) > Mn(+2) > Cr(+3) > Sn(+2)), and organic solvent (n-hexane, isooctane) tolerant, which is industrially and environmentally valuable.

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

PubMed

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

DOEpatents

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.

SOLVENT EXTRACTION PROCESS FOR THE RECOVERY OF METALS FROM PHOSPHORIC ACID

DOEpatents

Bailes, R.H.; Long, R.S.

1958-11-01

> A solvent extraction process is presented for recovering metal values including uranium, thorium, and other lanthanide and actinide elements from crude industrial phosphoric acid solutions. The process conslsts of contacting said solution with an immisclble organic solvent extractant containing a diluent and a material selected from the group consisting of mono and di alkyl phosphates, alkyl phosphonates and alkyl phosphites. The uranlum enters the extractant phase and is subsequently recovered by any of the methods known to the art. Recovery is improved if the phosphate solution is treated with a reducing agent such as iron or aluminum powder prior to the extraction step.

Organic Solvent Effects in Biomass Conversion Reactions.

PubMed

Shuai, Li; Luterbacher, Jeremy

2016-01-01

Transforming lignocellulosic biomass into fuels and chemicals has been intensely studied in recent years. A large amount of work has been dedicated to finding suitable solvent systems, which can improve the transformation of biomass into value-added chemicals. These efforts have been undertaken based on numerous research results that have shown that organic solvents can improve both conversion and selectivity of biomass to platform molecules. We present an overview of these organic solvent effects, which are harnessed in biomass conversion processes, including conversion of biomass to sugars, conversion of sugars to furanic compounds, and production of lignin monomers. A special emphasis is placed on comparing the solvent effects on conversion and product selectivity in water with those in organic solvents while discussing the origins of the differences that arise. We have categorized results as benefiting from two major types of effects: solvent effects on solubility of biomass components including cellulose and lignin and solvent effects on chemical thermodynamics including those affecting reactants, intermediates, products, and/or catalysts. Finally, the challenges of using organic solvents in industrial processes are discussed from the perspective of solvent cost, solvent stability, and solvent safety. We suggest that a holistic view of solvent effects, the mechanistic elucidation of these effects, and the careful consideration of the challenges associated with solvent use could assist researchers in choosing and designing improved solvent systems for targeted biomass conversion processes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption of alkali and alkaline earth metal atoms and dimers on monolayer germanium carbide

NASA Astrophysics Data System (ADS)

Gökçe, Aytaç Gürhan; Ersan, Fatih

2017-01-01

First-principles plane wave calculations have been performed to study the adsorption of alkali and alkaline earth metals on monolayer germanium carbide (GeC). We found that the favourable adsorption sites on GeC sheet for single alkali and alkaline earth adatoms are generally different from graphene or germanene. Among them, Mg, Na and their dimers have weakly bounded to GeC due to their closed valence electron shells, so they may have high mobility on GeC. Two different levels of adatom coverage (? and ?) have been investigated and we concluded that different electronic structures and magnetic moments for both coverages owing to alkali and alkaline earth atoms have long range electrostatic interactions. Lithium atom prefers to adsorbed on hollow site similar to other group-IV monolayers and the adsorption results in metallisation of GeC instead of semiconducting behaviour. Na and K adsorption can induce 1 ? total magnetic moment on GeC structures and they have shown semiconductor property which may have potential use in spintronic devices. We also showed that alkali or alkaline earth metal atoms can form dimer on GeC sheet. Calculated adsorption energies suggest that clustering of alkali and alkaline earth atoms is energetically favourable. All dimer adsorbed GeC systems have nonmagnetic semiconductor property with varying band gaps from 0.391 to 1.311 eV which are very suitable values for various device applications.

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.

PubMed

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.

Cathode architectures for alkali metal / oxygen batteries

DOEpatents

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.

Structures of Hydrated Alkali Metal Cations, M+(H2O)nAr (m = Li, Na, K, rb and Cs, n = 3-5), Using Infrared Photodissociation Spectroscopy and Thermodynamic Analysis

NASA Astrophysics Data System (ADS)

Ke, Haochen; van der Linde, Christian; Lisy, James M.

2014-06-01

Alkali metal cations play vital roles in chemical and biochemical systems. Lithium is widely used in psychiatric treatment of manic states and bipolar disorder; Sodium and potassium are essential elements, having major biological roles as electrolytes, balancing osmotic pressure on body cells and assisting the electroneurographic signal transmission; Rubidium has seen increasing usage as a supplementation for manic depression and depression treatment; Cesium doped compounds are used as essential catalysts in chemical production and organic synthesis. Since hydrated alkali metal cations are ubiquitous and the basic form of the alkali metal cations in chemical and biochemical systems, their structural and thermodynamic properties serve as the foundation for modeling more complex chemical and biochemical processes, such as ion transport and ion size-selectivity of ionophores and protein channels. By combining mass spectrometry and infrared photodissociation spectroscopy, we have characterized the structures and thermodynamic properties of the hydrated alkali metal cations, i.e. M+(H2O)nAr, (M = Li, Na, K, Rb and Cs, n = 3-5). Ab initio calculations and RRKM-EE (evaporative ensemble) calculations were used to assist in the spectral assignments and thermodynamic analysis. Results showed that the structures of hydrated alkali metal cations were determined predominantly by the competition between non-covalent interactions, i.e. the water---water hydrogen bonding interactions and the water---cation electrostatic interactions. This balance, however, is very delicate and small changes, i.e. different cations, different levels of hydration and different effective temperatures clearly impact the balance.

Phytoscreening as an efficient tool to delineate chlorinated solvent sources at a chlor-alkali facility.

PubMed

Yung, Loïc; Lagron, Jérôme; Cazaux, David; Limmer, Matt; Chalot, Michel

2017-05-01

Chlorinated ethenes (CE) are among the most common volatile organic compounds (VOC) that contaminate groundwater, currently representing a major source of pollution worldwide. Phytoscreening has been developed and employed through different applications at numerous sites, where it was generally useful for detection of subsurface chlorinated solvents. We aimed at delineating subsurface CE contamination at a chlor-alkali facility using tree core data that we compared with soil data. For this investigation a total of 170 trees from experimental zones was sampled and analyzed for perchloroethene (PCE) and trichloroethene (TCE) concentrations, measured by solid phase microextraction gas chromatography coupled to mass spectrometry. Within the panel of tree genera sampled, Quercus and Ulmus appeared to be efficient biomonitors of subjacent TCE and PCE contamination, in addition to the well known and widely used Populus and Salix genera. Among the 28 trees located above the dense non-aqueous phase liquid (DNAPL) phase zone, 19 tree cores contained detectable amounts of CE, with concentrations ranging from 3 to 3000 μg L -1 . Our tree core dataset was found to be well related to soil gas sampling results, although the tree coring data were more informative. Our data further emphasized the need for choosing the relevant tree species and sampling periods, as well as taking into consideration the nature of the soil and its heterogeneity. Overall, this low-invasive screening method appeared useful to delineate contaminants at a small-scale site impacted by multiple sources of chlorinated solvents. Copyright © 2017 Elsevier Ltd. All rights reserved.

Binding selectivity of dibenzo-18-crown-6 for alkali metal cations in aqueous solution: A density functional theory study using a continuum solvation model.

PubMed

Choi, Chang Min; Heo, Jiyoung; Kim, Nam Joon

2012-08-08

Dibenzo-18-crown-6 (DB18C6) exhibits the binding selectivity for alkali metal cations in solution phase. In this study, we investigate the main forces that determine the binding selectivity of DB18C6 for the metal cations in aqueous solution using the density functional theory (DFT) and the conductor-like polarizable continuum model (CPCM). The bond dissociation free energies (BDFE) of DB18C6 complexes with alkali metal cations (M+-DB18C6, M = Li, Na, K, Rb, and Cs) in aqueous solution are calculated at the B3LYP/6-311++G(d,p)//B3LYP/6-31 + G(d) level using the CPCM. It is found that the theoretical BDFE is the largest for K+-DB18C6 and decreases as the size of the metal cation gets larger or smaller than that of K+, which agrees well with previous experimental results. The solvation energy of M+-DB18C6 in aqueous solution plays a key role in determining the binding selectivity of DB18C6. In particular, the non-electrostatic dispersion interaction between the solute and solvent, which depends strongly on the complex structure, is largely responsible for the different solvation energies of M+-DB18C6. This study shows that the implicit solvation model like the CPCM works reasonably well in predicting the binding selectivity of DB18C6 in aqueous solution.

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

PubMed

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 < 2) and depends on the charge of the ligand, owing to the ionic nature of the interactions. At the same time, the size of the cation is an important factor that influences the stability: very often, but not always (e.g., for sulfate), it follows the trend Li(+) > 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).

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

PubMed

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.

The Alkali Metal Thermal-To-Electric Converter for Solar System Exploration

NASA Technical Reports Server (NTRS)

Ryan, M.

1999-01-01

AMTEC, the Alkali Metal Thermal to Electric Converter, is a direct thermal to electric energy conversion device; it has been demostrated to perform at high power densities, with open circuit voltages in single electrochemical cells up to 1.6 V and current desities up to 2.0 A/cm(sup 2).

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

NASA Astrophysics Data System (ADS)

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.

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

NASA Astrophysics Data System (ADS)

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.

Investigating the effects of alkali metal Na addition on catalytic activity of HZSM-5 for methyl mercaptan elimination

NASA Astrophysics Data System (ADS)

Yu, Jie; He, Dedong; Chen, Dingkai; Liu, Jiangping; Lu, Jichang; Liu, Feng; Liu, Pan; Zhao, Yutong; Xu, Zhizhi; Luo, Yongming

2017-10-01

Na-modified HZSM-5 catalysts with different Na loading amounts were prepared by incipient-wetness impregnation method and their catalytic activities for methyl mercaptan catalytic elimination were analyzed. XRD, N2 adsorption-desorption, NH3-TPD, CO2-TPD and FT-IR measurements were carried out to investigate the effects of modification of alkali metal Na on the physicochemical properties of the HZSM-5 zeolite catalyst. Research results illustrated that the introduction of alkali metal Na can improve catalytic activity for CH3SH catalytic elimination. CH3SH can be almost completely converted over 3%-Na/HZSM-5 at 450 °C compared to pure HZSM-5 at 600 °C based on our experimental results and the results from previous research. The improved catalytic activity could be attributed to the regulated acid-base properties of the HZSM-5 catalysts by doping with alkali metal Na. High alkali concentration treatment, however, may destroy the framework structure of the catalyst sample, thus causing the poor stability performance of the obtained catalyst.

S5 Lipase: an organic solvent tolerant enzyme.

PubMed

Rahman, Raja Noor Zaliha Abdul; Baharum, Syarul Nataqain; Salleh, Abu Bakar; Basri, Mahiran

2006-12-01

In this study, an organic solvent tolerant bacterial strain was isolated. This strain was identified as Pseudomonas sp. strain S5, and was shown to degrade BTEX (Benzene, Toluene, Ethyl-Benzene, and Xylene). Strain S5 generates an organic solvent-tolerant lipase in the late logarithmic phase of growth. Maximum lipase production was exhibited when peptone was utilized as the sole nitrogen source. Addition of any of the selected carbon sources to the medium resulted in a significant reduction of enzyme production. Lower lipase generation was noted when an inorganic nitrogen source was used as the sole nitrogen source. This bacterium hydrolyzed all tested triglycerides and the highest levels of production were observed when olive oil was used as a natural triglyceride. Basal medium containing Tween 60 enhanced lipase production to the most significant degree. The absence of magnesium ions (Mg2+) in the basal medium was also shown to stimulate lipase production. Meanwhile, an alkaline earth metal ion, Na+, was found to stimulate the production of S5 lipase.

Monitoring of photoluminescence decay by alkali and alkaline earth metal cations using a photoluminescent bolaamphiphile self-assembly as an optical probe.

PubMed

Kim, Sunhyung; Kwak, Jinyoung; Lee, Sang-Yup

2014-05-01

Photoluminescence (PL) decay induced by the displacement of an ionic fluorescence component, Tb(3+), with alkali and alkaline earth metal cations was investigated using photoluminescent spherical self-assemblies as optical probes. The photoluminescent spherical self-assembly was prepared by the self-organization of a tyrosine-containing bolaamphiphile molecule with a photosensitizer and Tb(3+) ion. The lanthanide ion, Tb(3+), electrically bound to the carboxyl group of the bolaamphiphile molecule, was displaced by alkali and alkaline earth metal cations that had stronger electrophilicity. The PL of the self-assembly decayed remarkably due to the substitution of lanthanide ions with alkali and alkaline earth metal cations. The PL decay showed a positive correlation with cation concentration and was sensitive to the cation valency. Generally, the PL decay was enhanced by the electrophilicity of the cations. However, Ca(2+) showed greater PL decay than Mg(2+) because Ca(2+) could create various complexes with the carboxyl groups of the bolaamphiphile molecule. Microscopic and spectroscopic investigations were conducted to study the photon energy transfer and displacement of Tb(3+) by the cation exchange. This study demonstrated that the PL decay by the displacement of the ionic fluorescent compound was applied to the detection of various cations in aqueous media and is applicable to the development of future optical sensors. Copyright © 2014 Elsevier B.V. All rights reserved.

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

PubMed

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.

A Study of the Hydration of the Alkali Metal Ions in Aqueous Solution

PubMed Central

2011-01-01

The hydration of the alkali metal ions in aqueous solution has been studied by large angle X-ray scattering (LAXS) and double difference infrared spectroscopy (DDIR). The structures of the dimethyl sulfoxide solvated alkali metal ions in solution have been determined to support the studies in aqueous solution. The results of the LAXS and DDIR measurements show that the sodium, potassium, rubidium and cesium ions all are weakly hydrated with only a single shell of water molecules. The smaller lithium ion is more strongly hydrated, most probably with a second hydration shell present. The influence of the rubidium and cesium ions on the water structure was found to be very weak, and it was not possible to quantify this effect in a reliable way due to insufficient separation of the O–D stretching bands of partially deuterated water bound to these metal ions and the O–D stretching bands of the bulk water. Aqueous solutions of sodium, potassium and cesium iodide and cesium and lithium hydroxide have been studied by LAXS and M–O bond distances have been determined fairly accurately except for lithium. However, the number of water molecules binding to the alkali metal ions is very difficult to determine from the LAXS measurements as the number of distances and the temperature factor are strongly correlated. A thorough analysis of M–O bond distances in solid alkali metal compounds with ligands binding through oxygen has been made from available structure databases. There is relatively strong correlation between M–O bond distances and coordination numbers also for the alkali metal ions even though the M–O interactions are weak and the number of complexes of potassium, rubidium and cesium with well-defined coordination geometry is very small. The mean M–O bond distance in the hydrated sodium, potassium, rubidium and cesium ions in aqueous solution have been determined to be 2.43(2), 2.81(1), 2.98(1) and 3.07(1) Å, which corresponds to six-, seven-, eight- and

General Solvent-dependent Strategy toward Enhanced Oxygen Reduction Reaction in Graphene/Metal Oxide Nanohybrids: Effects of Nitrogen-containing Solvent

NASA Astrophysics Data System (ADS)

Kao, Wei-Yao; Chen, Wei-Quan; Chiu, Yu-Hsiang; Ho, Yu-Hsuan; Chen, Chun-Hu

2016-11-01

A general solvent-dependent protocol directly influencing the oxygen reduction reaction (ORR) in metal oxide/graphene nanohybrids has been demonstrated. We conducted the two-step synthesis of cobalt oxide/N-doped graphene nanohybrids (CNG) with solvents of water, ethanol, and dimethylformamide (DMF), representing tree typical categories of aqueous, polar organic, and organic N-containing solvents commonly adopted for graphene nanocomposites preparation. The superior ORR performance of the DMF-hybrids can be attributed to the high nitrogen-doping, aggregation-free hybridization, and unique graphene porous structures. As DMF is the more effective N-source, the spectroscopic results support a catalytic nitrogenation potentially mediated by cobalt-DMF coordination complexes. The wide-distribution of porosity (covering micro-, meso-, to macro-pore) and micron-void assembly of graphene may further enhance the diffusion kinetics for ORR. As the results, CNG by DMF-synthesis exhibits the high ORR activities close to Pt/C (i.e. only 8 mV difference of half-wave potential with electron transfer number of 3.96) with the better durability in the alkaline condition. Additional graphene hybrids comprised of iron and manganese oxides also show the superior ORR activities by DMF-synthesis, confirming the general solvent-dependent protocol to achieve enhanced ORR activities.

General Solvent-dependent Strategy toward Enhanced Oxygen Reduction Reaction in Graphene/Metal Oxide Nanohybrids: Effects of Nitrogen-containing Solvent

PubMed Central

Kao, Wei-Yao; Chen, Wei-Quan; Chiu, Yu-Hsiang; Ho, Yu-Hsuan; Chen, Chun-Hu

2016-01-01

A general solvent-dependent protocol directly influencing the oxygen reduction reaction (ORR) in metal oxide/graphene nanohybrids has been demonstrated. We conducted the two-step synthesis of cobalt oxide/N-doped graphene nanohybrids (CNG) with solvents of water, ethanol, and dimethylformamide (DMF), representing tree typical categories of aqueous, polar organic, and organic N-containing solvents commonly adopted for graphene nanocomposites preparation. The superior ORR performance of the DMF-hybrids can be attributed to the high nitrogen-doping, aggregation-free hybridization, and unique graphene porous structures. As DMF is the more effective N-source, the spectroscopic results support a catalytic nitrogenation potentially mediated by cobalt-DMF coordination complexes. The wide-distribution of porosity (covering micro-, meso-, to macro-pore) and micron-void assembly of graphene may further enhance the diffusion kinetics for ORR. As the results, CNG by DMF-synthesis exhibits the high ORR activities close to Pt/C (i.e. only 8 mV difference of half-wave potential with electron transfer number of 3.96) with the better durability in the alkaline condition. Additional graphene hybrids comprised of iron and manganese oxides also show the superior ORR activities by DMF-synthesis, confirming the general solvent-dependent protocol to achieve enhanced ORR activities. PMID:27853187

Carbothermic reduction of uranium oxides into solvent metallic baths

NASA Astrophysics Data System (ADS)

Guisard Restivo, Thomaz A.; Capocchi, José D. T.

2004-09-01

The carbothermic reduction of UO 2 and U 3O 8 is studied employing tin and silicon solvent metallic baths in thermal analysis equipment, under Ar inert and N 2 reactive atmospheres. The metallic solvents are expected to lower the U activity by several orders of magnitude owing to strong interactions among the metals. The reduction products are composed of the solvent metal matrix and intermetallic U compounds. Silicon is more effective in driving the reduction since there is no residual UO 2 after the reaction. The gaseous product detected by mass spectrometer (MS) during the reduction is CO. A kinetic study for the Si case was accomplished by the stepwise isothermal analysis (SAI) method, leading to the identification of the controlling mechanisms as chemical reaction at the surface and nucleation, for UO 2 and U 3O 8 charges, respectively. One example for another system containing Al 2O 3 is also shown.

Alkali-metal silicate binders and methods of manufacture

NASA Technical Reports Server (NTRS)

Schutt, J. B. (Inventor)

1979-01-01

A paint binder is described which uses a potassium or sodium silicate dispersion having a silicon dioxide to alkali-metal oxide mol ratio of from 4.8:1 to 6.0:1. The binder exhibits stability during both manufacture and storage. The process of making the binder is predictable and repeatable and the binder may be made with inexpensive components. The high mol ratio is achieved with the inclusion of a silicon dioxide hydrogel. The binder, which also employs a silicone, is in the final form of a hydrogel sol.

Organic solvent regeneration of granular activated carbon

NASA Astrophysics Data System (ADS)

Cross, W. H.; Suidan, M. T.; Roller, M. A.; Kim, B. R.; Gould, J. P.

1982-09-01

The use of activated carbon for the treatment of industrial waste-streams was shown to be an effective treatment. The high costs associated with the replacement or thermal regeneration of the carbon have prohibited the economic feasibility of this process. The in situ solvent regeneration of activated carbon by means of organic solvent extraction was suggested as an economically alternative to thermal regeneration. The important aspects of the solvent regeneration process include: the physical and chemical characteristics of the adsorbent, the pore size distribution and energy of adsorption associated with the activated carbon; the degree of solubility of the adsorbate in the organic solvent; the miscibility of the organic solvent in water; and the temperature at which the generation is performed.

Study of the reaction of tungsten carbide in molten alkali metal nitrates. Syntheses of divalent (s and d blocks) metal tungstates

NASA Astrophysics Data System (ADS)

Deloume, Jean-Pierre; Marote, Pedro; Sigala, Catherine; Matei, Cristian

2003-08-01

WC is tested as precursor to synthesize metal tungstates by reaction in molten alkali metal nitrates. This constitutes a complex redox system with two reducing agents, W and C, and an oxidizer having several oxidation states. The mass loss due to the evolution of gases reveals the reaction steps. The infrared analyses of the gas phase show what kind of reaction develops according to the temperature. WC produces a water-soluble alkali metal tungstate. The reaction of a mixture of WC and a divalent metal chloride (Mg, Ca, Ba, Ni, Cu, Zn) leads to water-insoluble metal tungstates. As the reactivity of the cations increases in the order Zn, Ni, Cu, the reaction of WC is modified by their presence. The physico-chemical characterizations of the products show that some of them are contaminated either by WC or by metal oxide. Some others are rather pure products. These differences, in relationship with the other analyses, allow to propose first reaction pathways of the tungsten carbide in molten salts.

Solvent-induced assembly of two helical Eu(III) metal-organic frameworks and fluorescence sensing activities towards nitrobenzene and Cu2+ ions

NASA Astrophysics Data System (ADS)

Ma, Ranran; Chen, Zhiwei; Wang, Suna; Yao, Qingxia; Li, Yunwu; Lu, Jing; Li, Dacheng; Dou, Jianmin

2017-08-01

Two helical Eu(III) metal-organic frameworks, namely, {[Eu(L)(DMF)(H2O)]·0.5DMF}n (1) and [Eu(L)(DEF)(H2O)]n (2) (H3L=3,5-bis(2-carboxylphenoxy)benzoic acid, DMF=N,N-dimethylformamide, DEF=N,N-diethylformamide), have been solvothermally synthesized in different solvents, respectively. Both complexes possess helical structures through the connectivity of Eu atoms and phenolic-oxygen containing branches of the flexible multicarboxylate ligand. Based on different helices, these two complexes exhibited hexagonal and tetragonal channels, respectively. Both complexes possess (3,6)-connected (4.62)2(42.610.83) topology but with different long Schlafli symbol. The solvent plays an important role in the formation of the final frameworks. Both complexes can sensitively and selectively detect nitrobenzene and Cu2+ ions.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-31

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Oxidation behavior of Cr(III) during thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides.

PubMed

Mao, Linqiang; Gao, Bingying; Deng, Ning; Liu, Lu; Cui, Hao

2016-02-01

The oxidation behavior of Cr(III) during the thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides (NaCl, KCl, MgCl2, and CaCl2) was investigated. The amounts of Cr(III) oxidized at various temperatures and heating times were determined, and the Cr-containing species in the residues were characterized. During the transformation of chromium hydroxide to Cr2O3 at 300 °C approximately 5% of the Cr(III) was oxidized to form intermediate compounds containing Cr(VI) (i.e., CrO3), but these intermediates were reduced to Cr2O3 when the temperature was above 400 °C. Alkali and alkaline earth metals significantly promoted the oxidation of Cr(III) during the thermal drying process. Two pathways were involved in the influences the alkali and alkaline earth metals had on the formation of Cr(VI). In pathway I, the alkali and alkaline earth metals were found to act as electron transfer agents and to interfere with the dehydration process, causing more intermediate Cr(VI)-containing compounds (which were identified as being CrO3 and Cr5O12) to be formed. The reduction of intermediate compounds to Cr2O3 was also found to be hindered in pathway I. In pathway II, the alkali and alkaline earth metals were found to contribute to the oxidation of Cr(III) to form chromates. The results showed that the presence of alkali and alkaline earth metals significantly increases the degree to which Cr(III) is oxidized during the thermal drying of chromium-containing sludge. Copyright © 2015 Elsevier Ltd. All rights reserved.

pH tunability and influence of alkali metal basicity on the plasmonic resonance of silver nanoparticles

NASA Astrophysics Data System (ADS)

Yadav, Vijay D.; Akhil Krishnan, R.; Borade, Lalit; Shirolikar, Seema; Jain, Ratnesh; Dandekar, Prajakta

2017-07-01

Localized surface plasmon resonance has been a unique and intriguing feature of silver nanoparticles (AgNPs) that has attracted immense attention. This has led to an array of applications for AgNPs in optics, sensors, plasmonic imaging etc. Although numerous applications have been reported consistently, the importance of buffer and reaction parameters during the synthesis of AgNPs, is still unclear. In the present study, we have demonstrated the influence of parameters like pH, temperature and buffer conditions (0.1 M citrate buffer) on the plasmonic resonance of AgNPs. We found that neutral and basic pH (from alkali metal) provide optimum interaction conditions for nucleation of plasmon resonant AgNPs. Interestingly, this was not observed in the non-alkali metal base (ammonia). Also, when the nanoparticles synthesized from alkali metal base were incorporated in different buffers, it was observed that the nanoparticles dissolved in the acidic buffer and had reduced plasmonic resonance intensity. This, however, was resolved in the basic buffer, increasing the plasmonic resonance intensity and confirming that nucleation of nanoparticles required basic conditions. The above inference has been supported by characterization of AgNPs using UV-Vis spectrophotometer, Fluorimetry analysis, Infrared spectrometer and TEM analysis. The study concluded that the plasmonic resonance of AgNPs occurs due to the interaction of alkali (Na) and transition metal (Ag) salt in basic/neutral conditions, at a specific temperature range, in presence of a capping agent (citric acid), providing a pH tune to the overall system.

Biodegradable organic acid-crosslinked alkali-treated gelatins with anti-thrombogenic and endothelialization properties

PubMed Central

Inoue, Motoki; Sasaki, Makoto; Taguchi, Tetsushi

2012-01-01

Gelatins were crosslinked with organic acids and treated with alkali to impart to them endothelialization and anti-thrombogenic properties. These matrices were characterized by biochemical and physicochemical techniques. The amounts of residual amino groups in the matrices decreased with increasing crosslinker concentration. The matrices with the highest crosslinking densities showed excellent endothelial cell adhesion and proliferation. In addition, the adhesion of platelets and formation of fibrin networks on the matrices were suppressed with increasing crosslinker concentration. The matrices also exhibited excellent biodegradability, and the degradation rate decreased with increasing crosslinking density. All the organic acid-crosslinked alkali-treated gelatins showed excellent anti-thrombogenic and endothelialization properties, superior to those of glutaraldehyde-crosslinked alkali-treated gelatins. PMID:27877542

Solvent properties of hydrazine in the preparation of metal chalcogenide bulk materials and films.

PubMed

Yuan, Min; Mitzi, David B

2009-08-21

A combination of unique solvent properties of hydrazine enables the direct dissolution of a range of metal chalcogenides at ambient temperature, rendering this an extraordinarily simple and soft synthetic approach to prepare new metal chalcogenide-based materials. The extended metal chalcogenide parent framework is broken up during this process, and the resulting metal chalcogenide building units are re-organized into network structures (from 0D to 3D) based upon their interactions with the hydrazine/hydrazinium moieties. This Perspective will review recent crystal and materials chemistry developments within this family of compounds and will briefly discuss the utility of this approach in metal chalcogenide thin-film deposition.

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

DOE PAGES

Fabbris, G.; Lim, J.; Veiga, L. S. I.; ...

2015-02-17

Here, alkali metals display unexpected properties at high pressure, including emergence of low symmetry crystal structures, that 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 ab initio 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 oC84 phase in Cs. Both the experimental and theoretical results point to pressure-enhanced localization of themore » valence electrons characterized by pseudo-gap formation near the Fermi level and strong spd 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.« less

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

NASA Astrophysics Data System (ADS)

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.

Enhanced performance of dicationic ionic liquid electrolytes by organic solvents.

PubMed

Li, Song; Zhang, Pengfei; Fulvio Pasquale, F; Hillesheim Patrick, C; Feng, Guang; Dai, Sheng; Cummings Peter, T

2014-07-16

The use of dicationic ionic liquid (DIL) electrolytes in supercapacitors is impeded by the slow dynamics of DILs, whereas the addition of organic solvents into DIL electrolytes improves ion transport and then enhances the power density of supercapacitors. In this work, the influences of organic solvents on the conductivity of DILs and the electrical double layer (EDL) of DIL-based supercapacitors are investigated using classical molecular dynamics simulation. Two types of organic solvents, acetonitrile (ACN) and propylene carbonate (PC), were used to explore the effects of different organic solvents on the EDL structure and capacitance of DIL/organic solvent-based supercapacitors. Firstly, it was found that the conductivity of DIL electrolytes was greatly enhanced in the presence of the organic solvent ACN. Secondly, a stronger adsorption of PC on graphite results in different EDL structures formed by DIL/ACN and DIL/PC electrolytes. The expulsion of co-ions from EDLs was observed in DIL/organic solvent electrolytes rather than neat DILs and this feature is more evident in DIL/PC. Furthermore, the bell-shaped differential capacitance-electric potential curve was not essentially changed by the presence of organic solvents. Comparing DIL/organic solvent electrolytes with neat DILs, the capacitance is slightly increased by organic solvents, which is in agreement with experimental observation.

Aqueous Alkaline Cleaners: An Alternative to Organic Solvents

DTIC Science & Technology

1993-09-01

F021, F022, F023, F026, F027, F1028) Spent solvents (FOOl, F002, F003, F004, F005) July 8, 1987 California list wastes (Liquid hazardous wastes...installations and has been successful in developing a recycling program to reclaim spent Stoddard solvent and produce a material that meets Army specifications...metal parts it has cleaned. As the contamination level rises, it depletes the solvent’s effective cleaning power until the solvent becomes " spent

Crystal growth of sulfide materials from alkali polysulfide liquids

NASA Technical Reports Server (NTRS)

White, W. B.

1979-01-01

The fluids experiment system was designed for low temperature solution growth, nominally aqueous solution growth. The alkali polysulfides, compositions in the systems Na2S-S and K2S-S form liquids in the temperature range of 190 C to 400 C. These can be used as solvents for other important classes of materials such as transition metal and other sulfides which are not soluble in aqueous media. Among these materials are luminescent and electroluminescent crystals whose physical properties are sensitive functions of crystal perfection and which could, therefore, serve as test materials for perfection improvement under microgravity conditions.

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

NASA Astrophysics Data System (ADS)

Hummelshøj, J. S.; Landis, D. D.; Voss, J.; Jiang, T.; Tekin, A.; Bork, N.; Dułak, M.; Mortensen, J. J.; Adamska, L.; Andersin, J.; Baran, J. D.; Barmparis, G. D.; Bell, F.; Bezanilla, A. L.; Bjork, J.; Björketun, M. E.; Bleken, F.; Buchter, F.; Bürkle, M.; Burton, P. D.; Buus, B. B.; Calborean, A.; Calle-Vallejo, F.; Casolo, S.; Chandler, B. D.; Chi, D. H.; Czekaj, I.; Datta, S.; Datye, A.; DeLaRiva, A.; Despoja, V.; Dobrin, S.; Engelund, M.; Ferrighi, L.; Frondelius, P.; Fu, Q.; Fuentes, A.; Fürst, J.; García-Fuente, A.; Gavnholt, J.; Goeke, R.; Gudmundsdottir, S.; Hammond, K. D.; Hansen, H. A.; Hibbitts, D.; Hobi, E.; Howalt, J. G.; Hruby, S. L.; Huth, A.; Isaeva, L.; Jelic, J.; Jensen, I. J. T.; Kacprzak, K. A.; Kelkkanen, A.; Kelsey, D.; Kesanakurthi, D. S.; Kleis, J.; Klüpfel, P. J.; Konstantinov, I.; Korytar, R.; Koskinen, P.; Krishna, C.; Kunkes, E.; Larsen, A. H.; Lastra, J. M. G.; Lin, H.; Lopez-Acevedo, O.; Mantega, M.; Martínez, J. I.; Mesa, I. N.; Mowbray, D. J.; Mýrdal, J. S. G.; Natanzon, Y.; Nistor, A.; Olsen, T.; Park, H.; Pedroza, L. S.; Petzold, V.; Plaisance, C.; Rasmussen, J. A.; Ren, H.; Rizzi, M.; Ronco, A. S.; Rostgaard, C.; Saadi, S.; Salguero, L. A.; Santos, E. J. G.; Schoenhalz, A. L.; Shen, J.; Smedemand, M.; Stausholm-Møller, O. J.; Stibius, M.; Strange, M.; Su, H. B.; Temel, B.; Toftelund, A.; Tripkovic, V.; Vanin, M.; Viswanathan, V.; Vojvodic, A.; Wang, S.; Wellendorff, J.; Thygesen, K. S.; Rossmeisl, J.; Bligaard, T.; Jacobsen, K. W.; Nørskov, J. K.; Vegge, T.

2009-07-01

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 metal atom (M2) plus two to five (BH4)- groups, i.e., M1M2(BH4)2-5, using a number of model structures with trigonal, tetrahedral, octahedral, and free coordination of the metal borohydride complexes. Of the over 700 investigated structures, about 20 were predicted to form potentially stable alloys with promising decomposition energies. The M1(Al/Mn/Fe)(BH4)4, (Li/Na)Zn(BH4)3, and (Na/K)(Ni/Co)(BH4)3 alloys are found to be the most promising, followed by selected M1(Nb/Rh)(BH4)4 alloys.

Yarrowia lipolytica possesses two plasma membrane alkali metal cation/H+ antiporters with different functions in cell physiology.

PubMed

Papouskova, Klara; Sychrova, Hana

2006-04-03

The family of Nha antiporters mediating the efflux of alkali metal cations in exchange for protons across the plasma membrane is conserved in all yeast species. Yarrowia lipolytica is a dimorphic yeast, phylogenetically very distant from the model yeast Saccharomyces cerevisiae. A search in its sequenced genome revealed two genes (designated as YlNHA1 and YlNHA2) with homology to the S. cerevisiae NHA1 gene, which encodes a plasma membrane alkali metal cation/H+ antiporter. Upon heterologous expression of both YlNHA genes in S. cerevisiae, we showed that Y. lipolytica antiporters differ not only in length and sequence, but also in their affinity for individual substrates. While the YlNha1 protein mainly increased cell tolerance to potassium, YlNha2p displayed a remarkable transport capacity for sodium. Thus, Y. lipolytica is the first example of a yeast species with two plasma membrane alkali metal cation/H+ antiporters differing in their putative functions in cell physiology; cell detoxification vs. the maintenance of stable intracellular pH, potassium content and cell volume.

Structural basis for regioisomerization in the alkali-metal-mediated zincation (AMMZn) of trifluoromethyl benzene by isolation of kinetic and thermodynamic intermediates.

PubMed

Armstrong, David R; Blair, Victoria L; Clegg, William; Dale, Sophie H; Garcia-Alvarez, Joaquin; Honeyman, Gordon W; Hevia, Eva; Mulvey, Robert E; Russo, Luca

2010-07-14

Performed with a desire to advance knowledge of the structures and mechanisms governing alkali-metal-mediated zincation, this study monitors the reaction between the TMP-dialkylzincate reagent [(TMEDA)Na(TMP)((t)Bu)Zn((t)Bu)] 1 and trifluoromethyl benzene C(6)H(5)CF(3) 2. A complicated mixture of products is observed at room temperature. X-ray crystallography has identified two of these products as ortho- and meta-regioisomers of heterotrianionic [(TMEDA)Na(TMP)(C(6)H(4)-CF(3))Zn((t)Bu)], 3-ortho and 3-meta, respectively. Multinuclear NMR data of the bulk crystalline product confirm the presence of these two regioisomers as well as a third isomer, 3-para, in a respective ratio of 20:11:1, and an additional product 4, which also exhibits ortho-zincation of the aryl substrate. Repeating the reaction at 0 degrees C gave exclusively 4, which was crystallographically characterized as [{(TMEDA)(2)Na}(+){Zn(C(6)H(4)-CF(3))((t)Bu)(2)}(-)]. Mimicking the original room-temperature reaction, this kinetic product was subsequently reacted with TMP(H) to afford a complicated mixture of products, including significantly the three regioisomers of 3. Surprisingly, 4 adopts a solvent-separated ion pair arrangement in contrast to the contacted ion variants of 3-ortho and 3-meta. Aided by DFT calculations on model systems, discussion focuses on the different basicities, amido or alkyl, and steps, exhibited in these reactions, and how the structures and bonding within these isolated key metallic intermediates (prior to any electrophilic interception step), specifically the interactions involving the alkali metal, influence the regioselectivity of the Zn-H exchange process.

SEPARATION OF METAL VALUES FROM NUCLEAR REACTOR

DOEpatents

Campbell, D.O.; Cathers, G.I.

1962-06-19

A method is given for separating beryllium fluoride and an alkali metal fluoride from a mixture containing same and rare earth fluorides. The method comprises contacting said mixture with a liquid hydrogen fluoride solvent containing no more than about 30 per cent water by weight and saturated with a fluoride salt characterized by its solubility in anhydrous hydrogen fluoride for a period of time sufficient to dissolve said beryllium fluoride in said solvent. (AEC)

Alkali activation of recovered fuel-biofuel fly ash from fluidised-bed combustion: Stabilisation/solidification of heavy metals.

PubMed

Yliniemi, Juho; Pesonen, Janne; Tiainen, Minna; Illikainen, Mirja

2015-09-01

Recovered fuel-biofuel fly ash from a fluidized bed boiler was alkali-activated and granulated with a sodium-silicate solution in order to immobilise the heavy metals it contains. The effect of blast-furnace slag and metakaolin as co-binders were studied. Leaching standard EN 12457-3 was applied to evaluate the immobilisation potential. The results showed that Ba, Pb and Zn were effectively immobilised. However, there was increased leaching after alkali activation for As, Cu, Mo, Sb and V. The co-binders had minimal or even negative effect on the immobilisation. One exception was found for Cr, in which the slag decreased leaching, and one was found for Cu, in which the slag increased leaching. A sequential leaching procedure was utilized to gain a deeper understanding of the immobilisation mechanism. By using a sequential leaching procedure it is possible fractionate elements into watersoluble, acid-soluble, easily-reduced and oxidisable fractions, yielding a total 'bioavailable' amount that is potentially hazardous for the environment. It was found that the total bioavailable amount was lower following alkali activation for all heavy metals, although the water-soluble fraction was higher for some metals. Evidence from leaching tests suggests the immobilisation mechanism was chemical retention, or trapping inside the alkali activation reaction products, rather than physical retention, adsorption or precipitation as hydroxides. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

PubMed

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

Solvent-free fluidic organic dye lasers.

PubMed

Choi, Eun Young; Mager, Loic; Cham, Tran Thi; Dorkenoo, Kokou D; Fort, Alain; Wu, Jeong Weon; Barsella, Alberto; Ribierre, Jean-Charles

2013-05-06

We report on the demonstration of liquid organic dye lasers based on 9-(2-ethylhexyl)carbazole (EHCz), so-called liquid carbazole, doped with green- and red-emitting laser dyes. Both waveguide and Fabry-Perot type microcavity fluidic organic dye lasers were prepared by capillary action under solvent-free conditions. Cascade Förster-type energy transfer processes from liquid carbazole to laser dyes were employed to achieve color-variable amplified spontaneous emission and lasing. Overall, this study provides the first step towards the development of solvent-free fluidic organic semiconducting lasers and demonstrates a new kind of optoelectronic applications for liquid organic semiconductors.

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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). Na2/3[Mg0.28Mn0.72]O2 exhibits an excess capacity and here we show that this is caused by oxygen redox, even though Mg2+ 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, Na2/3[Mg0.28Mn0.72]O2 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 Mg2+ remains in Na2/3[Mg0.28Mn0.72]O2, which stabilizes oxygen.

Theoretical analysis of oxygen diffusion at startup in an alkali metal heat pipe with gettered alloy walls

NASA Technical Reports Server (NTRS)

Tower, L. K.

1973-01-01

The diffusion of oxygen into, or out of, a gettered alloy exposed to oxygenated alkali liquid metal coolant, a situation arising in some high temperature heat transfer systems, was analyzed. The relation between the diffusion process and the thermochemistry of oxygen in the alloy and in the alkali metal was developed by making several simplifying assumptions. The treatment is therefore theoretical in nature. However, a practical example pertaining to the startup of a heat pipe with walls of T-111, a tantalum alloy, and lithium working fluid illustrates the use of the figures contained in the analysis.

Effect of Alkali Metal Cations on Slow Inactivation of Cardiac Na+ Channels

PubMed Central

Townsend, Claire; Horn, Richard

1997-01-01

Human heart Na+ channels were expressed transiently in both mammalian cells and Xenopus oocytes, and Na+ currents measured using 150 mM intracellular Na+. The kinetics of decaying outward Na+ current in response to 1-s depolarizations in the F1485Q mutant depends on the predominant cation in the extracellular solution, suggesting an effect on slow inactivation. The decay rate is lower for the alkali metal cations Li+, Na+, K+, Rb+, and Cs+ than for the organic cations Tris, tetramethylammonium, N-methylglucamine, and choline. In whole cell recordings, raising [Na+]o from 10 to 150 mM increases the rate of recovery from slow inactivation at −140 mV, decreases the rate of slow inactivation at relatively depolarized voltages, and shifts steady-state slow inactivation in a depolarized direction. Single channel recordings of F1485Q show a decrease in the number of blank (i.e., null) records when [Na+]o is increased. Significant clustering of blank records when depolarizing at a frequency of 0.5 Hz suggests that periods of inactivity represent the sojourn of a channel in a slow-inactivated state. Examination of the single channel kinetics at +60 mV during 90-ms depolarizations shows that neither open time, closed time, nor first latency is significantly affected by [Na+]o. However raising [Na+]o decreases the duration of the last closed interval terminated by the end of the depolarization, leading to an increased number of openings at the depolarized voltage. Analysis of single channel data indicates that at a depolarized voltage a single rate constant for entry into a slow-inactivated state is reduced in high [Na+]o, suggesting that the binding of an alkali metal cation, perhaps in the ion-conducting pore, inhibits the closing of the slow inactivation gate. PMID:9234168

Mutations in M2 alter the selectivity of the mouse nicotinic acetylcholine receptor for organic and alkali metal cations

PubMed Central

1992-01-01

We measured the permeability ratios (PX/PNa) of 3 wild-type, 1 hybrid, 2 subunit-deficient, and 22 mutant nicotinic receptors expressed in Xenopus oocytes for alkali metal and organic cations using shifts in the bi-ionic reversal potential of the macroscopic current. Mutations at three positions (2', 6', 10') in M2 affected ion selectivity. Mutations at position 2' (alpha Thr244, beta Gly255, gamma Thr253, delta Ser258) near the intracellular end of M2 changed the organic cation permeability ratios as much as twofold and reduced PCs/PNa and PK/PNa by 16-18%. Mutations at positions 6' and 10' increased the glycine ethyl ester/Na+ and glycine methyl ester/Na+ permeability ratios. Two subunit alterations also affected selectivity: omission of the delta subunit reduced PCs/PNa by 16%, and substitution of Xenopus delta for mouse delta increased Pguanidinium/PNa more than twofold and reduced PCs/PNa by 34% and PLi/PNa by 20%. The wild-type mouse receptor displayed a surprising interaction with the primary ammonium cations; relative permeability peaked at a chain length equal to four carbons. Analysis of the organic permeability ratios for the wild-type mouse receptor shows that (a) the diameter of the narrowest part of the pore is 8.4 A; (b) the mouse receptor departs significantly from size selectivity for monovalent organic cations; and (c) lowering the temperature reduces Pguanidinium/PNa by 38% and Pbutylammonium/PNa more than twofold. The results reinforce present views that positions -1' and 2' are the narrowest part of the pore and suggest that positions 6' and 10' align some permeant organic cations in the pore in an interaction similar to that with channel blocker, QX-222. PMID:1431803

Integrated oil production and upgrading using molten alkali metal

DOEpatents

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

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

None

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 tomore » 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.« less

Radioisotope powered alkali metal thermoelectric converter design for space systems

NASA Technical Reports Server (NTRS)

Sievers, R. K.; Bankston, C. P.

1988-01-01

The design concept of an alkali-metal thermoelectric converter (AMTEC) for 15-30-percent-efficient conversion of heat from the General Purpose (radioisotope) Heat Source (GPHS) on spacecraft is presented. The basic physical principles of the conversion cycle are outlined; a theoretical model is derived; a modular design is described and illustrated with drawings; and the overall AMTEC/GPHS system design is characterized. Predicted performance data are presented in extensive tables and graphs and discussed in detail.

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

DOEpatents

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.

A fluorescent paramagnetic Mn metal–organic framework based on semi-rigid pyrene tetra­carboxylic acid: sensing of solvent polarity and explosive nitroaromatics

PubMed Central

Bajpai, Alankriti; Mukhopadhyay, Arindam; Krishna, Manchugondanahalli Shivakumar; Govardhan, Savitha; Moorthy, Jarugu Narasimha

2015-01-01

An Mn metal–organic framework (Mn-MOF), Mn-L, based on a pyrene-tetraacid linker (H4 L), displays a respectable fluorescence quantum yield of 8.3% in spite of the presence of the paramagnetic metal ions, due presumably to fixation of the metal ions in geometries that do not allow complete energy/charge-transfer quenching. Remarkably, the porous Mn-L MOF with ∼25% solvent-accessible volume exhibits a heretofore unprecedented solvent-dependent fluorescence emission maximum, permitting its use as a probe of solvent polarity; the emission maxima in different solvents correlate excellently with Reichardt’s solvent polarity parameter (E T N). Further, the applicability of Mn-L to the sensing of nitroaromatics via fluorescence quenching is demonstrated; the detection limit for TNT is shown to be 125 p.p.m. The results bring out the fact that MOFs based on paramagnetic metal ions can indeed find application when the quenching mechanisms are attenuated by certain geometries of the organic linkers of the MOF. PMID:26306197

Fluconazole affects the alkali-metal-cation homeostasis and susceptibility to cationic toxic compounds of Candida glabrata.

PubMed

Elicharova, Hana; Sychrova, Hana

2014-08-01

Candida glabrata is a salt-tolerant and fluconazole (FLC)-resistant yeast species. Here, we analyse the contribution of plasma-membrane alkali-metal-cation exporters, a cation/proton antiporter and a cation ATPase to cation homeostasis and the maintenance of membrane potential (ΔΨ). Using a series of single and double mutants lacking CNH1 and/or ENA1 genes we show that the inability to export potassium and toxic alkali-metal cations leads to a slight hyperpolarization of the plasma membrane of C. glabrata cells; this hyperpolarization drives more cations into the cells and affects cation homeostasis. Surprisingly, a much higher hyperpolarization of C. glabrata plasma membrane was produced by incubating cells with subinhibitory concentrations of FLC. FLC treatment resulted in a substantially increased sensitivity of cells to various cationic drugs and toxic cations that are driven into the cell by negative-inside plasma-membrane potential. The effect of the combination of FLC plus cationic drug treatment was enhanced by the malfunction of alkali-metal-cation transporters that contribute to the regulation of membrane potential and cation homeostasis. In summary, we show that the combination of subinhibitory concentrations of FLC and cationic drugs strongly affects the growth of C. glabrata cells. © 2014 The Authors.

Solvent-Assisted Linker Exchange: An Alternative to the De Novo Synthesis of Unattainable Metal-Organic Frameworks

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

Karagiaridi, Olga; Bury, Wojciech; Mondloch, Joseph E.

Metal-organic frameworks (MOFs) have gained considerable attention as hybrid materials—in part because of a multitude of potential useful applications, ranging from gas separation to catalysis and light harvesting. Unfortunately, de novo synthesis of MOFs with desirable function–property combinations is not always reliable and may suffer from vagaries such as formation of undesirable topologies, low solubility of precursors, and loss of functionality of the sensitive network components. The recently discovered synthetic approach coined solvent-assisted linker exchange (SALE) constitutes a simple to implement strategy for circumventing these setbacks; its use has already led to the generation of a variety of MOF materialsmore » previously unobtainable by direct synthesis methods. This Review provides a perspective of the achievements in MOF research that have been made possible with SALE and examines the studies that have facilitated the understanding and broadened the scope of use of this invaluable synthetic tool.« less

Charge transfer and injection barrier at the metal-organic interfaces

NASA Astrophysics Data System (ADS)

Yan, Li

2002-09-01

The metal-organic interface plays a critical role in determining the functionality and performance of many innovative organic based devices. It has attracted extensive research interests in recent years. This thesis presents investigations of the electronic structures of organic materials, such as tris-(8-hydroxyquinoline) aluminum (Alq3) and copper phthalocyanine (CuPc), during their interface formation with metals. The characterization is accomplished by X-ray and ultraviolet photoelectron spectroscopes (XPS and UPS) and inverse photoelectron spectroscopy (IPES). As discussed herein, both occupied and unoccupied electronic states at the interfaces are carefully examined in different aspects. In Chapter 4, the charge transfer and chemical reaction at various metal/Alq3 interfaces are investigated using XPS and UPS to study the electron injection into the Alga film. Electron transfer from the low work function metal and Al/LiF(CsF) bilayer to the Alga has been observed. The role of the dielectric and possible chemistry at the interface are discussed in comparison of the low work function metals. Further in Chapter 5, the origin of the metal-interface dipole and the estimation of charge injection barrier is explored using several organic materials. A thermodynamic equilibrium model is extended to explain the relation between the charge transfer process ad the interface dipole. Further, in Chapter 6 the combination of XPS, UPS and IPES detailed the evolution of both occupied and unoccupied energy states during the alkali metal doping. The energy gap modification in organic due to metal doping is observed directly for the spectra. Chapter 7 provides stability study of the organic thin films under x-ray and UV light. The results verify the usability of UPS and XPS for the organic materials used in the thesis. Chapter 7 also shows the secondary ion mass spectroscopy results of metal diffusion in organic thin films.

Raman and nuclear magnetic resonance investigation of alkali metal vapor interaction with alkene-based anti-relaxation coating

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

Tretiak, O. Yu., E-mail: otretiak@genphys.ru; Balabas, M. V.; Blanchard, J. W.

2016-03-07

The use of anti-relaxation coatings in alkali vapor cells yields substantial performance improvements compared to a bare glass surface by reducing the probability of spin relaxation in wall collisions by several orders of magnitude. Some of the most effective anti-relaxation coating materials are alpha-olefins, which (as in the case of more traditional paraffin coatings) must undergo a curing period after cell manufacturing in order to achieve the desired behavior. Until now, however, it has been unclear what physicochemical processes occur during cell curing, and how they may affect relevant cell properties. We present the results of nondestructive Raman-spectroscopy and magnetic-resonancemore » investigations of the influence of alkali metal vapor (Cs or K) on an alpha-olefin, 1-nonadecene coating the inner surface of a glass cell. It was found that during the curing process, the alkali metal catalyzes migration of the carbon-carbon double bond, yielding a mixture of cis- and trans-2-nonadecene.« less

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

DOEpatents

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.

Structural and dynamical trends in alkali-metal silanides characterized by neutron-scattering methods

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

Tang, Wan Si; Dimitrievska, Mirjana; Chotard, Jean -Noel

Structural, vibrational, and dynamical properties of the mono- and mixed-alkali silanides (MSiH 3, where M = K, Rb, Cs, K 0.5Rb 0.5, K 0.5Cs 0.5, and Rb 0.5Cs 0.5) were investigated by various neutron experiments, including neutron powder diffraction (NPD), neutron vibrational spectroscopy (NVS), neutron-scattering fixed-window scans (FWSs), and quasielastic neutron scattering (QENS) measurements. Structural characterization showed that the mixed compounds exhibit disordered (α) and ordered (β) phases for temperatures above and below about 200–250 K, respectively, in agreement with their monoalkali correspondents. Vibrational and dynamical properties are strongly influenced by the cation environment; in particular, there is a redmore » shift in the band energies of the librational and bending modes with increasing lattice size as a result of changes in the bond lengths and force constants. Additionally, slightly broader spectral features are observed in the case of the mixed compounds, indicating the presence of structural disorder caused by the random distribution of the alkali-metal cations within the lattice. FWS measurements upon heating showed that there is a large increase in reorientational mobility as the systems go through the order–disorder (β–α) phase transition, and measurements upon cooling of the α-phase revealed the known strong hysteresis for reversion back to the β-phase. Interestingly, at a given temperature, among the different alkali silanide compounds, the relative reorientational mobilities of the SiH 3 – anions in the α- and β-phases tended to decrease and increase, respectively, with increasing alkali-metal mass. Lastly, this dynamical result might provide some insights concerning the enthalpy–entropy compensation effect previously observed for these potentially promising hydrogen storage materials.« less

Structural and dynamical trends in alkali-metal silanides characterized by neutron-scattering methods

DOE PAGES

Tang, Wan Si; Dimitrievska, Mirjana; Chotard, Jean -Noel; ...

2016-09-02

Structural, vibrational, and dynamical properties of the mono- and mixed-alkali silanides (MSiH 3, where M = K, Rb, Cs, K 0.5Rb 0.5, K 0.5Cs 0.5, and Rb 0.5Cs 0.5) were investigated by various neutron experiments, including neutron powder diffraction (NPD), neutron vibrational spectroscopy (NVS), neutron-scattering fixed-window scans (FWSs), and quasielastic neutron scattering (QENS) measurements. Structural characterization showed that the mixed compounds exhibit disordered (α) and ordered (β) phases for temperatures above and below about 200–250 K, respectively, in agreement with their monoalkali correspondents. Vibrational and dynamical properties are strongly influenced by the cation environment; in particular, there is a redmore » shift in the band energies of the librational and bending modes with increasing lattice size as a result of changes in the bond lengths and force constants. Additionally, slightly broader spectral features are observed in the case of the mixed compounds, indicating the presence of structural disorder caused by the random distribution of the alkali-metal cations within the lattice. FWS measurements upon heating showed that there is a large increase in reorientational mobility as the systems go through the order–disorder (β–α) phase transition, and measurements upon cooling of the α-phase revealed the known strong hysteresis for reversion back to the β-phase. Interestingly, at a given temperature, among the different alkali silanide compounds, the relative reorientational mobilities of the SiH 3 – anions in the α- and β-phases tended to decrease and increase, respectively, with increasing alkali-metal mass. Lastly, this dynamical result might provide some insights concerning the enthalpy–entropy compensation effect previously observed for these potentially promising hydrogen storage materials.« less

Do group 1 metal salts form deep eutectic solvents?

PubMed

Abbott, A P; D'Agostino, C; Davis, S J; Gladden, L F; Mantle, M D

2016-09-14

Mixtures of metal salts such as ZnCl 2 , AlCl 3 and CrCl 3 ·6H 2 O form eutectic mixtures with complexing agents, such as urea. The aim of this research was to see if alkali metal salts also formed eutectics in the same way. It is shown that only a limited number of sodium salts form homogeneous liquids at ambient temperatures and then only with glycerol. None of these mixtures showed eutectic behaviour but the liquids showed the physical properties similar to the group of mixtures classified as deep eutectic solvents. This study focussed on four sodium salts: NaBr, NaOAc, NaOAc·3H 2 O and Na 2 B 4 O 7 ·10H 2 O. The ionic conductivity and viscosity of these salts with glycerol were studied, and it was found that unlike previous studies of quaternary ammonium salts with glycerol, where the salt decreased the viscosity, most of the sodium salts increased the viscosity. This suggests that sodium salts have a structure making effect on glycerol. This phenomenon is probably due to the high charge density of Na + , which coordinates to the glycerol. 1 H and 23 Na NMR diffusion and relaxation methods have been used to understand the molecular dynamics in the glycerol-salt mixtures, and probe the effect of water on some of these systems. The results reveal a complex dynamic behaviour of the different species within these liquids. Generally, the translational dynamics of the 1 H species, probed by means of PFG NMR diffusion coefficients, is in line with the viscosity of these liquids. However, 1 H and 23 Na T 1 relaxation measurements suggest that the Na-containing species also play a crucial role in the structure of the liquids.

Nonhazardous solvent composition and method for cleaning metal surfaces

DOEpatents

Googin, J.M.; Simandl, R.F.; Thompson, L.M.

1993-05-04

A solvent composition for displacing greasy and oily contaminants as well as water and/or aqueous residue from metallic surfaces, especially surfaces of radioactive materials so that such surfaces can be wiped clean of the displaced contaminants, water and/or aqueous residue. The solvent composition consists essentially of a blend of nonpolar aliphatic hydrocarbon solvent having a minimum flash point of about 140 F and 2 to 25 volume percent of a polar solvent having a flash point sufficiently high so as to provide the solvent composition with a minimum flash point of at least 140 F. The solvent composition is nonhazardous so that when it is used to clean the surfaces of radioactive materials the waste in the form of paper or cloth wipes, lab coats and the like used in the cleaning operation is not considered to be mixed waste composed of a hazardous solvent and a radioactive material.

Occupational exposure to organic solvents and sleep-disordered breathing.

PubMed

Ulfberg, J; Carter, N; Talbäck, M; Edling, C

1997-01-01

To investigate whether people with occupational exposure to organic solvents have a higher prevalence of obstructive sleep apnea syndrome (OSAS) than the general population and to examine the relationship between snoring and exposure to organic solvents. Consecutive patients, aged 30-64 years, referred during a 3-year period to the sleep laboratory at Avesta Hospital, Sweden, because of suspected OSAS made up the patient groups. Following admission, patients underwent a simplified sleep apnea investigation and were divided into two groups, OSAS (n = 320) and snorers (n = 443). A random sample of 296 men and 289 women aged 30-64 years obtained from a register of all country residents maintained by the county tax authority served as referents (controls). Both patients and referents responded to two questionnaires, including questions about occupation, exposure to organic solvents, and other chemical and physical agents. Men with OSAS or snoring and women with snoring had more often been occupationally exposed to organic solvents than the referents, showing an almost twofold increase in risk for those exposed during whole workdays. For men, the risk of OSAS or snoring increased with increasing exposure. The result indicates that occupational exposure to organic solvents might cause sleep apnea. A new observation is that even snoring could be caused by exposure to organic solvents. It is important to elucidate whether exposure to organic solvents is a cause of OSAS, because such a finding may have important implications for prevention and treatment of sleep disturbances.

Extraction process for removing metallic impurities from alkalide metals

DOEpatents

Royer, L.T.

1987-03-20

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.

Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling in a Green Alcohol Solvent for an Undergraduate Organic Chemistry Laboratory.

PubMed

Hie, Liana; Chang, Jonah J; Garg, Neil K

2015-03-10

A modern undergraduate organic chemistry laboratory experiment involving the Suzuki-Miyaura coupling is reported. Although Suzuki-Miyaura couplings typically employ palladium catalysts in environmentally harmful solvents, this experiment features the use of inexpensive nickel catalysis, in addition to a "green" alcohol solvent. The experiment employs heterocyclic substrates, which are important pharmaceutical building blocks. Thus, this laboratory procedure exposes students to a variety of contemporary topics in organic chemistry, including transition metal-catalyzed cross-couplings, green chemistry, and the importance of heterocycles in drug discovery, none of which are well represented in typical undergraduate organic chemistry curricula. The experimental protocol uses commercially available reagents and is useful in both organic and inorganic instructional laboratories.

Sleep disturbances and exposure to organic solvents

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

Lindelof, B.; Almkvist, O.; Goethe, C.

An inquiry about sleep habits and sleep disturbances revealed a significantly higher prevalence of insomnia in a solvent-exposed group than in a comparable group that had no occupational exposure to organic solvents. The solvent-exposed group has also registered an increased consumption of hypnotics, and a significant increase occurred in the number of individuals who had consulted physicians because of sleep disorders. The results indicate that solvent exposure could induce sleep disturbances.

Nonhazardous solvent composition and method for cleaning metal surfaces

DOEpatents

Googin, John M.; Simandl, Ronald F.; Thompson, Lisa M.

1993-01-01

A solvent composition for displacing greasy and oily contaminants as well as water and/or aqueous residue from metallic surfaces, especially surfaces of radioactive materials so that such surfaces can be wiped clean of the displaced contaminants, water and/or aqueous residue. The solvent composition consists essentially of a blend of nonpolar aliphatic hydrocarbon solvent having a minimum flash point of about 140.degree. F. and 2 to 25 volume percent of a polar solvent having a flash point sufficiently high so as to provide the solvent composition with a minimum flash point of at least 140.degree. F. The solvent composition is nonhazardous so that when it is used to clean the surfaces of radioactive materials the waste in the form of paper or cloth wipes, lab coats and the like used in the cleaning operation is not considered to be mixed waste composed of a hazardous solvent and a radioactive material.

Occupational exposure to solvents, metals and welding fumes and risk of Parkinson's disease.

PubMed

van der Mark, Marianne; Vermeulen, Roel; Nijssen, Peter C G; Mulleners, Wim M; Sas, Antonetta M G; van Laar, Teus; Huss, Anke; Kromhout, Hans

2015-06-01

The aim of this study was to investigate the potential association between occupational exposure to solvents, metals and/or welding fumes and risk of developing Parkinson's disease (PD). Data of a hospital based case-control study including 444 PD patients and 876 age and sex matched controls was used. Occupational histories and lifestyle information of cases and controls were collected in a structured telephone interview. Exposures to aromatic solvents, chlorinated solvents and metals were estimated by linking the ALOHA+ job-exposure matrix to the occupational histories. Exposure to welding fumes was estimated using self-reported information on welding activities. No statistically significant associations with any of the studied metal and solvent exposures were found. However, for self-reported welding activities we observed non-statistically significant reduced risk estimates (third tertile cumulative exposure: OR = 0.51 (95% CI: 0.21-1.24)). The results of our study did not provide support for an increased chance on developing PD after occupational exposure to aromatic solvents, chlorinated solvents or exposure to metals. The results showed reduced risk estimates for welding, which is in line with previous research, but no clear explanation for these findings is available. Copyright © 2015 Elsevier Ltd. All rights reserved.

Chemically modified graphite for electrochemical cells

DOEpatents

Greinke, R.A.; Lewis, I.C.

1998-05-26

This invention relates to chemically modified graphite particles: (a) that are useful in alkali metal-containing electrode of a electrochemical cell comprising: (1) the electrode, (2) a non-aqueous electrolytic solution comprising an organic aprotic solvent which solvent tends to decompose when the electrochemical cell is in use, and an electrically conductive salt of an alkali metal, and (3) a counter electrode; and (b) that are chemically modified with fluorine, chlorine, iodine or phosphorus to reduce such decomposition. This invention also relates to electrodes comprising such chemically modified graphite and a binder and to electrochemical cells containing such electrodes. 3 figs.

Chemically modified graphite for electrochemical cells

DOEpatents

Greinke, Ronald Alfred; Lewis, Irwin Charles

1998-01-01

This invention relates to chemically modified graphite particles: (a) that are useful in alkali metal-containing electrode of a electrochemical cell comprising: (i) the electrode, (ii) a non-aqueous electrolytic solution comprising an organic aprotic solvent which solvent tends to decompose when the electrochemical cell is in use, and an electrically conductive salt of an alkali metal, and (iii) a counterelectrode; and (b) that are chemically modified with fluorine, chlorine, iodine or phosphorus to reduce such decomposition. This invention also relates to electrodes comprising such chemically modified graphite and a binder and to electrochemical cells containing such electrodes.

Metal retention in human transferrin: consequences of solvent composition in analytical sample preparation methods.

PubMed

Quarles, C Derrick; Randunu, K Manoj; Brumaghim, Julia L; Marcus, R Kenneth

2011-10-01

The analysis of metal-binding proteins requires careful sample manipulation to ensure that the metal-protein complex remains in its native state and the metal retention is preserved during sample preparation or analysis. Chemical analysis for the metal content in proteins typically involves some type of liquid chromatography/electrophoresis separation step coupled with an atomic (i.e., inductively coupled plasma-optical emission spectroscopy or -mass spectrometry) or molecular (i.e., electrospray ionization-mass spectrometry) analysis step that requires altered-solvent introduction techniques. UV-VIS absorbance is employed here to monitor the iron content in human holo-transferrin (Tf) under various solvent conditions, changing polarity, pH, ionic strength, and the ionic and hydrophobic environment of the protein. Iron loading percentages (i.e. 100% loading equates to 2 Fe(3+):1 Tf) were quantitatively determined to evaluate the effect of solvent composition on the retention of Fe(3+) in Tf. Maximum retention of Fe(3+) was found in buffered (20 mM Tris) solutions (96 ± 1%). Exposure to organic solvents and deionized H(2)O caused release of ~23-36% of the Fe(3+) from the binding pocket(s) at physiological pH (7.4). Salt concentrations similar to separation conditions used for ion exchange had little to no effect on Fe(3+) retention in holo-Tf. Unsurprisingly, changes in ionic strength caused by additions of guanidine HCl (0-10 M) to holo-Tf resulted in unfolding of the protein and loss of Fe(3+) from Tf; however, denaturing and metal loss was found not to be an instantaneous process for additions of 1-5 M guanidinium to Tf. In contrast, complete denaturing and loss of Fe(3+) was instantaneous with ≥6 M additions of guanidinium, and denaturing and loss of iron from Tf occurred in parallel proportions. Changes to the hydrophobicity of Tf (via addition of 0-14 M urea) had less effect on denaturing and release of Fe(3+) from the Tf binding pocket compared to changes

Lipase in aqueous-polar organic solvents: Activity, structure, and stability

PubMed Central

Kamal, Md Zahid; Yedavalli, Poornima; Deshmukh, Mandar V; Rao, Nalam Madhusudhana

2013-01-01

Studying alterations in biophysical and biochemical behavior of enzymes in the presence of organic solvents and the underlying cause(s) has important implications in biotechnology. We investigated the effects of aqueous solutions of polar organic solvents on ester hydrolytic activity, structure and stability of a lipase. Relative activity of the lipase monotonically decreased with increasing concentration of acetone, acetonitrile, and DMF but increased at lower concentrations (upto ∼20% v/v) of dimethylsulfoxide, isopropanol, and methanol. None of the organic solvents caused any appreciable structural change as evident from circular dichorism and NMR studies, thus do not support any significant role of enzyme denaturation in activity change. Change in 2D [15N, 1H]-HSQC chemical shifts suggested that all the organic solvents preferentially localize to a hydrophobic patch in the active-site vicinity and no chemical shift perturbation was observed for residues present in protein's core. This suggests that activity alteration might be directly linked to change in active site environment only. All organic solvents decreased the apparent binding of substrate to the enzyme (increased Km); however significantly enhanced the kcat. Melting temperature (Tm) of lipase, measured by circular dichroism and differential scanning calorimetry, altered in all solvents, albeit to a variable extent. Interestingly, although the effect of all organic solvents on various properties on lipase is qualitatively similar, our study suggest that magnitudes of effects do not appear to follow bulk solvent properties like polarity and the solvent effects are apparently dictated by specific and local interactions of solvent molecule(s) with the protein. PMID:23625694

Electron core ionization in compressed alkali metal cesium

NASA Astrophysics Data System (ADS)

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.

Sonochemical method for producing titanium metal powder.

PubMed

Halalay, Ion C; Balogh, Michael P

2008-07-01

We demonstrate a sonochemical method for producing titanium metal powder. The method uses low intensity ultrasound in a hydrocarbon solvent at near-ambient temperatures to first create a colloidal suspension of liquid sodium-potassium alloy in the solvent and then to reduce liquid titanium tetrachloride to titanium metal under cavitation conditions. XRD data collected for the reaction products after the solvent removal show only NaCl and KCl, with no diffraction peaks attributable to titanium metal or other titanium compounds, indicating either the formation of amorphous metal or extremely small crystallite size. TEM micrographs show that hollow spheres formed of halide salts and titanium metal, with diameters with diameters ranging from 100 to 500 nm and a shell thickness of 20 to 40 nm form during the synthesis, suggesting that the sonochemical reaction occurs inside the liquid shell surrounding the cavitation bubbles. Metal particle sizes are estimated to be significantly smaller than 40 nm from TEM data. XRD data of the powder after annealing and prior to removal of the alkali chloride salts provides direct evidence that titanium metal was formed during the sonochemical synthesis.

Perspectives on Computational Organic Chemistry

PubMed Central

Streitwieser, Andrew

2009-01-01

The author reviews how his early love for theoretical organic chemistry led to experimental research and the extended search for quantitative correlations between experiment and quantum calculations. The experimental work led to ion pair acidities of alkali-organic compounds and most recently to equilibria and reactions of lithium and cesium enolates in THF. This chemistry is now being modeled by ab initio calculations. An important consideration is the treatment of solvation in which coordination of the alkali cation with the ether solvent plays a major role. PMID:19518150

Alkali metal/halide thermal energy storage systems performance evaluation

NASA Technical Reports Server (NTRS)

Phillips, W. M.; Stearns, J. W.

1986-01-01

A pseudoheat-pipe heat transfer mechanism has been demonstrated effective in terms of both total heat removal efficiency and rate, on the one hand, and system isothermal characteristics, on the other, for solar thermal energy storage systems of the kind being contemplated for spacecraft. The selection of appropriate salt and alkali metal substances for the system renders it applicable to a wide temperature range. The rapid heat transfer rate obtainable makes possible the placing of the thermal energy storage system around the solar receiver canister, and the immersing of heat transfer fluid tubes in the phase change salt to obtain an isothermal heat source.

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

NASA Astrophysics Data System (ADS)

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.

Adsorption Characteristics of Bixin on Acid- and Alkali-Treated Kaolinite in Aprotic Solvents

PubMed Central

Rahmalia, Winda; Fabre, Jean-François; Usman, Thamrin

2018-01-01

The adsorption of bixin in aprotic solvents onto acid- and alkali-treated kaolinite was investigated. Kaolinite was treated three times, for 6 h each, with 8 M HCl or 5 M KOH. The adsorbents were characterized by XRD, FT-IR, EDS, and BET-N2. The effects of contact time and dye concentration on adsorption capacity and kinetics, electronic transition of bixin before and after adsorption, and also mechanism of bixin-kaolinite adsorption were investigated. Dye adsorption followed pseudo-second order kinetics and was faster in acetone than in dimethyl carbonate. The best adsorption results were obtained for KOH-treated kaolinite. In both of the solvents, the adsorption isotherm followed the Langmuir model and adsorption capacity was higher in dimethyl carbonate (q m = 0.43 mg/g) than in acetone (0.29 mg/g). The adsorption capacity and kinetics of KOH-treated kaolinite (q m = 0.43 mg/g, k 2 = 3.27 g/mg·min) were better than those of HCl-treated kaolinite (q m = 0.21 mg/g, k 2 = 0.25 g/mg·min) and natural kaolinite (q m = 0.18 mg/g, k 2 = 0.32 g/mg·min). There are shift in the band position of maximum intensity of bixin after adsorption on this adsorbent. Adsorption in this system seemed to be based essentially on chemisorption due to the electrostatic interaction of bixin with the strong basic and reducing sites of kaolinite. PMID:29581720

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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.

PubMed

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.

Rational enhancement of enzyme performance in organic solvents. Final technical report, 1992--1996

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

Klibanov, A.M.

1996-12-31

This research focused on the following: the dependence of enzymatic activity of several model hydrolases in nonaqueous solvents; control of substrate selectivity of the protease subtilisin Carlsberg by the solvent; control of catalytic activity and enantioselectivity of this enzyme in organic solvents by immobilization support; lipase-catalyzed acylation of sugars in anhydrous hydrophobic media; the possibility of accelerating enzymatic processes in organic solvents by certain cosolvents; whether lipase catalysis in organic solvents can be enhanced by introducing interfaces in the in the reaction medium; the structure of proteins suspended in organic solvents; improving enzymatic enantioselectivity in organic solvents; analyzing the plungemore » in enzymatic activity upon replacing water with organic solvents; and the structural basis for the phenomenon of molecular memory of imprinted proteins in organic solvents.« less

Electrolytic systems and methods for making metal halides and refining metals

DOEpatents

Holland, Justin M.; Cecala, David M.

2015-05-26

Disclosed are electrochemical cells and methods for producing a halide of a non-alkali metal and for electrorefining the halide. The systems typically involve an electrochemical cell having a cathode structure configured for dissolving a hydrogen halide that forms the halide into a molten salt of the halogen and an alkali metal. Typically a direct current voltage is applied across the cathode and an anode that is fabricated with the non-alkali metal such that the halide of the non-alkali metal is formed adjacent the anode. Electrorefining cells and methods involve applying a direct current voltage across the anode where the halide of the non-alkali metal is formed and the cathode where the non-alkali metal is electro-deposited. In a representative embodiment the halogen is chlorine, the alkali metal is lithium and the non-alkali metal is uranium.

Heavier alkali-metal monosulfides (KS, RbS, CsS, and FrS) and their cations.

PubMed

Lee, Edmond P F; Wright, Timothy G

2005-10-08

The heavier alkali-metal monosulfides (KS, RbS, CsS, and FrS) have been studied by high-level ab initio calculations. The RCCSD(T) method has been employed, combined with large flexible valence basis sets. All-electron basis sets are used for potassium and sulfur, with effective core potentials being used for the other metals, describing the core electrons. Potential-energy curves are calculated for the lowest two neutral and cationic states: all neutral monosulfide species have a (2)Pi ground state, in contrast with the alkali-metal monoxide species, which undergo a change in the electronic ground state from (2)Pi to (2)Sigma(+) as the group is descended. In the cases of KS, RbS, and CsS, spin-orbit curves are also calculated. We also calculate potential-energy curves for the lowest (3)Sigma(-) and (3)Pi states of the cations. From the potential-energy curves, spectroscopic constants are derived, and for KS the spectroscopic results are compared to experimental spectroscopic values. Ionization energies, dissociation energies, and heats of formation are also calculated; for KS, we explore the effects of relativity and basis set extrapolation on these values.

Surface Tension of Liquid Alkali, Alkaline, and Main Group Metals: Theoretical Treatment and Relationship Investigations

NASA Astrophysics Data System (ADS)

Aqra, Fathi; Ayyad, Ahmed

2011-09-01

An improved theoretical method for calculating the surface tension of liquid metals is proposed. A recently derived equation that allows an accurate estimate of surface tension to be made for the large number of elements, based on statistical thermodynamics, is used for a means of calculating reliable values for the surface tension of pure liquid alkali, alkaline earth, and main group metals at the melting point, In order to increase the validity of the model, the surface tension of liquid lithium was calculated in the temperature range 454 K to 1300 K (181 °C to 1027 °C), where the calculated surface tension values follow a straight line behavior given by γ = 441 - 0.15 (T-Tm) (mJ m-2). The calculated surface excess entropy of liquid Li (- dγ/ dT) was found to be 0.15 mJ m-2 K-1, which agrees well with the reported experimental value (0.147 mJ/m2 K). Moreover, the relations of the calculated surface tension of alkali metals to atomic radius, heat of fusion, and specific heat capacity are described. The results are in excellent agreement with the existing experimental data.

Challenges and Prospect of Non-aqueous Non-alkali (NANA) Metal-Air Batteries.

PubMed

Gelman, Danny; Shvartsev, Boris; Ein-Eli, Yair

2016-12-01

Non-aqueous non-alkali (NANA) metal-air battery technologies promise to provide electrochemical energy storage with the highest specific energy density. Metal-air battery technology is particularly advantageous being implemented in long-range electric vehicles. Up to now, almost all the efforts in the field are focused on Li-air cells, but other NANA metal-air battery technologies emerge. The major concern, which the research community should be dealing with, is the limited and rather poor rechargeability of these systems. The challenges we are covering in this review are related to the initial limited discharge capacities and cell performances. By comprehensively reviewing the studies conducted so far, we show that the implementation of advanced materials is a promising approach to increase metal-air performance and, particularly, metal surface activation as a prime achievement leading to respectful discharge currents. In this review, we address the most critical areas that need careful research attention in order to achieve progress in the understanding of the physical and electrochemical processes in non-aqueous electrolytes applied in beyond lithium and zinc air generation of metal-air battery systems.

Tunable solvation effects on the size-selective fractionation of metal nanoparticles in CO2 gas-expanded solvents.

PubMed

Anand, Madhu; McLeod, M Chandler; Bell, Philip W; Roberts, Christopher B

2005-12-08

This paper presents an environmentally friendly, inexpensive, rapid, and efficient process for size-selective fractionation of polydisperse metal nanoparticle dispersions into multiple narrow size populations. The dispersibility of ligand-stabilized silver and gold nanoparticles is controlled by altering the ligand tails-solvent interaction (solvation) by the addition of carbon dioxide (CO2) gas as an antisolvent, thereby tailoring the bulk solvent strength. This is accomplished by adjusting the CO2 pressure over the liquid, resulting in a simple means to tune the nanoparticle precipitation by size. This study also details the influence of various factors on the size-separation process, such as the types of metal, ligand, and solvent, as well as the use of recursive fractionation and the time allowed for settling during each fractionation step. The pressure range required for the precipitation process is the same for both the silver and gold particles capped with dodecanethiol ligands. A change in ligand or solvent length has an effect on the interaction between the solvent and the ligand tails and therefore the pressure range required for precipitation. Stronger interactions between solvent and ligand tails require greater CO2 pressure to precipitate the particles. Temperature is another variable that impacts the dispersibility of the nanoparticles through changes in the density and the mole fraction of CO2 in the gas-expanded liquids. Recursive fractionation for a given system within a particular pressure range (solvent strength) further reduces the polydispersity of the fraction obtained within that pressure range. Specifically, this work utilizes the highly tunable solvent properties of organic/CO2 solvent mixtures to selectively size-separate dispersions of polydisperse nanoparticles (2 to 12 nm) into more monodisperse fractions (+/-2 nm). In addition to providing efficient separation of the particles, this process also allows all of the solvent and

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

PubMed

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.

Theoretical study of mixed MLaX(4) (M = Na, K, Cs; X = F, Cl, Br, I) rare earth/alkali metal halide complexes.

PubMed

Groen, Cornelis Petrus; Oskam, Ad; Kovács, Attila

2003-02-10

The structure, bonding, and vibrational properties of the mixed MLaX(4) (M = Na, K, Cs; X = F, Cl, Br, I) rare earth/alkali metal halide complexes have been studied using the MP2 method in conjunction with polarized triple-zeta valence basis sets and quasi-relativistic effective core potentials for the heavy atoms. From the three characteristic structures, possessing 1- (C(3)(v)), 2- (C(2)(v)), or 3-fold coordination (C(3)(v)) between the alkali metal and the bridging halide atoms, the bi- and tridentate forms are stable isomers with close dissociation energies. In general, for the complexes existing of lighter alkali metals and halogens, the bidentate structure corresponds to the global minimum of the potential energy surface, while the heavier analogues favor the tridentate structure. At experimentally relevant temperatures (T > 800 K), however, the isomerization entropy leads to a domination of the bidentate structures over the tridentate forms for all complexes. An important effect of the size of the alkali metal is manifested in the larger stabilities of the K and Cs complexes. The natural atomic charges are in agreement with strong electrostatic interactions in the title complexes. The marginal covalent contributions show a slight increasing trend in the heavier analogues. The calculated vibrational data indicate that infrared spectroscopy may be an effective tool for experimental investigation and characterization of MLaX(4) molecules.

Thin Metallic Films From Solvated Metal Atoms

NASA Astrophysics Data System (ADS)

Trivino, Galo C.; Klabunde, Kenneth J.; Dale, Brock

1988-02-01

Metals were evaporated under vacuum and the metal atoms solvated by excess organic solvents at low temperature. Upon warming stable colloidal metal particles were formed by controlled metal atom clustering. The particles were stabilized toward flocculation by solvation and electrostatic effects. Upon solvent removal the colloidal particles grew to form thin films that were metallic in appearance, but showed higher resistivities than pure metallic films. Gold, palladium, platinium, and especially indium are discussed.

Bond-length distributions for ions bonded to oxygen: alkali and alkaline-earth metals.

PubMed

Gagné, Olivier Charles; Hawthorne, Frank Christopher

2016-08-01

Bond-length distributions have been examined for 55 configurations of alkali-metal ions and 29 configurations of alkaline-earth-metal ions bonded to oxygen, for 4859 coordination polyhedra and 38 594 bond distances (alkali metals), and for 3038 coordination polyhedra and 24 487 bond distances (alkaline-earth metals). Bond lengths generally show a positively skewed Gaussian distribution that originates from the variation in Born repulsion and Coulomb attraction as a function of interatomic distance. The skewness and kurtosis of these distributions generally decrease with increasing coordination number of the central cation, a result of decreasing Born repulsion with increasing coordination number. We confirm the following minimum coordination numbers: ([3])Li(+), ([3])Na(+), ([4])K(+), ([4])Rb(+), ([6])Cs(+), ([3])Be(2+), ([4])Mg(2+), ([6])Ca(2+), ([6])Sr(2+) and ([6])Ba(2+), but note that some reported examples are the result of extensive dynamic and/or positional short-range disorder and are not ordered arrangements. Some distributions of bond lengths are distinctly multi-modal. This is commonly due to the occurrence of large numbers of structure refinements of a particular structure type in which a particular cation is always present, leading to an over-representation of a specific range of bond lengths. Outliers in the distributions of mean bond lengths are often associated with anomalous values of atomic displacement of the constituent cations and/or anions. For a sample of ([6])Na(+), the ratio Ueq(Na)/Ueq(bonded anions) is partially correlated with 〈([6])Na(+)-O(2-)〉 (R(2) = 0.57), suggesting that the mean bond length is correlated with vibrational/displacement characteristics of the constituent ions for a fixed coordination number. Mean bond lengths also show a weak correlation with bond-length distortion from the mean value in general, although some coordination numbers show the widest variation in mean bond length for zero distortion, e.g. Li(+) in

Synthesis of metal oxide nanoparticles via a robust ``solvent-deficient'' method

NASA Astrophysics Data System (ADS)

Smith, Stacey J.; Huang, Baiyu; Liu, Shengfeng; Liu, Qingyuan; Olsen, Rebecca E.; Boerio-Goates, Juliana; Woodfield, Brian F.

2014-11-01

We report an efficient, general methodology for producing high-surface area metal oxide nanomaterials for a vast range of metal oxides, including at least one metal oxide nanomaterial from nearly every transition metal and semi-metal group in the periodic table (groups 3-4 and 6-15) as well as several from the lanthanide group (see Table 1). The method requires only 2-3 simple steps; a hydrated metal salt (usually a nitrate or chloride salt) is ground with bicarbonate (usually NH4HCO3) for 10-30 minutes to form a precursor that is then either untreated or rinsed before being calcined at relatively low temperatures (220-550 °C) for 1-3 hours. The method is thus similar to surfactant-free aqueous methods such as co-precipitation but is unique in that no solvents are added. The resulting ``solvent-deficient'' environment has interesting and unique consequences, including increased crystallinity of the products over other aqueous methods and a mesoporous nature in the inevitable agglomerates. The products are chemically pure and phase pure with crystallites generally 3-30 nm in average size that aggregate into high surface area, mesoporous agglomerates 50-300 nm in size that would be useful for catalyst and gas sensing applications. The versatility of products and efficiency of the method lend its unique potential for improving the industrial viability of a broad family of useful metal oxide nanomaterials. In this paper, we outline the methodology of the solvent-deficient method using our understanding of its mechanism, and we describe the range and quality of nanomaterials it has produced thus far.We report an efficient, general methodology for producing high-surface area metal oxide nanomaterials for a vast range of metal oxides, including at least one metal oxide nanomaterial from nearly every transition metal and semi-metal group in the periodic table (groups 3-4 and 6-15) as well as several from the lanthanide group (see Table 1). The method requires only 2

Influence of Organic Solvents on Chalcopyrite Oxidation Ability of Thiobacillus ferrooxidans

PubMed Central

Torma, Arpad E.; Itzkovitch, Irwin J.

1976-01-01

It has been shown that organic solvents used primarily for the extraction of metals from aqueous leach liquors decrease both the surface tension of the aqueous phase and the chalcopyrite oxidation ability of Thiobacillus ferrooxidans. For the reagents and modifiers investigated, the order of inhibition was found to be LIX 70 < LIX 73 < LIX 71 < LIX 64N < LIX 65N < TBP ∼ isodecanol ∼ nonylphenol < LIX 63 <<< D2EHPA ∼ Kelex 100 < Kelex 120 <<< Alamine 336 ∼ Alamine 308 ∼ Alamine 310 < Alamine 304 < Adogen 381 ∼ Aliquat 336 < Adogen 364. To avoid limitation in bacterial activity, organic matter should be removed from the recycling liquor prior to leaching. PMID:16345164

Alkali metal complexes of a phosphine-borane-stabilised carbanion: influence of co-ligands on structure.

PubMed

Izod, Keith; Wills, Corinne; Clegg, William; Harrington, Ross W

2007-09-07

The adducts [[(Me(3)Si)(2){Me(2)P(BH(3))}C]K(L)(n)](m) [L = THF, n = 0.5, m = infinity (2a); L = tmeda (2b), pmdeta (2c), n = 1, m = 2] may be synthesised by treatment of solvent-free [[(Me(3)Si)(2){Me(2)P(BH(3))}C]K](infinity) (2) with the corresponding Lewis base (tmeda = N,N,N',N'-tetramethylethylenediamine; pmdeta = N,N,N',N'',N''-pentamethyldiethylenetriamine). X-Ray crystallography reveals that, whereas 2 crystallises with a complex 2-dimensional sheet structure, 2a crystallises as a ribbon-type one-dimensional polymer and both 2b and 2c crystallise as dimers. The corresponding complex with 12-crown-4, [K(12-crown-4)(2)][(Me(3)Si)(2){Me(2)P(BH(3))}C] (2d) crystallises as a separated ion pair. The complexes [[(Me(3)Si)(2){Me(2)P(BH(3))}C]M(pmdeta)](n) [M = Na, n = 1 (6); M = Rb, n = 2 (7)] may be synthesised by treatment of [(Me(3)Si)(2){Me(2)P(BH(3))}C]M with pmdeta. Whereas crystallises as a discrete monomer, compound 7 crystallises as a dimer. Compounds 2, 2a-2d, 6, 7 and the corresponding caesium derivative [[(Me(3)Si)(2){Me(2)P(BH(3))}C]Cs(pmdeta)](2) () provide an opportunity to consider the influence of the ionic radius of the metal and the nature of the co-ligands on the structures of alkali metal complexes of a phosphine-borane-stabilised carbanion.

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

PubMed

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.

Doping of alkali, alkaline-earth, and transition metals in covalent-organic frameworks for enhancing CO2 capture by first-principles calculations and molecular simulations.

PubMed

Lan, Jianhui; Cao, Dapeng; Wang, Wenchuan; Smit, Berend

2010-07-27

We use the multiscale simulation approach, which combines the first-principles calculations and grand canonical Monte Carlo simulations, to comprehensively study the doping of a series of alkali (Li, Na, and K), alkaline-earth (Be, Mg, and Ca), and transition (Sc and Ti) metals in nanoporous covalent organic frameworks (COFs), and the effects of the doped metals on CO2 capture. The results indicate that, among all the metals studied, Li, Sc, and Ti can bind with COFs stably, while Be, Mg, and Ca cannot, because the binding of Be, Mg, and Ca with COFs is very weak. Furthermore, Li, Sc, and Ti can improve the uptakes of CO2 in COFs significantly. However, the binding energy of a CO2 molecule with Sc and Ti exceeds the lower limit of chemisorptions and, thus, suffers from the difficulty of desorption. By the comparative studies above, it is found that Li is the best surface modifier of COFs for CO2 capture among all the metals studied. Therefore, we further investigate the uptakes of CO2 in the Li-doped COFs. Our simulation results show that at 298 K and 1 bar, the excess CO2 uptakes of the Li-doped COF-102 and COF-105 reach 409 and 344 mg/g, which are about eight and four times those in the nondoped ones, respectively. As the pressure increases to 40 bar, the CO2 uptakes of the Li-doped COF-102 and COF-105 reach 1349 and 2266 mg/g at 298 K, respectively, which are among the reported highest scores to date. In summary, doping of metals in porous COFs provides an efficient approach for enhancing CO2 capture.

Solvent extraction of gold using ionic liquid based process

NASA Astrophysics Data System (ADS)

Makertihartha, I. G. B. N.; Zunita, Megawati; Rizki, Z.; Dharmawijaya, P. T.

2017-01-01

In decades, many research and mineral processing industries are using solvent extraction technology for metal ions separation. Solvent extraction technique has been used for the purification of precious metals such as Au and Pd, and base metals such as Cu, Zn and Cd. This process uses organic compounds as solvent. Organic solvents have some undesired properties i.e. toxic, volatile, excessive used, flammable, difficult to recycle, low reusability, low Au recovery, together with the problems related to the disposal of spent extractants and diluents, even the costs associated with these processes are relatively expensive. Therefore, a lot of research have boosted into the development of safe and environmentally friendly process for Au separation. Ionic liquids (ILs) are the potential alternative for gold extraction because they possess several desirable properties, such as a the ability to expanse temperature process up to 300°C, good solvent properties for a wide range of metal ions, high selectivity, low vapor pressures, stability up to 200°C, easy preparation, environmentally friendly (commonly called as "green solvent"), and relatively low cost. This review paper is focused in investigate of some ILs that have the potentials as solvent in extraction of Au from mineral/metal alloy at various conditions (pH, temperature, and pressure). Performances of ILs extraction of Au are studied in depth, i.e. structural relationship of ILs with capability to separate Au from metal ions aggregate. Optimal extraction conditon in order to gain high percent of Au in mineral processing is also investigated.

Spin relaxation in ultracold collisions of molecular radicals with alkali-metal atoms

NASA Astrophysics Data System (ADS)

Tscherbul, Timur; Klos, Jacek; Zukowski, Piotr

2016-05-01

We present accurate quantum scattering calculations of spin relaxation in ultracold collisions of alkali-metal atoms and polar 2 Σ molecules CaH, SrF, and SrOH. The calculations employ state-of-the-art ab initio interaction potentials and a rigorous quantum theory of atom-molecule collisions in a magnetic field based on the total angular momentum representation. We will further discuss the relevance of the results to atom-molecule sympathetic cooling experiments in a magnetic trap.

Alkali Metal CO2 Sorbents and the Resulting Metal Carbonates: Potential for Process Intensification of Sorption-Enhanced Steam Reforming.

PubMed

Memon, Muhammad Zaki; Zhao, Xiao; Sikarwar, Vineet Singh; Vuppaladadiyam, Arun K; Milne, Steven J; Brown, Andy P; Li, Jinhui; Zhao, Ming

2017-01-03

Sorption-enhanced steam reforming (SESR) is an energy and cost efficient approach to produce hydrogen with high purity. SESR makes it economically feasible to use a wide range of feedstocks for hydrogen production such as methane, ethanol, and biomass. Selection of catalysts and sorbents plays a vital role in SESR. This article reviews the recent research aimed at process intensification by the integration of catalysis and chemisorption functions into a single material. Alkali metal ceramic powders, including Li 2 ZrO 3 , Li 4 SiO 4 and Na 2 ZrO 3 display characteristics suitable for capturing CO 2 at low concentrations (<15% CO 2 ) and high temperatures (>500 °C), and thus are applicable to precombustion technologies such as SESR, as well as postcombustion capture of CO 2 from flue gases. This paper reviews the progress made in improving the operational performance of alkali metal ceramics under conditions that simulate power plant and SESR operation, by adopting new methods of sorbent synthesis and doping with additional elements. The paper also discusses the role of carbonates formed after in situ CO 2 chemisorption during a steam reforming process in respect of catalysts for tar cracking.

Self-healing Microencapsulation of Biomacromolecules without Organic Solvents**

PubMed Central

Reinhold, Samuel E.; Desai, Kashappa-Goud H.; Zhang, Li; Olsen, Karl F.

2012-01-01

Microencapsulation of biomacromolecules in PLGA is routinely performed with organic solvent through multiple complex steps deleterious to the biomacromolecule. The new self-healing based PLGA microencapsulation obviates micronization- and organic solvent-induced protein damage, provides very high encapsulation efficiency, exhibit stabilization and slow release of labile tetanus protein antigen, and provides long-term testosterone suppression in rats following a single injection of encapsulated leuprolide. PMID:23011773

Ultralow-power local laser control of the dimer density in alkali-metal vapors through photodesorption

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

Jha, Pankaj K.; Scully, Marlan O.; Princeton University, Princeton, New Jersey 08544

2012-08-27

Ultralow-power diode-laser radiation is employed to induce photodesorption of cesium from a partially transparent thin-film cesium adsorbate on a solid surface. Using resonant Raman spectroscopy, we demonstrate that this photodesorption process enables an accurate local optical control of the density of dimer molecules in alkali-metal vapors.

Pseudopotential theoretical study of the alkali metals under arbitrary pressure: Density, bulk modulus, and shear moduli

NASA Astrophysics Data System (ADS)

Rasky, Daniel J.; Milstein, Frederick

1986-02-01

Milstein and Hill previously derived formulas for computing the bulk and shear moduli, κ, μ, and μ', at arbitrary pressures, for cubic crystals in which interatomic interaction energies are modeled by pairwise functions, and they carried out the moduli computations using the complete family of Morse functions. The present study extends their work to a pseudopotential description of atomic binding. Specifically: (1) General formulas are derived for determining these moduli under hydrostatic loading within the framework of a pseudopotential model. (2) A two-parameter pseudopotential model is used to describe atomic binding of the alkali metals, and the two parameters are determined from experimental data (the model employs the Heine-Abarenkov potential with the Taylor dielectric function). (3) For each alkali metal (Li, Na, K, Rb, and Cs), the model is used to compute the pressure-versus-volume behavior and, at zero pressure, the binding energy, the density, and the elastic moduli and their pressure derivatives; the theoretical behavior is found to be in excellent agreement with experiment. (4) Calculations are made of κ, μ, and μ' of the bcc alkali metals over wide ranges of hydrostatic compression and expansion. (5) The pseudopotential results are compared with those of arbitrary-central-force models (wherein κ-(2/3)μ=μ'+2P) and with the specific Morse-function results. The pressures, bulk moduli, and zero-pressure shear moduli (as determined for the Morse and pseudopotential models) are in excellent agreement, but important differences appear in the shear moduli under high compressions. The computations in the present paper are for the bcc metals; a subsequent paper will extend this work to include both the bcc and fcc structures, at compressions and expansions where elastic stability or lattice cohesion is, in practice, lost.

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

DOE PAGES

Resasco, Joaquin; Chen, Leanne D.; Clark, Ezra; ...

2017-07-24

The electrochemical reduction of CO 2 is known to be influenced by the identity of the alkali metal cation in the electrolyte; however, a satisfactory explanation for this phenomenon has not been developed. Here we present the results of experimental and theoretical studies aimed at elucidating the effects of electrolyte cation size on the intrinsic activity and selectivity of metal catalysts for the reduction of CO 2. Experiments were conducted under conditions where the influence of electrolyte polarization is minimal in order to show that cation size affects the intrinsic rates of formation of certain reaction products, most notably formore » HCOO –, C 2H 4, and C 2H 5OH over Cu(100)- and Cu(111)-oriented thin films, and for CO and HCOO– over polycrystalline Ag and Sn. Interpretation of the findings for CO 2 reduction was informed by studies of the reduction of glyoxal and CO, key intermediates along the reaction pathway to final products. Density functional theory calculations show that the alkali metal cations influence the distribution of products formed as a consequence of electrostatic interactions between solvated cations present at the outer Helmholtz plane and adsorbed species having large dipole moments. As a result, the observed trends in activity with cation size are attributed to an increase in the concentration of cations at the outer Helmholtz plane with increasing cation size.« less

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

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

Resasco, Joaquin; Chen, Leanne D.; Clark, Ezra

The electrochemical reduction of CO 2 is known to be influenced by the identity of the alkali metal cation in the electrolyte; however, a satisfactory explanation for this phenomenon has not been developed. Here we present the results of experimental and theoretical studies aimed at elucidating the effects of electrolyte cation size on the intrinsic activity and selectivity of metal catalysts for the reduction of CO 2. Experiments were conducted under conditions where the influence of electrolyte polarization is minimal in order to show that cation size affects the intrinsic rates of formation of certain reaction products, most notably formore » HCOO –, C 2H 4, and C 2H 5OH over Cu(100)- and Cu(111)-oriented thin films, and for CO and HCOO– over polycrystalline Ag and Sn. Interpretation of the findings for CO 2 reduction was informed by studies of the reduction of glyoxal and CO, key intermediates along the reaction pathway to final products. Density functional theory calculations show that the alkali metal cations influence the distribution of products formed as a consequence of electrostatic interactions between solvated cations present at the outer Helmholtz plane and adsorbed species having large dipole moments. As a result, the observed trends in activity with cation size are attributed to an increase in the concentration of cations at the outer Helmholtz plane with increasing cation size.« less

Silicon halide-alkali metal flames as a source of solar grade silicon

NASA Technical Reports Server (NTRS)

Olsen, D. B.; Miller, W. J.

1979-01-01

The feasibility of using alkali metal-silicon halide diffusion flames to produce solar-grade silicon in large quantities and at low cost is demonstrated. Prior work shows that these flames are stable and that relatively high purity silicon can be produced using Na + SiCl4 flames. Silicon of similar purity is obtained from Na + SiF4 flames although yields are lower and product separation and collection are less thermochemically favored. Continuous separation of silicon from the byproduct alkali salt was demonstrated in a heated graphite reactor. The process was scaled up to reduce heat losses and to produce larger samples of silicon. Reagent delivery systems, scaled by a factor of 25, were built and operated at a production rate of 0.5 kg Si/h. Very rapid reactor heating rates are observed with wall temperatures reaching greater than 2000 K. Heat release parameters were measured using a cooled stainless steel reactor tube. A new reactor was designed.

Multiple neutral alkali halide attachments onto oligosaccharides in electrospray ionization mass spectrometry

NASA Astrophysics Data System (ADS)

Striegel, André M.; Timpa, Judy D.; Piotrowiak, Piotr; Cole, Richard B.

1997-03-01

Oligosaccharides perform essential functions in a variety of biological and agricultural processes. Recent approaches to characterization of these molecules by mass spectrometry have utilized mainly soft-ionization methods such as electrospray ionization (ESI) and thermospray (TS), as well as fast atom bombardment (FAB). The behavior of a series of maltooligosaccharides with [alpha]-(1 --> 4) linkages, maltose (G2) through maltoheptaose (G7), under ESI conditions, has been investigated here. The oligosaccharides were dissolved in N,N-dimethylacetamide containing lithium chloride (DMAc/LiCl) prior to analysis by ESI-MS. A highly unusual feature, evident in all mass spectra obtained using this solvent system, was the presence of multiple [`]neutral' salt attachments onto lithium adducts of the sugars. Resultant ions took the form of [Gx + Li + nLiCl+, where n may reach a value as high as eight. Compared to LiCl, the propensity for alkali halide attachment using other alkali chlorides or lithium halides was greatly reduced. An investigation of this phenomenon is presented in which the organic and inorganic portions of the employed solvent were systematically varied, and semi-empirical computer modeling was performed to better understand lithium coordination by the sugars.

Method of treating alkali metal sulfide and carbonate mixtures

DOEpatents

Kohl, Arthur L.; Rennick, Robert D.; Savinsky, Martin W.

1978-01-01

A method of removing and preferably recovering sulfur values from an alkali metal sulfide and carbonate mixture comprising the steps of (1) introducing the mixture in an aqueous medium into a first carbonation zone and reacting the mixture with a gas containing a major amount of CO.sub.2 and a minor amount of H.sub.2 S; (2) introducing the resultant product from step 1 into a stripping zone maintained at subatmospheric pressure, and contacting this product with steam to produce a gaseous mixture, comprising H.sub.2 S and water vapor, and a liquor of reduced sulfide content; (3) introducing the liquor of reduced sulfide content into a second carbonation zone, and reacting the liquor with substantially pure gaseous CO.sub.2 in an amount sufficient to precipitate bicarbonate crystals and produce an offgas containing CO.sub.2 and H.sub.2 S for use in step 1; (4) recovering the bicarbonate crystals from step 3, and thermally decomposing the crystals to produce an alkaline metal carbonate product and a substantially pure CO.sub.2 offgas for use in step 3.

Dispersion and separation of nanostructured carbon in organic solvents

NASA Technical Reports Server (NTRS)

Evans, Christopher M. (Inventor); Ruf, Herbert J. (Inventor); Landi, Brian J. (Inventor); Raffaelle, Ryne P. (Inventor)

2011-01-01

The present invention relates to dispersions of nanostructured carbon in organic solvents containing alkyl amide compounds and/or diamide compounds. The invention also relates to methods of dispersing nanostructured carbon in organic solvents and methods of mobilizing nanostructured carbon. Also disclosed are methods of determining the purity of nanostructured carbon.

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

NASA Astrophysics Data System (ADS)

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.

Effects of metals on the transformation of hexabromocyclododecane (HBCD) in solvents: implications for solvent-based recycling of brominated flame retardants.

PubMed

Zhong, Yin; Peng, Ping'an; Yu, Zhiqiang; Deng, Haopeng

2010-09-01

The management of electronic wastes (e-wastes) has become a global issue as it may release large quantities of hazardous materials such as heavy metals and brominated flame retardants (BFRs) to the environment. Solvent-based recycling is a newly developed, efficient and environmentally beneficial technology for the removal or recovery of BFRs from e-wastes. However, little is known about the behavior of BFRs in the solvents and to what extent they may be affected by co-existing heavy metals. This study quantified the rates of transformation of hexabromocyclododecane (HBCD), a widely used BFR, in the presence of different solvents (i.e. acetone, methanol or toluene) and metals (i.e. Ni, Cu, Zn, Fe or Al). Our experimental results showed that less than 20% of HBCD was transformed in all pure solvent systems within 24h at 50 degrees C. The presence of Ni greatly increased the transformation of HBCD (45-99%) in these solvent systems, whereas other metals had little or no effect on extraction process. The kinetics study showed that transformation of HBCD in Ni-containing systems followed pseudo-first-order kinetics and that the highest transformation rate constant (1.2+/-0.1h(-1)) of HBCD was recorded in the Ni+acetone system. The formation of HBr and pentabromocyclododecene in the acetone+Ni system suggested that transformation of HBCD proceeded via dehydrobromination. Collectively, these results indicated that acetone should not be applied in the recycling or extraction of HBCD from Ni-rich e-wastes, as debromination of HBCD may occur during these processes, even at mild extraction temperatures. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Reactive Precipitation of Anhydrous Alkali Sulfide Nanocrystals with Concomitant Abatement of Hydrogen Sulfide and Cogeneration of Hydrogen.

PubMed

Li, Xuemin; Zhao, Yangzhi; Brennan, Alice; McCeig, Miranda; Wolden, Colin A; Yang, Yongan

2017-07-21

Anhydrous alkali sulfide (M 2 S, M=Li or Na) nanocrystals (NCs) are important materials central to the development of next generation cathodes and solid-state electrolytes for advanced batteries, but not commercially available at present. This work reports an innovative method to directly synthesize M 2 S NCs through alcohol-mediated reactions between alkali metals and hydrogen sulfide (H 2 S). In the first step, the alkali metal is complexed with alcohol in solution, forming metal alkoxide (ROM) and releasing hydrogen (H 2 ). Next, H 2 S is bubbled through the ROM solution, where both chemicals are completely consumed to produce phase-pure M 2 S NC precipitates and regenerate alcohol that can be recycled. The M 2 S NCs morphology may be tuned through the choice of the alcohol and solvent. Both synthetic steps are thermodynamically favorable (ΔG m o <-100 kJ mol -1 ), proceeding rapidly to completion at ambient temperature with almost 100 % atom efficiency. The net result, H 2 S+2 m→M 2 S+H 2 , makes good use of a hazardous chemical (H 2 S) and delivers two value-added products that naturally phase separate for easy recovery. This scalable approach provides an energy-efficient and environmentally benign solution to the production of nanostructured materials required in emerging battery technologies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Implementation of Hydrodynamic Simulation Code in Shock Experiment Design for Alkali Metals

NASA Astrophysics Data System (ADS)

Coleman, A. L.; Briggs, R.; Gorman, M. G.; Ali, S.; Lazicki, A.; Swift, D. C.; Stubley, P. G.; McBride, E. E.; Collins, G.; Wark, J. S.; McMahon, M. I.

2017-10-01

Shock compression techniques enable the investigation of extreme P-T states. In order to probe off-Hugoniot regions of P-T space, target makeup and laser pulse parameters must be carefully designed. HYADES is a hydrodynamic simulation code which has been successfully utilised to simulate shock compression events and refine the experimental parameters required in order to explore new P-T states in alkali metals. Here we describe simulations and experiments on potassium, along with the techniques required to access off-Hugoniot states.

Prediction of the solvent affecting site and the computational design of stable Candida antarctica lipase B in a hydrophilic organic solvent.

PubMed

Park, Hyun June; Joo, Jeong Chan; Park, Kyungmoon; Kim, Yong Hwan; Yoo, Young Je

2013-02-10

Enzyme reactions in organic solvent such as for organic synthesis have great industrial potential. However, enzymes lose their stability in hydrophilic organic solvents due to the deformation of the enzyme by the solvent. It is thus important to enhance the stability of enzymes in hydrophilic organic solvents. Previous approaches have not considered on the interaction between enzymes and solvents due to the lack of information. In this study, the structural motions of the enzyme in methanol cosolvent and the interaction between the enzyme surface and the solvent molecule were investigated using molecular dynamics simulation (MD). By analyzing the MD simulation results, the surface residues of Candida antarctica lipase B (CalB) with higher root mean square deviation (RMSD) in a methanol solvent were considered as methanol affecting site and selected for site-directed mutagenesis. The methanol affecting site was computationally redesigned by lowering the RMSD. Among the candidate mutants, the A8T, A92E, N97Q and T245S mutants showed higher organic solvent stability at various methanol concentrations. The rational approach developed in this study could be applied to the stabilization of other industrial enzymes used in organic solvents. Copyright © 2012 Elsevier B.V. All rights reserved.

Molecular simulations of self-assembly processes in metal-organic frameworks: Model dependence

NASA Astrophysics Data System (ADS)

Biswal, Debasmita; Kusalik, Peter G.

2017-07-01

Molecular simulation is a powerful tool for investigating microscopic behavior in various chemical systems, where the use of suitable models is critical to successfully reproduce the structural and dynamic properties of the real systems of interest. In this context, molecular dynamics simulation studies of self-assembly processes in metal-organic frameworks (MOFs), a well-known class of porous materials with interesting chemical and physical properties, are relatively challenging, where a reasonably accurate representation of metal-ligand interactions is anticipated to play an important role. In the current study, we both investigate the performance of some existing models and introduce and test new models to help explore the self-assembly in an archetypal Zn-carboxylate MOF system. To this end, the behavior of six different Zn-ion models, three solvent models, and two ligand models was examined and validated against key experimental structural parameters. To explore longer time scale ordering events during MOF self-assembly via explicit solvent simulations, it is necessary to identify a suitable combination of simplified model components representing metal ions, organic ligands, and solvent molecules. It was observed that an extended cationic dummy atom (ECDA) Zn-ion model combined with an all-atom carboxylate ligand model and a simple dipolar solvent model can reproduce characteristic experimental structures for the archetypal MOF system. The successful use of these models in extensive sets of molecular simulations, which provide key insights into the self-assembly mechanism of this archetypal MOF system occurring during the early stages of this process, has been very recently reported.

Generalized syntheses of nanocrystal-graphene hybrids in high-boiling-point organic solvents.

PubMed

Pang, Danny Wei-Ping; Yuan, Fang-Wei; Chang, Yan-Cheng; Li, Guo-An; Tuan, Hsing-Yu

2012-08-07

Nanocrystal-graphene have been proposed as a new kind of promising hybrid for a wide range of application areas including catalysts, electronics, sensors, biomedicine, and energy storage, etc. Although a variety of methods have been developed for the preparation of hybrids, a facile and general synthetic approach is still highly required. In this study, nanocrystal-graphene hybrids were successfully synthesized in high-boiling-point organic solvents. Graphene oxide (GO) nanosheets were modified by oleylamine (OLA) to form a OLA-GO complex in order to be readily incorporated into hydrophobic synthesis. A rich library of highly crystalline nanocrystals, with types including noble metal, metal oxide, magnetic material and semiconductor were successfully grown on chemically converted graphene (CCG), which is simultaneously reduced from GO during the synthesis. High boiling-point solvents afford sufficient thermal energy to assure the high-quality crystalline nature of NCs, therefore the post-annealing process is obviated. Controlled experiments revealed that OLA-GO triggers heterogeneous nucleation and serves as excellent nuclei anchorage media. The protocol developed here brings one step closer to achieve "unity in diversity" on the preparation of nanocrystal-graphene hybrids.

A QSPR study on the solvent-induced frequency shifts of acetone and dimethyl sulfoxide in organic solvents.

PubMed

Ou, Yu Heng; Chang, Chia Ming; Chen, Ying Shao

2016-06-05

In this study, solvent-induced frequency shifts (SIFS) in the infrared spectrum of acetone and dimethyl sulfoxide in organic solvents were investigated by using four types of quantum-chemical reactivity descriptors. The results showed that the SIFS of acetone is mainly affected by the electron-acceptance chemical potential and the maximum nucleophilic condensed local softness of organic solvents, which represent the electron flow and the polarization between acetone and solvent molecules. On the other hand, the SIFS of dimethyl sulfoxide changes with the maximum positive charge of hydrogen atom and the inverse of apolar surface area of solvent molecules, showing that the electrostatic and hydrophilic interactions are main mechanisms between dimethyl sulfoxide and solvent molecules. The introduction of the four-element theory model-based quantitative structure-property relationship approach improved the assessing quality and provided a basis for interpreting the solute-solvent interactions. Copyright © 2016 Elsevier B.V. All rights reserved.

Ion chromatography with the indirect ultraviolet detection of alkali metal ions and ammonium using imidazolium ionic liquid as ultraviolet absorption reagent and eluent.

PubMed

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.

NOVEL POLYMERIC MEMBRANE FOR DEHYDRATION OF ORGANIC SOLVENTS

EPA Science Inventory

Pervaporation has emerged as an economically viable alternative technology for dehydration of organic solvents, removal of organic compounds and organic/organic separations. Development of a membrane system with suitable flux and selectivity characteristics plays a critical role...

EVALUATION OF ALTERNATIVES TO CHLORINATED SOLVENTS FOR METAL CLEANING

EPA Science Inventory

This project report details results of investigations into alternatives to chlorinated solvents used for metal degreasing. Three companies participated in this project. The results reported for one company document a situation where the conversion to an aqueous cleaning system ha...

Ionic conductivity of β-cyclodextrin-polyethylene-oxide/alkali-metal-salt complex.

PubMed

Yang, Ling-Yun; Fu, Xiao-Bin; Chen, Tai-Qiang; Pan, Li-Kun; Ji, Peng; Yao, Ye-Feng; Chen, Qun

2015-04-20

Highly conductive, crystalline, polymer electrolytes, β-cyclodextrin (β-CD)-polyethylene oxide (PEO)/LiAsF6 and β-CD-PEO/NaAsF6 , were prepared through supramolecular self-assembly of PEO, β-CD, and LiAsF6 /NaAsF6 . The assembled β-CDs form nanochannels in which the PEO/X(+) (X=Li, Na) complexes are confined. The nanochannels provide a pathway for directional motion of the alkali metal ions and, at the same time, separate the cations and the anions by size exclusion. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Olfactory function in painters exposed to organic solvents.

PubMed

Sandmark, B; Broms, I; Löfgren, L; Ohlson, C G

1989-02-01

The olfactory receptor cells are in direct contact with the exterior environment, and some chemical agents can impair olfactory function. The olfactory function of 54 painters exposed to organic solvents was compared with that of 42 unexposed referents. A new clinical test validated for the sense of smell was used, the University of Pennsylvania Smell Identification Test. Age, smoking habits, exposure to organic solvents, and medical disorders of importance for the sense of smell were recorded. The painters had a somewhat lower test score than the referents. However, the influence of the exposure variable was not statistically significant in a multiple regression analysis including age and smoking habits. The exposure to organic solvents was low, and therefore an effect of high exposure on olfactory function cannot be ruled out. Since some of the painters had earlier been highly exposed, the effects of high exposure are likely to be reversible.

An organic solvent-, detergent-, and thermo-stable alkaline protease from the mesophilic, organic solvent-tolerant Bacillus licheniformis 3C5.

PubMed

Rachadech, W; Navacharoen, A; Ruangsit, W; Pongtharangkul, T; Vangnai, A S

2010-01-01

Bacillus licheniformis 3C5, isolated as mesophilic bacterium, exhibited tolerance towards a wide range of non-polar and polar organic solvents at 45 degrees C. It produced an extracellular organic solvent-stable protease with an apparent molecular mass of approximately 32 kDa. The inhibitory effect of PMSF and EDTA suggested it is likely to be an alkaline serine protease. The protease was active over abroad range of temperatures (45-70 degrees C) and pH (8-10) range with an optimum activity at pH 10 and 65 degrees C. It was comparatively stable in the presence ofa relatively high concentration (35% (v/v)) of organic solvents and various types of detergents even at a relatively high temperature (45 degrees C). The protease production by B. licheniformis 3C5 was growth-dependent. The optimization of carbon and nitrogen sources for cell growth and protease production revealed that yeast extract was an important medium component to support both cell growth and the protease production. The overall properties of the protease produced by B. licheniformis 3C5 suggested that this thermo-stable, solvent-stable, detergent-stable alkaline protease is a promising potential biocatalyst for industrial and environmental applications.

Analysis of Supercritical-Extracted Chelated Metal Ions From Mixed Organic-Inorganic Samples

NASA Technical Reports Server (NTRS)

Sinha, Mahadeva P. (Inventor)

1996-01-01

Organic and inorganic contaminants of an environmental sample are analyzed by the same GC-MS instrument by adding an oxidizing agent to the sample to oxidize metal or metal compounds to form metal ions. The metal ions are converted to chelate complexes and the chelate complexes are extracted into a supercritical fluid such as CO2. The metal chelate extract after flowing through a restrictor tube is directly injected into the ionization chamber of a mass spectrometer, preferably containing a refractory metal filament such as rhenium to fragment the complex to release metal ions which are detected. This provides a fast, economical method for the analysis of metal contaminants in a sample and can be automated. An organic extract of the sample in conventional or supercritical fluid solvents can be detected in the same mass spectrometer, preferably after separation in a supercritical fluid chromatograph.

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

NASA Astrophysics Data System (ADS)

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.

Simultaneous Separation of Manganese, Cobalt, and Nickel by the Organic-Aqueous-Aqueous Three-Phase Solvent Extraction

NASA Astrophysics Data System (ADS)

Shirayama, Sakae; Uda, Tetsuya

2016-04-01

This research outlines an organic-aqueous-aqueous three-phase solvent extraction method and proposes its use in a new metal separation process for the recycling of manganese (Mn), cobalt (Co), and nickel (Ni) from used lithium ion batteries (LIBs). The three-phase system was formed by mixing xylene organic solution, 50 pct polyethylene glycol (PEG) aqueous solution, and 1 mol L-1 sodium sulfate (Na2SO4) aqueous solution. The xylene organic solution contained 2-ethylhexylphosphonic acid (D2EHPA) as an extractant for Mn ion, and the Na2SO4 aqueous solution contained 1 mol L-1 potassium thiocyanate (KSCN) as an extractant for Co ion. Concentrations of the metal ions were varied by dissolving metal sulfates in the Na2SO4 aqueous solution. As a result of the experiments, Mn, Co, and Ni ions were distributed in the xylene organic phase, PEG-rich aqueous phase, and Na2SO4-rich aqueous phase, respectively. The separation was effective when the pH value was around 4. Numerical simulation was also conducted in order to predict the distribution of metal ions after the multi-stage counter-current extractions.

Process for extracting technetium from alkaline solutions

DOEpatents

Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.

1995-01-01

A process for extracting technetium values from an aqueous alkaline solution containing at least one alkali metal hydroxide and at least one alkali metal nitrate, the at least one alkali metal nitrate having a concentration of from about 0.1 to 6 molar. The solution is contacted with a solvent consisting of a crown ether in a diluent for a period of time sufficient to selectively extract the technetium values from the aqueous alkaline solution. The solvent containing the technetium values is separated from the aqueous alkaline solution and the technetium values are stripped from the solvent.

Mechanism of transport and distribution of organic solvents in blood

NASA Technical Reports Server (NTRS)

Lam, C. W.; Galen, T. J.; Boyd, J. F.; Pierson, D. L.

1990-01-01

Little is known about the mechanism of transport and distribution of volatile organic compounds in blood. Studies were conducted on five typical organic solvents to investigate how these compounds are transported and distributed in blood. Groups of four to five rats were exposed for 2 hr to 500 ppm of n-hexane, toluene, chloroform, methyl isobutyl ketone (MIBK), or diethyl ether vapor; 94, 66, 90, 51, or 49%, respectively, of these solvents in the blood were found in the red blood cells (RBCs). Very similar results were obtained in vitro when aqueous solutions of these solvents were added to rat blood. In vitro studies were also conducted on human blood with these solvents; 66, 43, 65, 49, or 46%, respectively, of the added solvent was taken up by the RBCs. These results indicate that RBCs from humans and rats exhibited substantial differences in affinity for the three more hydrophobic solvents studied. When solutions of these solvents were added to human plasma and RBC samples, large fractions (51-96%) of the solvents were recovered from ammonium sulfate-precipitated plasma proteins and hemoglobin. Smaller fractions were recovered from plasma water and red cell water. Less than 10% of each of the added solvents in RBC samples was found in the red cell membrane ghosts. These results indicate that RBCs play an important role in the uptake and transport of these solvents. Proteins, chiefly hemoglobin, are the major carriers of these compounds in blood. It can be inferred from the results of the present study that volatile lipophilic organic solvents are probably taken up by the hydrophobic sites of blood proteins.

Poly(ethylene glycol)-based ionic liquids: properties and uses as alternative solvents in organic synthesis and catalysis.

PubMed

Cecchini, Martina Maya; Charnay, Clarence; De Angelis, Francesco; Lamaty, Frédéric; Martinez, Jean; Colacino, Evelina

2014-01-01

PEG-based ionic liquids are a new appealing group of solvents making the link between two distinct but very similar fluids: ionic liquids and poly(ethylene glycol)s. They find applications across a range of innumerable disciplines in science, technology, and engineering. In the last years, the possibility to use these as alternative solvents for organic synthesis and catalysis has been increasingly explored. This Review highlights strategies for their synthesis, their physical properties (critical point, glass transition temperature, density, rheological properties), and their application in reactions catalyzed by metals (such as Pd, Cu, W, or Rh) or as organic solvent (for example for multicomponent reactions, organocatalysis, CO2 transformation) with special emphasis on their toxicity, environmental impact, and biodegradability. These aspects, very often neglected, need to be considered in addition to the green criteria usually considered to establish ecofriendly processes. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extracting organic matter on Mars: A comparison of methods involving subcritical water, surfactant solutions and organic solvents

NASA Astrophysics Data System (ADS)

Luong, Duy; Court, Richard W.; Sims, Mark R.; Cullen, David C.; Sephton, Mark A.

2014-09-01

The first step in many life detection protocols on Mars involves attempts to extract or isolate organic matter from its mineral matrix. A number of extraction options are available and include heat and solvent assisted methods. Recent operations on Mars indicate that heating samples can cause the loss or obfuscation of organic signals from target materials, raising the importance of solvent-based systems for future missions. Several solvent types are available (e.g. organic solvents, surfactant based solvents and subcritical water extraction) but a comparison of their efficiencies in Mars relevant materials is missing. We have spiked the well characterised Mars analogue material JSC Mars-1 with a number of representative organic standards. Extraction of the spiked JSC Mars-1 with the three solvent methods provides insights into the relative efficiency of these methods and indicates how they may be used on future Mars missions.

Effect of Organic Solvents on Microalgae Growth, Metabolism and Industrial Bioproduct Extraction: A Review.

PubMed

Miazek, Krystian; Kratky, Lukas; Sulc, Radek; Jirout, Tomas; Aguedo, Mario; Richel, Aurore; Goffin, Dorothee

2017-07-04

In this review, the effect of organic solvents on microalgae cultures from molecular to industrial scale is presented. Traditional organic solvents and solvents of new generation-ionic liquids (ILs), are considered. Alterations in microalgal cell metabolism and synthesis of target products (pigments, proteins, lipids), as a result of exposure to organic solvents, are summarized. Applications of organic solvents as a carbon source for microalgal growth and production of target molecules are discussed. Possible implementation of various industrial effluents containing organic solvents into microalgal cultivation media, is evaluated. The effect of organic solvents on extraction of target compounds from microalgae is also considered. Techniques for lipid and carotenoid extraction from viable microalgal biomass (milking methods) and dead microalgal biomass (classical methods) are depicted. Moreover, the economic survey of lipid and carotenoid extraction from microalgae biomass, by means of different techniques and solvents, is conducted.

Acquired intolerance to organic solvents and results of vestibular testing

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

Gyntelberg, F.; Vesterhauge, S.; Fog, P.

1986-01-01

Among 160 consecutive patients referred to the Clinic of Occupational Medicine, Rigshospitalet, for symptoms connected with exposure to organic solvents, 20 exhibited symptoms of acquired intolerance to minor amounts of organic solvents. Later, an additional 30 consecutive patients with symptoms of acquired intolerance were included, yielding a total of 43 men and 7 women. The characteristics of the clinical syndrome described are complaints of dizziness, nausea, and weakness after exposure to minimal solvent vapor concentrations. After having tolerated long-term occupational exposure to moderate or high air concentrations of various organic solvents, the patients became intolerant within a short period ofmore » time. Since dizziness was a frequent complaint, we tried to obtain a measure of the patients' complaints using vestibular tests. As a diagnostic test the combined vestibular tests had a sensitivity of 0.55 and a specificity of 0.87. No differences between patients with and without intolerance could be detected by the vestibular tests used. We conclude that acquired intolerance to organic solvents is a new but characteristic and easily recognizable syndrome, often with severe consequences for the patient's working ability.« less

Chemical effects of alkali atoms on critical temperature in superconducting alkali-doped fullerides

NASA Astrophysics Data System (ADS)

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.

Alkali-Resistant Mechanism of a Hollandite DeNOx Catalyst.

PubMed

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.

Effect of Organic Solvents on Microalgae Growth, Metabolism and Industrial Bioproduct Extraction: A Review

PubMed Central

Miazek, Krystian; Sulc, Radek; Jirout, Tomas; Aguedo, Mario; Goffin, Dorothee

2017-01-01

In this review, the effect of organic solvents on microalgae cultures from molecular to industrial scale is presented. Traditional organic solvents and solvents of new generation-ionic liquids (ILs), are considered. Alterations in microalgal cell metabolism and synthesis of target products (pigments, proteins, lipids), as a result of exposure to organic solvents, are summarized. Applications of organic solvents as a carbon source for microalgal growth and production of target molecules are discussed. Possible implementation of various industrial effluents containing organic solvents into microalgal cultivation media, is evaluated. The effect of organic solvents on extraction of target compounds from microalgae is also considered. Techniques for lipid and carotenoid extraction from viable microalgal biomass (milking methods) and dead microalgal biomass (classical methods) are depicted. Moreover, the economic survey of lipid and carotenoid extraction from microalgae biomass, by means of different techniques and solvents, is conducted. PMID:28677659

Water Adsorption on Various Metal Organic Framework

NASA Astrophysics Data System (ADS)

Teo, H. W. B.; Chakraborty, A.

2017-12-01

In this paper, Metal Organic Framework (MOF) undergoes N2 and water adsorption experiment to observe how the material properties affects the water sorption performance. The achieved N2 isotherms is used to estimate the BET surface area, pore volume and, most importantly, the pore size distribution of the adsorbent material. It is noted that Aluminium Fumarate and CAU-10 has pore distribution of about 6Å while MIL-101(Cr) has 16 Å. The water adsorption isotherms at 25°C shows MIL-101(Cr) has a long hydrophobic length from relative pressure of 0 ≤ P/Ps ≤ 0.4 with a maximum water uptake of 1kg/kg sorbent. Alkali metal ions doped MIL-101(Cr) reduced the hydrophobic length and maximum water uptake of original MIL-101(Cr). Aluminium Fumarate and CAU-10 has lower water uptake, but the hydrophobic length of both materials is within relative pressure of P/Ps ≤ 0.2. The kinetic behaviour of doped MIL-101(Cr), Aluminium Fumarate and CAU-10 are faster than MIL-101(Cr).

Insight from first principles into the stability and magnetism of alkali-metal superoxide nanoclusters

NASA Astrophysics Data System (ADS)

Arcelus, Oier; Suaud, Nicolas; Katcho, Nebil A.; Carrasco, Javier

2017-05-01

Alkali-metal superoxides are gaining increasing interest as 2p magnetic materials for information and energy storage. Despite significant research efforts on bulk materials, gaps in our knowledge of the electronic and magnetic properties at the nanoscale still remain. Here, we focused on the role that structural details play in determining stability, electronic structure, and magnetic couplings of (MO2)n (M = Li, Na, and K, with n = 2-8) clusters. Using first-principles density functional theory based on the Perdew-Burke-Ernzerhof and Heyd-Scuseria-Ernzerhof functionals, we examined the effect of atomic structure on the relative stability of different polymorphs within each investigated cluster size. We found that small clusters prefer to form planar-ring structures, whereas non-planar geometries become more stable when increasing the cluster size. However, the crossover point depends on the nature of the alkali metal. Our analysis revealed that electrostatic interactions govern the highly ionic M-O2 bonding and ultimately control the relative stability between 2-D and 3-D geometries. In addition, we analyzed the weak magnetic couplings between superoxide molecules in (NaO2)4 clusters comparing model Hamiltonian methods based on Wannier function projections onto πg states with wave function-based multi-reference calculations.

Experimental and Theoretical Study of Molecular Response of Amine Bases in Organic Solvents

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

Kathmann, Shawn M.; Cho, Herman M.; Chang, Tsun-Mei

2014-05-08

Reorientational correlation times of various amine bases (viz., pyridine, 2,6-lutidene, 2,2,6,6-tetramethylpiperidine) and organic solvents (dichloromethane, toluene) were determined by solution-state NMR relaxation time measurements and compared with predictions from molecular dynamics (MD) simulations. The bases and solvents are reagents in complex reactions involving Frustrated Lewis Pairs (FLP), which display remarkable catalytic activity in metal-free H2 scission. The comparison of measured and simulated correlation times is a key test of the ability of recent MD and quantum electronic structure calculations to elucidate the mechanism of FLP activity. Correla- tion times were found to be in the range 1.4-3.4 ps (NMR) andmore » 1.23-5.28 ps (MD) for the amines, and 0.9-2.3 ps (NMR) and 0.2-1.7 ps (MD) for the solvent molecules. This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacic Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.« less

Calculating the thermodynamic properties of aqueous solutions of alkali metal carboxylates

NASA Astrophysics Data System (ADS)

Rudakov, A. M.; Sergievskii, V. V.; Zhukova, T. V.

2014-06-01

A modified Robinson-Stokes equation with terms that consider the formation of ionic hydrates and associates is used to describe thermodynamic properties of aqueous solutions of electrolytes. The model is used to describe data on the osmotic coefficients of aqueous solutions of alkali metal carboxylates, and to calculate the mean ionic activity coefficients of salts and excess Gibbs energies. The key contributions from ionic hydration and association to the nonideality of solutions is determined by analyzing the contributions of various factors. Relations that connect the hydration numbers of electrolytes with the parameters of the Pitzer-Mayorga equation and a modified Hückel equation are developed.

Detergent-compatible, organic solvent-tolerant alkaline protease from Bacillus circulans MTCC 7942: Purification and characterization.

PubMed

Patil, Ulhas; Mokashe, Narendra; Chaudhari, Ambalal

2016-01-01

Proteases are now recognized as the most indispensable industrial biocatalyst owing to their diverse microbial sources and innovative applications. In the present investigation, a thermostable, organic solvent-tolerant, alkaline serine protease from Bacillus circulans MTCC 7942, was purified and characterized. The protease was purified to 37-fold by a three-step purification scheme with 39% recovery. The optimum pH and temperature for protease was 10 and 60 °C, respectively. The apparent molecular mass of the purified enzyme was 43 kD as revealed by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). The Km and Vmax values using casein-substrate were 3.1 mg/mL and 1.8 µmol/min, respectively. The protease remained stable in the presence of organic solvents with higher (>3.2) log P value (cyclohexane, n-octane, n-hexadecane, n-decane, and n-dodecane), as compared to organic solvents with lower (<3.2) log P value (acetone, butanol, benzene, chloroform, toluene). Remarkably, the protease showed profound stability even in the presence of organic solvents with less log P values (glycerol, dimethyl sulfate [DMSO], p-xylene), indicating the possibility of nonaqueous enzymatic applications. Also, protease activity was improved in the presence of metal ions (Ca(2+), Mg(2+), Mn(2+)); enhanced by biosurfactants; hardly affected by bleaching agents, oxidizing agents, and chemical surfactants; and stable in commercial detergents. In addition, a protease-detergent formulation effectively washed out egg and blood stains as compared to detergent alone. The protease was suitable for various commercial applications like processing of gelatinous film and as a compatible additive to detergent formulation with its operative utility in hard water.

Integration of ceramic membrane and compressed air-assisted solvent extraction (CASX) for metal recovery.

PubMed

Li, Chi-Wang; Chiu, Chun-Hao; Lee, Yu-Cheng; Chang, Chia-Hao; Lee, Yu-Hsun; Chen, Yi-Ming

2010-01-01

In our previous publications, compressed air-assisted solvent extraction process (CASX) was developed and proved to be kinetically efficient process for metal removal. In the current study, CASX with a ceramic MF membrane integrated for separation of spent solvent was employed to remove and recover metal from wastewater. MF was operated either in crossflow mode or dead-end with intermittent flushing mode. Under crossflow mode, three distinct stages of flux vs. TMP (trans-membrane pressure) relationship were observed. In the first stage, flux increases with increasing TMP which is followed by the stage of stable flux with increasing TMP. After reaching a threshold TMP which is dependent of crossflow velocity, flux increases again with increasing TMP. At the last stage, solvent was pushed through membrane pores as indicated by increasing permeate COD. In dead-end with intermittent flushing mode, an intermittent flushing flow (2 min after a 10-min or a 30-min dead-end filtration) was incorporated to reduce membrane fouling by flush out MSAB accumulated on membrane surface. Effects of solvent concentration and composition were also investigated. Solvent concentrations ranging from 0.1 to 1% (w/w) have no adverse effect in terms of membrane fouling. However, solvent composition, i.e. D(2)EHPA/kerosene ratio, shows impact on membrane fouling. The type of metal extractants employed in CASX has significant impact on both membrane fouling and the quality of filtrate due to the differences in their viscosity and water solubility. Separation of MSAB was the limiting process controlling metal removal efficiency, and the removal efficiency of Cd(II) and Cr(VI) followed the same trend as that for COD.

Non-Adiabatic Atomic Transitions: Computational Cross Section Calculations of Alkali Metal-Noble Gas Collisions

DTIC Science & Technology

2011-09-01

there a one time transfer of prob- ability between Coriolis coupled states. One possible way to answer this question would be to literally create and... time -dependent numerical algorithm was developed using FORTRAN 90 to predict S-Matrix elements for alkali metal - noble gas (MNg) collisions. The...committee and the physics department for their time and effort to see me through the completion of my doctorate degree. Charlton D. Lewis, II v Table of

3718-F Alkali Metal Treatment and Storage Facility Closure Plan

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

None

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; wastemore » characteristics; groundwater; closure strategy and performance standards; closure activities; postclosure; and references.« less

Development of processes for the production of solar grade silicon from halides and alkali metals

NASA Technical Reports Server (NTRS)

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.

CHARACTERIZATION OF MERCURY EMISSIONS AT A CHLOR-ALKALI PLANT: STUDY ORGANIZATION AND IMPLEMENTATION

EPA Science Inventory

The paper describes the organization and implementation of a detailed emissions measurement campaign conducted over a 2-week period at the Olin Corporation's mercury chlor-alkali plant in Augusta, GA. (NOTE: Since data analysis is continuing, study results will be provided later...

Structure-directing effects of ionic liquids in the ionothermal synthesis of metal-organic frameworks.

PubMed

Vaid, Thomas P; Kelley, Steven P; Rogers, Robin D

2017-07-01

Traditional synthesis of metal-organic frameworks (MOFs) involves the reaction of a metal-containing precursor with an organic linker in an organic solvent at an elevated temperature, in what is termed a 'solvothermal' reaction. More recently, many examples have been reported of MOF synthesis in ionic liquids (ILs), rather than an organic solvent, in 'ionothermal' reactions. The high concentration of both cations and anions in an ionic liquid allows for the formation of new MOF structures in which the IL cation or anion or both are incorporated into the MOF. Most commonly, the IL cation is included in the open cavities of the MOF, countering the anionic charge of the MOF framework itself and acting as a template around which the MOF structure forms. Ionic liquids can also serve other structure-directing roles, for example, when an IL containing a single enantiomer of a chiral anion leads to a homochiral MOF, even though the IL anion is not itself incorporated into the MOF. A comprehensive review of ionothermal syntheses of MOFs, and the structure-directing effects of the ILs, is given.

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

PubMed

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.

Solvent tuning configurational conversion of lycopene aggregates in organic-aqueous mixing solvent

NASA Astrophysics Data System (ADS)

Dong, Jia; Zhang, Di; Wang, Xin-Yue; Wang, Peng

2018-06-01

In general cases, carotenoid aggregates are prepared in organic-water mixing solvent depending on its hydrophobic character. It is well-known that one of carotenoids, lycopene, is more likely to form typical H-aggregates. In this study, new type lycopene J-aggregates were prepared in DMSO-water mixing solvent with small amount of toluene, which was observed for the first time. We proposed a potential structure model combining with exciton model to interpret the mechanism of spectra changes. Our finding has provided new methods and novel ideas for controlling carotenoid aggregates formation.

RECOVERY OF METAL VALUES FROM AQUEOUS SOLUTIONS BY SOLVENT EXTRACTION

DOEpatents

Moore, R.L.

1959-09-01

An organic solvent mixure is described for extracting actinides from aqueous solutions; the solvent mixture consists of from 10 to 25% by volume of tributyl phosphate and the remainder a chlorine-fluorine-substituted saturated hydrocarbon having two carbon atoms in the molecule.

Alkali-earth metal bridges formed in biofilm matrices regulate the uptake of fluoroquinolone antibiotics and protect against bacterial apoptosis.

PubMed

Kang, Fuxing; Wang, Qian; Shou, Weijun; Collins, Chris D; Gao, Yanzheng

2017-01-01

Bacterially extracellular biofilms play a critical role in relieving toxicity of fluoroquinolone antibiotic (FQA) pollutants, yet it is unclear whether antibiotic attack may be defused by a bacterial one-two punch strategy associated with metal-reinforced detoxification efficiency. Our findings help to assign functions to specific structural features of biofilms, as they strongly imply a molecularly regulated mechanism by which freely accessed alkali-earth metals in natural waters affect the cellular uptake of FQAs at the water-biofilm interface. Specifically, formation of alkali-earth-metal (Ca 2+ or Mg 2+ ) bridge between modeling ciprofloxacin and biofilms of Escherichia coli regulates the trans-biofilm transport rate of FQAs towards cells (135-nm-thick biofilm). As the addition of Ca 2+ and Mg 2+ (0-3.5 mmol/L, CIP: 1.25 μmol/L), the transport rates were reduced to 52.4% and 63.0%, respectively. Computational chemistry analysis further demonstrated a deprotonated carboxyl in the tryptophan residues of biofilms acted as a major bridge site, of which one side is a metal and the other is a metal girder jointly connected to the carboxyl and carbonyl of a FQA. The bacterial growth rate depends on the bridging energy at anchoring site, which underlines the environmental importance of metal bridge formed in biofilm matrices in bacterially antibiotic resistance. Copyright © 2016 Elsevier Ltd. All rights reserved.

Metal-mediated aminocatalysis provides mild conditions: Enantioselective Michael addition mediated by primary amino catalysts and alkali-metal ions

PubMed Central

Leven, Matthias; Neudörfl, Jörg M

2013-01-01

Summary 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. PMID:23400419

Separation and recovery of heavy metals from waste water using synergistic solvent extraction

NASA Astrophysics Data System (ADS)

Li, Yan; Yang, Limei; Xu, Zheng; Sun, Qi

2017-01-01

Heavy metal wastewater pollution is one of the three major water pollutions in the world. The zinc hydrometallurgy smelting process usually discharge large quantities of heavy metal wastewater into the environment. In this paper, a synergistic solvent extraction process has been developed to recover copper, nickel, zinc and cadmium respectively from calcium and magnesium. The synergistic organic system contained 0.50 M Versatic 10 and 0.5 M Mextral 984H in DT100. Adjusting pH to 2.0 at 40 °C, the copper will be extracted preferentially with the extraction rate more than 99%. Continuing to adjust pH to 4.2 at 40 °C, the nickel will be extracted secondly with an extraction rate more than 98%; the zinc and cadmium in raffinate could be extracted separately while pH is about 6.5.

Occupational exposures to solvents and metals are associated with fixed airflow obstruction.

PubMed

Alif, Sheikh M; Dharmage, Shyamali C; Benke, Geza; Dennekamp, Martine; Burgess, John A; Perret, Jennifer L; Lodge, Caroline J; Morrison, Stephen; Johns, David P; Giles, Graham G; Gurrin, Lyle C; Thomas, Paul S; Hopper, John L; Wood-Baker, Richard; Thompson, Bruce R; Feather, Iain H; Vermeulen, Roel; Kromhout, Hans; Walters, E Haydn; Abramson, Michael J; Matheson, Melanie C

2017-11-01

Objectives This study investigated the associations between occupational exposures to solvents and metals and fixed airflow obstruction (AO) using post-bronchodilator spirometry. Methods We included 1335 participants from the 2002-2008 follow-up of the Tasmanian Longitudinal Health Study. Ever-exposure and cumulative exposure-unit (EU) years were calculated using the ALOHA plus job exposure matrix (JEM). Fixed AO was defined as post-bronchodilator forced expiratory volume in one second (FEV1)/forced vital capacity (FVC) <0.7 and FEV 1 /FVCmetals was associated with fixed AO [relative risk (RR) 1.71, 95% CI 1.03-2.85] and fixed AO lower limit of normal (RR 1.67, 95% CI 1.00-2.78). Women had lower cumulative EU years to chlorinated solvents [mean 20.9, standard deviation (SD) 13.4] than men (mean 28.6, SD 36.9). However, the risk of developing fixed AO and fixed AO plus low DLCO associated with each cumulative EU year of chlorinated solvents were higher among women than men (RR 1.08 versus 0.99, P-value for effect measure modification=0.006; RR 1.08 versus 1.00, P-value for effect measure modification=0.02). Conclusions We have shown ever-exposure to metals and chlorinated solvents are important risk factors for fixed AO. The effects for solvents were strongest among women. Preventive strategies need to be followed to reduce these exposures at the workplace.

Hydrogen generation using silicon nanoparticles and their mixtures with alkali metal hydrides

NASA Astrophysics Data System (ADS)

Patki, Gauri Dilip

mole of Si. We compare our silicon nanoparticles (˜10nm diameter) with commercial silicon nanopowder (<100nm diameter) and ball-milled silicon powder (325 mesh). The increase in 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 <100 nm to ˜10 nm particles, the hydrogen production 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.

Heating rates in collisionally opaque alkali-metal atom traps: Role of secondary collisions

NASA Astrophysics Data System (ADS)

Beijerinck, H. C. W.

2000-12-01

Grazing collisions with background gas are the major cause of trap loss and trap heating in atom traps. To first order, these effects do not depend on the trap density. In collisionally opaque trapped atom clouds, however, scattered atoms with an energy E larger than the effective trap depth Eeff, which are destined to escape from the atom cloud, will have a finite probability for a secondary collision. This results in a contribution to the heating rate that depends on the column density of the trapped atoms, i.e., the product of density and characteristic size of the trap. For alkali-metal atom traps, secondary collisions are quite important due to the strong long-range interaction with like atoms. We derive a simple analytical expression for the secondary heating rate, showing a dependency proportional to E1/2eff. When extrapolating to a vanishing column density, only primary collisions with the background gas will contribute to the heating rate. This contribution is rather small, due to the weak long-range interaction of the usual background gas species in an ultrahigh-vacuum system-He, Ne, or Ar-with the trapped alkali-metal atoms. We conclude that the transition between trap-loss collisions and heating collisions is determined by a cutoff energy 200 μK<=Eeff<=400 μK, much smaller than the actual trap depth E in most magnetic traps. Atoms with an energy Eeffalkali-metal atoms Li through Cs as a function of the effective trap depth, the column density of the trap, and the species in the background gas. The predictions of our model are in good agreement with the experimental data of Myatt for heating rates in high-density 87Rb-atom magnetic traps at JILA, including the effect of the rf shield and the composition of the background gas. It is shown that collisions with atoms from the Oort

Properties and Synthetic Applications of Enzymes in Organic Solvents.

PubMed

Carrea; Riva

2000-07-03

Biotransformations already represent an effective and sometimes preferable alternative to chemical synthesis for the production of fine chemicals and optically active compounds. To further widen the versatility of the biological approach, the so-called "nonaqueous enzymology", which now represents an important area of research and biotechnological development, has emerged in the last ten years or so. This new methodology is especially suitable for the modification of precursors of pharmaceutical compounds and fine chemicals, which, in most cases, are insoluble or poorly soluble in water. Even though the idea of carrying out an enzymatic process in organic solvent was initially considered with scepticism, biocatalysis in such media is now investigated and exploited in numerous academic and industrial laboratories. One of the reasons that makes enzymatic catalysis in nonaqueous media so appealing, is the important new properties that enzymes exhibit in organic solvents. For example, they are often more stable and can catalyze reactions that are impossible or difficult in water. Furthermore, enzyme selectivity can also differ from that in water and can change, or even reverse, from one solvent to another. This phenomenon, which can be called "medium engineering", can be exploited as a valid alternative to protein engineering. The first part of this review examines the thermodynamic, kinetic, spectroscopic, and physical approaches that have been adopted to investigate the factors that affect activity, stability, structure, and selectivity of enzymes in organic solvents. These combined studies have brought the understanding of enzyme catalysis in organic solvents to a level almost comparable to that reached for biocatalysis in aqueous media. The second part surveys a number of the synthetic applications of enzymes in organic media, which span from the preparation of milligrams of specifically labeled compounds to the modification of fats on multiton scale and from the

Intracellular acidification-induced alkali metal cation/H+ exchange in human neutrophils

PubMed Central

1987-01-01

Pretreatment of isolated human neutrophils (resting pHi congruent to 7.25 at pHo 7.40) with 30 mM NH4Cl for 30 min leads to an intracellular acidification (pHi congruen to 6.60) when the NH4Cl prepulse is removed. Thereafter, in 140 mM Na+ medium, pHi recovers exponentially with time (initial rate, approximately 0.12 pH/min) to reach the normal resting pHi by approximately 20 min, a process that is accomplished mainly, if not exclusively, though an exchange of internal H+ for external Na+. This Na+/H+ countertransport is stimulated by external Na+ (Km congruent to 21 mM) and by external Li+ (Km congruent to 14 mM), though the maximal transport rate for Na+ is about twice that for Li+. Both Na+ and Li+ compete as substrates for the same translocation sites on the exchange carrier. Other alkali metal cations, such as K+, Rb+, or Cs+, do not promote pHi recovery, owing to an apparent lack of affinity for the carrier. The exchange system is unaffected by ouabain or furosemide, but can be competitively inhibited by the diuretic amiloride (Ki congruent to 8 microM). The influx of Na+ or Li+ is accompanied by an equivalent counter-reflux of H+, indicating a 1:1 stoichiometry for the exchange reaction, a finding consistent with the lack of voltage sensitivity (i.e., electroneutrality) of pHi recovery. These studies indicate that the predominant mechanism in human neutrophils for pHi regulation after intracellular acidification is an amiloride-sensitive alkali metal cation/H+ exchange that shares a number of important features with similar recovery processes in a variety of other mammalian cell types. PMID:3694176

Enzymatic synthesis of esculin ester in ionic liquids buffered with organic solvents.

PubMed

Hu, Yifan; Guo, Zheng; Lue, Bena-Marie; Xu, Xuebing

2009-05-13

The enzymatic esterification of esculin catalyzed by Candida antarctica lipase B (Novozym 435) was carried out in ionic liquid (IL)-organic solvent mixed systems in comparison with individual systems. The reaction behaviors in IL-organic solvents were systemically evaluated using acetone as a model solvent. With organic solvents as media, the esterification rates of esculin depended mainly on its solubility in solvents; for the reactions in ILs, the reaction rates were generally low, and the anion part of the IL played a critical role in enzyme activity. Therefore, the esterification of esculin in IL-acetone mixtures made it possible to improve the solubility of esculin while the effects of ILs on lipase activity were minimized. Following the benignity of ILs to lipase activity, the anions of ILs were ranked in the order as [Tf(2)N](-) > [PF(6)](-) > [BF(4)](-) > [CF(3)SO(3)](-) > [C(4)F(9)SO(3)](-) > [TAF](-) > [MDEGSO(4)](-) > [OctSO(4)](-) > [ES](-) = [DMP](-) = [OTs](- )= Cl(-). The reaction behaviors differed in different systems and largely depended on the properties of the ILs and organic solvents. In general, improvements were observed in terms of both solubility and reaction efficiency. The knowledge acquired in this work gives a better understanding of multiple interactions in IL-organic solvent systems, which provide guidance for system design and optimization.

Occupational exposure to organic solvents as a cause of sleep apnoea.

PubMed Central

Edling, C; Lindberg, A; Ulfberg, J

1993-01-01

A high prevalence of sleep apnoea was found in a group of men occupationally exposed to organic solvents. Workers with long term exposure to organic solvents often report symptoms such as fatigue, forgetfulness, and concentration difficulties. These symptoms are strikingly similar to those reported by patients with obstructive sleep apnoea syndrome (OSAS). This is a frequently diagnosed disorder characterised by disturbed sleep causing psychic or somatic complications and daytime sleepiness. A study was undertaken to evaluate whether people with long term occupational exposure to organic solvents have a higher prevalence of sleep apnoea than the general population. Patients exposed to solvents (66 men) were invited to participate in a screening for sleep apnoea. A static charge sensitive bed was used for the monitoring of respiration movements and pulse oximetry during one night. A classical sleep apnoea was diagnosed if periodic respiration movement exceeded 45% of estimated sleep time and the oxygen desaturation index exceeded 6. The prevalence of sleep apnoea among the men exposed to solvents was compared with the prevalence in the general population (1.4%). The prevalence among the participating exposed men was 19.7% which gave a conservative relative risk estimate of 14.1 (95% confidence interval (95% CI) 7.5-24.2). The results indicate that exposure to organic solvents causes sleep apnoea. An alternative possibility is that people with sleep apnoea are misdiagnosed as cases of solvent induced toxic encephalopathy. The interpretation has importance for the caring of the patient. PMID:8457496

James C. McGroddy Prize Talk: Superconductivity in alkali-metal doped Carbon-60

NASA Astrophysics Data System (ADS)

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.

The role of oxygen in porous molybdenum electrodes for the alkali metal thermoelectric converter

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

Williams, R.M.; Nagasubramanian, G.; Khanna, S.K.

1986-08-01

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/submore » 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.« less

Neutral glycoconjugated amide-based calix[4]arenes: complexation of alkali metal cations in water.

PubMed

Cindro, Nikola; Požar, Josip; Barišić, Dajana; Bregović, Nikola; Pičuljan, Katarina; Tomaš, Renato; Frkanec, Leo; Tomišić, Vladislav

2018-02-07

Cation complexation in water presents a unique challenge in calixarene chemistry, mostly due to the fact that a vast majority of calixarene-based cation receptors is not soluble in water or their solubility has been achieved by introducing functionalities capable of (de)protonation. Such an approach inevitably involves the presence of counterions which compete with target cations for the calixarene binding site, and also rather often requires the use of ion-containing buffer solutions in order to control the pH. Herein we devised a new strategy towards the solution of this problem, based on introducing carbohydrate units at the lower or upper rim of calix[4]arenes which comprise efficient cation binding sites. In this context, we prepared neutral, water-soluble receptors with secondary or tertiary amide coordinating groups, and studied their complexation with alkali metal cations in aqueous and methanol (for the comparison purpose) solutions. Complexation thermodynamics was quantitatively characterized by UV spectrometry and isothermal titration calorimetry, revealing that one of the prepared tertiary amide derivatives is capable of remarkably efficient (log K ≈ 5) and selective binding of sodium cations among alkali metal cations in water. Given the ease of the synthetic procedure used, and thus the variety of accessible analogues, this study can serve as a platform for the development of reagents for diverse purposes in aqueous media.

Rare-gas impurities in alkali metals: Relation to optical absorption

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

Meltzer, D.E.; Pinski, F.J.; Stocks, G.M.

1988-04-15

An investigation of the nature of rare-gas impurity potentials in alkali metals is performed. Results of calculations based on simple models are presented, which suggest the possibility of resonance phenomena. These could lead to widely varying values for the exponents which describe the shape of the optical-absorption spectrum at threshold in the Mahan--Nozieres--de Dominicis theory. Detailed numerical calculations are then performed with the Korringa-Kohn-Rostoker coherent-potential-approximation method. The results of these highly realistic calculations show no evidence for the resonance phenomena, and lead to predictions for the shape of the spectra which are in contradiction to observations. Absorption and emission spectramore » are calculated for two of the systems studied, and their relation to experimental data is discussed.« less

Metallated metal-organic frameworks

DOEpatents

Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

2017-02-07

Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

Metallated metal-organic frameworks

DOEpatents

Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

2017-08-22

Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

Photothermal Activation of Metal-Organic Frameworks Using a UV-Vis Light Source.

PubMed

Espín, Jordi; Garzón-Tovar, Luis; Carné-Sánchez, Arnau; Imaz, Inhar; Maspoch, Daniel

2018-03-21

Metal-organic frameworks (MOFs) usually require meticulous removal of the solvent molecules to unlock their potential porosity. Herein, we report a novel one-step method for activating MOFs based on the photothermal effect induced by directly irradiating them with a UV-vis lamp. The localized light-to-heat conversion produced in the MOF crystals upon irradiation enables a very fast solvent removal, thereby significantly reducing the activation time to as low as 30 min and suppressing the need for time-consuming solvent-exchange procedures and vacuum conditions. This approach is successful for a broad range of MOFs, including HKUST-1, UiO-66-NH 2 , ZIF-67, CPO-27-M (M = Zn, Ni, and Mg), Fe-MIL-101-NH 2 , and IRMOF-3, all of which exhibit absorption bands in the light emission range. In addition, we anticipate that this photothermal activation can also be used to activate covalent organic frameworks (COFs).

Polarization studies on zinc in hydrochloric acid solution containing some organic solvents

NASA Astrophysics Data System (ADS)

Mohamed, A. K.

1999-05-01

The corrosion behaviour of zinc metal in some organic solvents was tested electrochemically using galvanometric polarization measurements. The results showed that the studied organic solvents act as mixed type inhibitors. The inhibition was assumed to occur via physical adsorption of the inhibitor molecules fitting a Temkin's isotherm. The inhibition eficiency of the solvents increase in the order: glycerol>ethylene glycol>DMSO>dioxane. This order is not affected by the variation in temperature in the range 35-55 circC. The increase in temperature was found to increase the corrosion in absence and in presence of inhibitors. Some thermodynamic parameters for adsorption were also computed and discussed. Le comportement de corrosion du zinc métallique dans certains solvants organiques a été testé électrochimiquement en utilisant les mesures de polarisation galvanométrique. Les résultats ont montré que les solvants organiques étudiés agissent comme des inhibiteurs de type mixte. L'inhibition semble se produire par l'adsorption physique des molécules inhibitrices selon une isotherme de Temkin. L'efficacité d'inhibition des solvants augmente dans l'ordre suivant : glycérol>éthylène glycol>DMSO>dioxane. Cet ordre n'est pas affecté par une variation de température dans l'intervalle compris entre 35 et 55 circC. La corrosion augmente avec la température, en absence ou en présence d'inhibiteurs. Certains paramètres thermodynamiques d'adsorption ont été calculés et discutés.

A Quantitative Tunneling/Desorption Model for the Exchange Current at the Porous Electrode/Beta - Alumina/Alkali Metal Gas Three Phase Zone at 700-1300K

NASA Technical Reports Server (NTRS)

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.

Catalyst Of A Metal Heteropoly Acid Salt That Is Insoluble In A Polar Solvent On A Non-Metallic Porous Support And Method Of Making

DOEpatents

Wang. Yong; Peden. Charles H. F.; Choi. Saemin

2004-11-09

The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

Catalyst of a metal heteropoly acid salt that is insoluble in a polar solvent on a non-metallic porous support and method of making

DOEpatents

Wang, Yong [Richland, WA; Peden, Charles H. F. [West Richland, WA; Choi, Saemin [Richland, WA

2002-10-29

The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

Solution based zinc tin oxide TFTs: the dual role of the organic solvent

NASA Astrophysics Data System (ADS)

Salgueiro, Daniela; Kiazadeh, Asal; Branquinho, Rita; Santos, Lídia; Barquinha, Pedro; Martins, Rodrigo; Fortunato, Elvira

2017-02-01

Chemical solution deposition is a low cost, scalable and high performance technique to obtain metal oxide thin films. Recently, solution combustion synthesis has been introduced as a chemical route to reduce the processing temperature. This synthesis method takes advantage of the chemistry of the precursors as a source of energy for localized heating. According to the combustion chemistry some organic solvents can have a dual role in the reaction, acting both as solvent and fuel. In this work, we studied the role of 2-methoxyethanol in solution based synthesis of ZTO thin films and its influence on the performance of ZTO TFTs. The thermal behaviour of ZTO precursor solutions confirmed that 2-methoxyethanol acts simultaneously as a solvent and fuel, replacing the fuel function of urea. The electrical characterization of the solution based ZTO TFTs showed a slightly better performance and lower variability under positive gate bias stress when urea was not used as fuel, confirming that the excess fuel contributes negatively to the device operation and stability. Solution based ZTO TFTs demonstrated a low hysteresis (ΔV  =  -0.3 V) and a saturation mobility of 4-5 cm2 V-1 s-1.

Cation and anion dependence of stable geometries and stabilization energies of alkali metal cation complexes with FSA(-), FTA(-), and TFSA(-) anions: relationship with physicochemical properties of molten salts.

PubMed

Tsuzuki, Seiji; Kubota, Keigo; Matsumoto, Hajime

2013-12-19

Stable geometries and stabilization energies (Eform) of the alkali metal complexes with bis(fluorosulfonyl)amide, (fluorosulfonyl)(trifluoromethylslufonyl)amide and bis(trifluoromethylsulfonyl)amide (FSA(-), FTA(-) and TFSA(-)) were studied by ab initio molecular orbital calculations. The FSA(-) complexes prefer the bidentate structures in which two oxygen atoms of two SO2 groups have contact with the metal cation. The FTA(-) and TFSA(-) complexes with Li(+) and Na(+) prefer the bidentate structures, while the FTA(-) and TFSA(-) complexes with Cs(+) prefer tridentate structures in which the metal cation has contact with two oxygen atoms of an SO2 group and one oxygen atom of another SO2 group. The two structures are nearly isoenergetic in the FTA(-) and TFSA(-) complexes with K(+) and Rb(+). The magnitude of Eform depends on the alkali metal cation significantly. The Eform calculated for the most stable TFSA(-) complexes with Li(+), Na(+), K(+), Rb(+) and Cs(+) cations at the MP2/6-311G** level are -137.2, -110.5, -101.1, -89.6, and -84.1 kcal/mol, respectively. The viscosity and ionic conductivity of the alkali TFSA molten salts have strong correlation with the magnitude of the attraction. The viscosity increases and the ionic conductivity decreases with the increase of the attraction. The melting points of the alkali TFSA and alkali BETA molten salts also have correlation with the magnitude of the Eform, which strongly suggests that the magnitude of the attraction play important roles in determining the melting points of these molten salts. The anion dependence of the Eform calculated for the complexes is small (less than 2.9 kcal/mol). This shows that the magnitude of the attraction is not the cause of the low melting points of alkali FTA molten salts compared with those of corresponding alkali TFSA molten salts. The electrostatic interactions are the major source of the attraction in the complexes. The electrostatic energies for the most stable TFSA

Rydberg States of Alkali Metal Atoms on Superfluid Helium Droplets - Theoretical Considerations

NASA Astrophysics Data System (ADS)

Pototschnig, Johann V.; Lackner, Florian; Hauser, Andreas W.; Ernst, Wolfgang E.

2017-06-01

The bound states of electrons on the surface of superfluid helium have been a research topic for several decades. One of the first systems treated was an electron bound to an ionized helium cluster. Here, a similar system is considered, which consists of a helium droplet with an ionized dopant inside and an orbiting electron on the outside. In our theoretical investigation we select alkali metal atoms (AK) as central ions, stimulated by recent experimental studies of Rydberg states for Na, Rb, and Cs attached to superfluid helium nanodroplets. Experimental spectra , obtained by electronic excitation and subsequent ionization, showed blueshifts for low lying electronic states and redshifts for Rydberg states. In our theoretical treatment the diatomic AK^+-He potential energy curves are first computed with ab initio methods. These potentials are then used to calculate the solvation energy of the ion in a helium droplet as a function of the number of atoms. Additional potential terms, derived from the obtained helium density distribution, are added to the undisturbed atomic pseudopotential in order to simulate a 'modified' potential felt by the outermost electron. This allows us to compute a new set of eigenstates and eigenenergies, which we compare to the experimentally observed energy shifts for highly excited alkali metal atoms on helium nanodroplets. A. Golov and S. Sekatskii, Physica B, 1994, 194, 555-556 E. Loginov, C. Callegari, F. Ancilotto, and M. Drabbels, J. Phys. Chem. A, 2011, 115, 6779-6788 F. Lackner, G. Krois, M. Koch, and W. E. Ernst, J. Phys. Chem. Lett., 2012, 3, 1404-1408 F. Lackner, G. Krois, M. Theisen, M. Koch, and W. E. Ernst, Phys. Chem. Chem. Phys., 2011, 13, 18781-18788

Organic solvent pretreatment of lignocellulosic biomass for biofuels and biochemicals: A review.

PubMed

Zhang, Ke; Pei, Zhijian; Wang, Donghai

2016-01-01

Lignocellulosic biomass represents the largest potential volume and lowest cost for biofuel and biochemical production. Pretreatment is an essential component of biomass conversion process, affecting a majority of downstream processes, including enzymatic hydrolysis, fermentation, and final product separation. Organic solvent pretreatment is recognized as an emerging way ahead because of its inherent advantages, such as the ability to fractionate lignocellulosic biomass into cellulose, lignin, and hemicellulose components with high purity, as well as easy solvent recovery and solvent reuse. Objectives of this review were to update and extend previous works on pretreatment of lignocellulosic biomass for biofuels and biochemicals using organic solvents, especially on ethanol, methanol, ethylene glycol, glycerol, acetic acid, and formic acid. Perspectives and recommendations were given to fully describe implementation of proper organic solvent pretreatment for future research. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of charging on silicene with alkali metal atom adsorption

NASA Astrophysics Data System (ADS)

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.

CFA-7: an interpenetrated metal-organic framework of the MFU-4 family.

PubMed

Schmieder, Phillip; Grzywa, Maciej; Denysenko, Dmytro; Hambach, Manuel; Volkmer, Dirk

2015-08-07

The novel interpenetrated metal-organic framework CFA-7 (Coordination Framework Augsburg University-7), [Zn5Cl4(tqpt)3], has been synthesized containing the organic linker {H2-tqpt = 6,6,14,14-tetramethyl-6,14-dihydroquinoxalino[2,3-b]phenazinebistriazole}. Reaction of H2-tqpt and anhydrous ZnCl2 in N,N-dimethylformamide (DMF) yields CFA-7 as pseudo-cubic crystals. CFA-7 serves as precursor for the synthesis of isostructural frameworks with redox-active metal centers, which is demonstrated by postsynthetic metal exchange of Zn(2+) by different M(2+) (M = Co, Ni, Cu) ions. The novel framework is robust upon solvent removal and has been structurally characterized by single-crystal X-ray diffraction, TGA and IR spectroscopy, as well as gas sorption (Ar, CO2 and H2).

H-1 NMR study of ternary ammonia-alkali metal-graphite intercalation compounds

NASA Technical Reports Server (NTRS)

Tsang, T.; Fronko, R. M.; Resing, H. A.; Qian, X. W.; Solin, S. A.

1987-01-01

For the first-stage ternary ammonia-alkali metal-graphite intercalation compounds M(NH3)(x)C24(x of about 4, M = K, Rb, Cs), three sets of triplet H-1 NMR spectral lines have been observed at various temperatures and orientations due to the H-1 - H-1 and N-14 - H-1 dipolar interactions. The structures of these compounds have been inferred as mobile (liquid-like) intercalant layers of planar M(NH3)4 ions in between the carbon layers. For the intercalated ammonia molecules, the potential barrier is about 0.2 eV and the molecular geometry is very close to the free NH3 in gas phase.

Treatment of organic waste

DOEpatents

Grantham, LeRoy F.

1979-01-01

An organic waste containing at least one element selected from the group consisting of strontium, cesium, iodine and ruthenium is treated to achieve a substantial reduction in the volume of the waste and provide for fixation of the selected element in an inert salt. The method of treatment comprises introducing the organic waste and a source of oxygen into a molten salt bath maintained at an elevated temperature to produce solid and gaseous reaction products. The gaseous reaction products comprise carbon dioxide and water vapor, and the solid reaction products comprise the inorganic ash constituents of the organic waste and the selected element which is retained in the molten salt. The molten salt bath comprises one or more alkali metal carbonates, and may optionally include from 1 to about 25 wt.% of an alkali metal sulfate.

Control of wavepacket dynamics in mixed alkali metal clusters by optimally shaped fs pulses

NASA Astrophysics Data System (ADS)

Bartelt, A.; Minemoto, S.; Lupulescu, C.; Vajda, Š.; Wöste, L.

We have performed adaptive feedback optimization of phase-shaped femtosecond laser pulses to control the wavepacket dynamics of small mixed alkali-metal clusters. An optimization algorithm based on Evolutionary Strategies was used to maximize the ion intensities. The optimized pulses for NaK and Na2K converged to pulse trains consisting of numerous peaks. The timing of the elements of the pulse trains corresponds to integer and half integer numbers of the vibrational periods of the molecules, reflecting the wavepacket dynamics in their excited states.

Dissolution of covalent adaptable network polymers in organic solvent

NASA Astrophysics Data System (ADS)

Yu, Kai; Yang, Hua; Dao, Binh H.; Shi, Qian; Yakacki, Christopher M.

2017-12-01

It was recently reported that thermosetting polymers can be fully dissolved in a proper organic solvent utilizing a bond-exchange reaction (BER), where small molecules diffuse into the polymer, break the long polymer chains into short segments, and eventually dissolve the network when sufficient solvent is provided. The solvent-assisted dissolution approach was applied to fully recycle thermosets and their fiber composites. This paper presents the first multi-scale modeling framework to predict the dissolution kinetics and mechanics of thermosets in organic solvent. The model connects the micro-scale network dynamics with macro-scale material properties: in the micro-scale, a model is developed based on the kinetics of BERs to describe the cleavage rate of polymer chains and evolution of chain segment length during the dissolution. The micro-scale model is then fed into a continuum-level model with considerations of the transportation of solvent molecules and chain segments in the system. The model shows good prediction on conversion rate of functional groups, degradation of network mechanical properties, and dissolution rate of thermosets during the dissolution. It identifies the underlying kinetic factors governing the dissolution process, and reveals the influence of different material and processing variables on the dissolution process, such as time, temperature, catalyst concentration, and chain length between cross-links.

Alkali metals levels in the human brain tissue: Anatomical region differences and age-related changes.

PubMed

Ramos, Patrícia; Santos, Agostinho; Pinto, Edgar; Pinto, Nair Rosas; Mendes, Ricardo; Magalhães, Teresa; Almeida, Agostinho

2016-12-01

The link between trace elements imbalances (both "toxic" and "essential") in the human brain and neurodegenerative disease has been subject of extensive research. More recently, some studies have highlighted the potential role of the homeostasis deregulation of alkali metals in specific brain regions as key factor in the pathogenesis of neurodegenerative diseases such as multiple sclerosis and Alzheimer's disease. Using flame atomic emission spectrometry and inductively coupled plasma-mass spectrometry after microwave-assisted acid digestion of the samples, alkali metals (Na, K, Li, Rb and Cs) were determined in 14 different areas of the human brain (frontal cortex, superior and middle temporal gyri, caudate nucleus, putamen, globus pallidus, cingulated gyrus, hippocampus, inferior parietal lobule, visual cortex of the occipital lobe, midbrain, pons, medulla and cerebellum) of adult individuals (n=42; 71±12, range: 50-101 years old) with no known history and evidence of neurodegenerative, neurological or psychiatric disorder. Potassium was found as the most abundant alkali metal, followed by Na, Rb, Cs and Li. Lithium, K and Cs distribution showed to be quite heterogeneous. On the contrary, Rb and Na appeared quite homogeneously distributed within the human brain tissue. The lowest levels of Na, K, Rb and Li were found in the brainstem (midbrain, medulla and pons) and cerebellum, while the lowest levels of Cs were found in the frontal cortex. The highest levels of K (mean±sd; range 15.5±2.5; 8.9-21.8mg/g) Rb (17.2±6.1; 3.9-32.4μg/g and Cs (83.4±48.6; 17.3-220.5ng/g) were found in putamen. The highest levels of Na and Li were found in the frontal cortex (11.6±2.4; 6.6-17.1mg/g) and caudate nucleus (7.6±4.6 2.2-21.3ng/g), respectively. Although K, Cs and Li levels appear to remain largely unchanged with age, some age-related changes were observed for Na and Rb levels in particular brain regions (namely in the hippocampus). Copyright © 2016 Elsevier GmbH. All

Alkali metal thermal to electric conversion

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

Sievers, R.K.; Ivanenok, J.F. III; Hunt, T.K.

1995-10-01

With potential efficiencies of up to 40%, AMTEC technology offers reliability and fuel flexibility for aerospace and ground power applications. Alkali Metal Thermal to Electric Conversion (AMTEC), a direct power-conversion technology, is emerging from the laboratory for use in a number of applications that require lightweight, long-running, efficient power systems. AMTEC is compatible with many heat and fuel sources, and it offers the reliability of direct (that is, no moving parts) thermal to electric conversion. These features make it an attractive technology for small spacecraft used in deep-space missions and for ground power applications, such as self-powered furnaces and themore » generators used in recreational vehicles. Researchers at Ford Scientific Laboratories, in Dearborn, Michigan, first conceived AMTEC technology in 1968 when they identified and patented a converter known as the sodium heat engine. This heat engine was based on the unique properties of {beta}-alumina solid electrolyte (BASE), a ceramic material that is an excellent sodium ion conductor but a poor electronic conductor. BASE was used to form a structural barrier across which a sodium concentration gradient could be produced from thermal energy. The engine provided a way to isothermally expand sodium through the BASE concentration gradient without moving mechanical components. Measured power density and calculated peak efficiencies were impressive, which led to funding from the Department of Energy for important material technology development.« less

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

Gordon, John Howard; Alvare, Javier

Alkali metals and sulfur may be recovered from alkali monosulfide and polysulfides in an electrolytic process that utilizes an electrolytic cell having an alkali ion conductive membrane. An anolyte solution includes an alkali monosulfide, an alkali polysulfide, or a mixture thereof and a solvent that dissolves elemental sulfur. A catholyte includes molten alkali metal. Applying an electric current oxidizes sulfide and polysulfide in the anolyte compartment, causes alkali metal ions to pass through the alkali ion conductive membrane to the catholyte compartment, and reduces the alkali metal ions in the catholyte compartment. Liquid sulfur separates from the anolyte solution andmore » may be recovered. The electrolytic cell is operated at a temperature where the formed alkali metal and sulfur are molten.« less

Spectroscopic studies of transition metal ions in molten alkali metal carboxylates

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

Maroni, V.A.; Maciejewski, M.L.

Electronic absorption and C-13 NMR spectroscopic studies were carried out to investigate the structure of (i) alkali metal formate (Fm) and acetate (Ac) eutectic melts and (ii) solutions of 3d transition metal (TM) cations in these eutectics. Measurements were made over the temperature range 90..-->..190/sup 0/C. The most stable oxidation states of the individual TMs in the Fm and Ac eutectics were: Ti/sup 3 +/, V/sup 3 +/, VO/sup 2 +/, Cr/sup 3 +/, Mn/sup 2 +/, Fe/sup 2 +/, Co/sup 2 +/, Ni/sup 2 +/, and Cu/sup 2 +/. The ligand field absorption spectra obtained in these carboxylate meltsmore » bore a consistent resemblance to the spectra of these same cations in aqueous media, but the absorptivities were generally higher than are observed for the hexaquo complexes. The results were interpreted in terms of the existence of bidentate coordination in some (if not all) cases, leading to noncentrosymmetric complexation geometries. Key results of the NMR measurements included the apparent observation of two different carboxylate anion environments in Ni/sup 2 +/ solutions. C-13 spin-lattice relaxation of the carboxylate anions in the TM-free eutectics was found to be controlled by dipolar coupling to another nucleus. In the TM-containing solutions, the spin-lattice relaxation times were reduced by a factor of 10 to 1000, evidencing the expected shift to electron-nuclear dipolar coupling. Activation energies for viscous flow derived from the spin-lattice relaxation measurements on TM-free melts were in the 10..-->..11 kcal/mol range, reflecting the highly ordered, glassy nature of the eutectics studied.« less

Carbonation of metal silicates for long-term CO2 sequestration

DOEpatents

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).

Impaired colour vision in workers exposed to organic solvents: A systematic review.

PubMed

Betancur-Sánchez, A M; Vásquez-Trespalacios, E M; Sardi-Correa, C

2017-01-01

To evaluate recent evidence concerning the relationship between the exposure to organic solvents and the impairment of colour vision. A bibliographic search was conducted for scientific papers published in the last 15 years, in the LILACS, PubMed, Science Direct, EBSCO, and Cochrane databases that included observational studies assessing the relationship between impairment in colour vision and exposure to organic solvents. Eleven studies were selected that were performed on an economically active population and used the Lanthony D-15 desaturated test (D-15d), measured the exposure to organic solvents, and included unexposed controls. It was found that there is a statistically significant relationship between the exposure to organic solvents and the presence of an impairment in colour vision. The results support the hypothesis that exposure to organic solvents could induce acquired dyschromatopsia. The evaluation of colour vision with the D-15d test is simple and sensitive for diagnosis. More studies need to be conducted on this subject in order to better understand the relationship between impaired colour vision and more severe side effects caused by this exposure. Copyright © 2016 Sociedad Española de Oftalmología. Publicado por Elsevier España, S.L.U. All rights reserved.

Chromium metal organic frameworks and synthesis of metal organic frameworks

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

Zhou, Hong-Cai; Liu, Tian-Fu; Lian, Xizhen

The present invention relates to monocrystalline metal organic frameworks comprising chromium ions and carboxylate ligands and the use of the same, for example their use for storing a gas. The invention also relates to methods for preparing metal organic frameworks comprising chromium, titanium or iron ions and carboxylate ligands. The methods of the invention allow such metal organic frameworks to be prepared in monocrystalline or polycrystalline forms.

Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table.

PubMed

Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

2017-10-05

We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium, potassium, rubidium and cesium cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all anionic (XH n-1 - ) constituted by main group-element hydrides of groups 14-17 along the periods 2-6. In particular, we wish to establish the trend in affinity for a cation as the latter varies from proton to, and along, the alkali cations. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn-Sham molecular orbital theory together with a quantitative bond energy decomposition analyses (EDA). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorophore Metal-Organic Complexes: High-Throughput Optical Screening for Aprotic Electrochemical Systems.

PubMed

Park, Sung Hyeon; Choi, Chang Hyuck; Lee, Seung Yong; Woo, Seong Ihl

2017-02-13

Combinatorial optical screening of aprotic electrocatalysts has not yet been achieved primarily due to H + -associated mechanisms of fluorophore modulation. We have overcome this problem by using fluorophore metal-organic complexes. In particular, eosin Y and quinine can be coordinated with various metallic cations (e.g., Li + , Na + , Mg 2+ , Zn 2+ , and Al 3+ ) in aprotic solvents, triggering changes in their fluorescent properties. These interactions have been used in a reliable screening method to determine oxygen reduction/evolution reaction activities of 100 Mn-based binary catalysts for the aprotic Li-air battery.

SOLVENT-FREE ACCELERATED ORGANIC SYNTHESES USING MICROWAVES

EPA Science Inventory

Abstract: A solvent-free approach for organic synthesis is described which involves microwave (MW) exposure of neat reactants (undiluted) either in presence of a catalyst or catalyzed by the surfaces of inexpensive and recyclable mineral supports such as alumina, silica, clay, or...

Metal inks

DOEpatents

Ginley, David S; Curtis, Calvin J; Miedaner, Alex; van Hest, Marinus Franciscus Antonius Maria; Kaydanova, Tatiana

2014-02-04

Self-reducing metal inks and systems and methods for producing and using the same are disclosed. In an exemplary embodiment, a method may comprise selecting metal-organic (MO) precursor, selecting a reducing agent, and dissolving the MO precursor and the reducing agent in an organic solvent to produce a metal ink that remains in a liquid phase at room temperature. Metal inks, including self-reducing and fire-through metal inks, are also disclosed, as are various applications of the metal inks.

Metal Hydride and Alkali Halide Opacities in Extrasolar Giant Planets and Cool Stellar Atmospheres

NASA Technical Reports Server (NTRS)

Weck, Philippe F.; Stancil, Phillip C.; Kirby, Kate; Schweitzer, Andreas; Hauschildt, Peter H.

2006-01-01

The lack of accurate and complete molecular line and continuum opacity data has been a serious limitation to developing atmospheric models of cool stars and Extrasolar Giant Planets (EGPs). We report our recent calculations of molecular opacities resulting from the presence of metal hydrides and alkali halides. The resulting data have been included in the PHOENIX stellar atmosphere code (Hauschildt & Baron 1999). The new models, calculated using spherical geometry for all gravities considered, also incorporate our latest database of nearly 670 million molecular lines, and updated equations of state.

Azo compounds as a family of organic electrode materials for alkali-ion batteries.

PubMed

Luo, Chao; Borodin, Oleg; Ji, Xiao; Hou, Singyuk; Gaskell, Karen J; Fan, Xiulin; Chen, Ji; Deng, Tao; Wang, Ruixing; Jiang, Jianjun; Wang, Chunsheng

2018-02-27

Organic compounds are desirable for sustainable Li-ion batteries (LIBs), but the poor cycle stability and low power density limit their large-scale application. Here we report a family of organic compounds containing azo group (N=N) for reversible lithiation/delithiation. Azobenzene-4,4'-dicarboxylic acid lithium salt (ADALS) with an azo group in the center of the conjugated structure is used as a model azo compound to investigate the electrochemical behaviors and reaction mechanism of azo compounds. In LIBs, ADALS can provide a capacity of 190 mAh g -1 at 0.5 C (corresponding to current density of 95 mA g -1 ) and still retain 90%, 71%, and 56% of the capacity when the current density is increased to 2 C, 10 C, and 20 C, respectively. Moreover, ADALS retains 89% of initial capacity after 5,000 cycles at 20 C with a slow capacity decay rate of 0.0023% per cycle, representing one of the best performances in all organic compounds. Superior electrochemical behavior of ADALS is also observed in Na-ion batteries, demonstrating that azo compounds are universal electrode materials for alkali-ion batteries. The highly reversible redox chemistry of azo compounds to alkali ions was confirmed by density-functional theory (DFT) calculations. It provides opportunities for developing sustainable batteries.

A review of the high temperature oxidation of uranium oxides in molten salts and in the solid state to form alkali metal uranates, and their composition and properties

NASA Astrophysics Data System (ADS)

Griffiths, Trevor R.; Volkovich, Vladimir A.

An extensive review of the literature on the high temperature reactions (both in melts and in the solid state) of uranium oxides (UO 2, U 3O 8 and UO 3) resulting in the formation of insoluble alkali metal (Li to Cs) uranates is presented. Their uranate(VI) and uranate(V) compounds are examined, together with mixed and oxygen-deficient uranates. The reactions of uranium oxides with carbonates, oxides, per- and superoxides, chlorides, sulfates, nitrates and nitrites under both oxidising and non-oxidising conditions are critically examined and systematised, and the established compositions of a range of uranate(VI) and (V) compounds formed are discussed. Alkali metal uranates(VI) are examined in detail and their structural, physical, thermodynamic and spectroscopic properties considered. Chemical properties of alkali metal uranates(VI), including various methods for their reduction, are also reported. Errors in the current theoretical treatment of uranate(VI) spectra are identified and the need to develop routes for the preparation of single crystals is stressed.

Organic microchemical performance of solvent resistant polycarbosilane based microreactor.

PubMed

Yoon, Tae-Ho; Jung, Sang-Hee; Kim, Dong-Pyo

2011-05-01

We report the successful fabrication of preceramic polymer allylhydridopolycarbosilane (AHPCS) derived microchannels with excellent organic solvent resistance and optical transparency via economic imprinting process, followed by UV and post thermal curing process at 160 degrees C for 3 h. The microchemical performance of the fabricated microreactors was evaluated by choosing two model micro chemical reactions under organic solvent conditions; syntheses of 2-aminothiazole in DMF and dimethylpyrazole in THF, and compared with glass-based microreactor having identical dimensions and batch system with analogy. It is clear that AHPCS derived microreactor showed excellent solvent resistance and chemical stability compare with glass derived microreactor made by high cost of photolithography and thermal bonding process. The novel preceramic polymer derived microreactors showed reliable mechanical and chemical stability and conversion yields compare with that of glass derived microreactors, which is very promising for developing an integrated microfluidics by adopting available microstructuring techniques of the polymers.

Heteroatom incorporated coke for electrochemical cell electrode

DOEpatents

Lewis, Irwin Charles; Greinke, Ronald Alfred

1997-01-01

This invention relates to an electrode for a coke/alkali metal electrochemical cell comprising: (a) calcined coke particles: (i) that contain at least 0.5 weight percent of nitrogen heteroatoms and at least 1.0 weight percent sulfur heteroatoms, and (ii) that have an average particle size from 2 microns to 40 microns with essentially no particles being greater than 50 microns. (b) a binder This invention also relates to a coke/alkali metal electrochemical cell comprising: (a) an electrode as described above, (b) a non-aqueous electrolytic solution comprising an organic aprotic solvent and an electrically conductive salt, and (c) a counterelectrode.

Automated process for solvent separation of organic/inorganic substance

DOEpatents

Schweighardt, Frank K.

1986-01-01

There is described an automated process for the solvent separation of organic/inorganic substances that operates continuously and unattended and eliminates potential errors resulting from subjectivity and the aging of the sample during analysis. In the process, metered amounts of one or more solvents are passed sequentially through a filter containing the sample under the direction of a microprocessor control apparatus. The mixture in the filter is agitated by ultrasonic cavitation for a timed period and the filtrate is collected. The filtrate of each solvent extraction is collected individually and the residue on the filter element is collected to complete the extraction process.

Solvent wash solution

DOEpatents

Neace, J.C.

1984-03-13

A process is claimed for removing diluent degradation products from a solvent extraction solution, which has been used to recover uranium and plutonium from spent nuclear fuel. A wash solution and the solvent extraction solution are combined. The wash solution contains (a) water and (b) up to about, and including, 50 vol % of at least one-polar water-miscible organic solvent based on the total volume of the water and the highly-polar organic solvent. The wash solution also preferably contains at least one inorganic salt. The diluent degradation products dissolve in the highly-polar organic solvent and the organic solvent extraction solvent do not dissolve in the highly-polar organic solvent. The highly-polar organic solvent and the extraction solvent are separated.

Solvent wash solution

DOEpatents

Neace, James C.

1986-01-01

Process for removing diluent degradation products from a solvent extraction solution, which has been used to recover uranium and plutonium from spent nuclear fuel. A wash solution and the solvent extraction solution are combined. The wash solution contains (a) water and (b) up to about, and including, 50 volume percent of at least one-polar water-miscible organic solvent based on the total volume of the water and the highly-polar organic solvent. The wash solution also preferably contains at least one inorganic salt. The diluent degradation products dissolve in the highly-polar organic solvent and the organic solvent extraction solvent do not dissolve in the highly-polar organic solvent. The highly-polar organic solvent and the extraction solvent are separated.

Carbonation of metal silicates for long-term CO.sub.2 sequestration

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

Blencoe, James G.; Palmer, Donald A.; Anovitz, Lawrence M.

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 producemore » a carbonate of the metal formerly contained in the metal silicate of step (a).« less

Carbonation of metal silicates for long-term CO.sub.2 sequestration

DOEpatents

Blencoe, James G [Harriman, TN; Palmer, Donald A [Oliver Springs, TN; Anovitz, Lawrence M [Knoxville, TN; Beard, James S [Martinsville, VA

2012-02-14

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).

Binding of Alkali Metal Ions with 1,3,5-Tri(phenyl)benzene and 1,3,5-Tri(naphthyl)benzene: The Effect of Phenyl and Naphthyl Ring Substitution on Cation-π Interactions Revealed by DFT Study.

PubMed

Mirchi, Ali; Sizochenko, Natalia; Dinadayalane, Tandabany; Leszczynski, Jerzy

2017-11-22

The effect of substitution of phenyl and naphthyl rings to benzene was examined to elucidate the cation-π interactions involving alkali metal ions with 1,3,5-tri(phenyl)benzene (TPB) and 1,3,5-tri(naphthyl)benzene (TNB). Benzene, TPB, and four TNB isomers (with ααα, ααβ, αββ, and βββ types of fusion) and their complexes with Li + , Na + , K + , Rb + , and Cs + were optimized using DFT approach with B3LYP and M06-2X functionals in conjunction with the def2-QZVP basis set. Higher relative stability of β,β,β-TNB over α,α,α-TNB can be attributed to peri repulsion, which is defined as the nonbonding repulsive interaction between substituents in the 1- and the 8-positions on the naphthalene core. Binding energies, distances between ring centroid and the metal ions, and the distance to metal ions from the center of other six-membered rings were compared for all complexes. Our computational study reveals that the binding affinity of alkali metal cations increases significantly with the 1,3,5-trisubstitution of phenyl and naphthyl rings to benzene. The detailed computational analyses of geometries, partial charges, binding energies, and ligand organization energies reveal the possibility of favorable C-H···M + interactions when a α-naphthyl group exists in complexes of TNB structures. Like benzene-alkali metal ion complexes, the binding affinity of metal ions follows the order: Li + > Na + > K + > Rb + > Cs + for any considered 1,3,5-trisubstituted benzene systems. In case of TNB, we found that the strength of interactions increases as the fusion point changes from α to β position of naphthalene.

Solvent Selection for Recrystallization: An Undergraduate Organic Experiment.

ERIC Educational Resources Information Center

Baumann, Jacob B.

1979-01-01

This experiment develops the students' ability to carry out a simple recrystallization effectively, and demonstrates how a solvent may be selected or rejected for the recrystallization of a specific organic compound. (Author/BB)

High-Throughput Synthetic Chemistry Enabled by Organic Solvent Disintegrating Tablet.

PubMed

Li, Tingting; Xu, Lei; Xing, Yanjun; Xu, Bo

2017-01-17

Synthetic chemistry remains a time- and labor-intensive process of inherent hazardous nature. Our organic solvent disintegrating tablet (O-Tab) technology has shown potential to make industrial/synthetic chemistry more efficient. As is the case with pharmaceutical tablets, our reagent-containing O-Tabs are mechanically strong, but disintegrate rapidly when in contact with reaction media (organic solvents). For O-Tabs containing sensitive chemicals, they can be further coated to insulate them from air and moisture. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method for synthesizing metal bis(borano) hypophosphite complexes

DOEpatents

Cordaro, Joseph G.

2013-06-18

The present invention describes the synthesis of a family of metal bis(borano) hypophosphite complexes. One procedure described in detail is the syntheses of complexes beginning from phosphorus trichloride and sodium borohydride. Temperature, solvent, concentration, and atmosphere are all critical to ensure product formation. In the case of sodium bis(borano) hypophosphite, hydrogen gas was evolved upon heating at temperatures above 150.degree. C. Included in this family of materials are the salts of the alkali metals Li, Na and K, and those of the alkaline earth metals Mg and Ca. Hydrogen storage materials are possible. In particular the lithium salt, Li[PH.sub.2(BH.sub.3).sub.2], theoretically would contain nearly 12 wt % hydrogen. Analytical data for product characterization and thermal properties are given.

Selectivity of bis(calix[4]diquinone) ionophores towards metal ions in solvent dimethylsulfoxide: a molecular mechanics and molecular dynamics study.

PubMed

Felix, Vitor; Drew, Michael G B; Webber, Philip R A; Beer, Paul D

2006-01-28

Molecular modelling studies have been carried out on two bis(calix[4]diquinone) ionophores, each created from two (calix[4]diquinone)arenes bridged at their bottom rims via alkyl chains (CH(2))(n), 1: n = 3, 2; n = 4, in order to understand the reported selectivity of these ligands towards different sized metal ions such as Na(+), K(+), Rb(+), and Cs(+) in dmso solution. Conformational analyses have been carried out which show that in the lowest energy conformations of the two macrocycles, the individual calix[4]diquinones exhibit a combination of partial cone, 1,3-alternate and cone conformations. The interactions of these alkali metals with the macrocycles have been studied in the gas phase and in a periodic box of solvent dmso by molecular mechanics and molecular dynamics calculations. Molecular mechanics calculations have been carried out on the mode of entry of the ions into the macrocycles and suggest that this is likely to occur from the side of the central cavity, rather than through the main axis of the calix[4]diquinones. There are energy barriers of ca. 19 kcal mol(-1) for this entry path in the gas phase, but in solution no energy barrier is found. Molecular dynamics simulations show that in both 1 and 2, though particularly in the latter macrocycle, one or two solvent molecules are bonded to the metal throughout the course of the simulation, often to the exclusion of one or more of the ether oxygen atoms. By contrast the carbonyl oxygen atoms remain bonded to the metal atoms throughout with bond lengths that remain significantly less than those to the ether oxygen atoms. Free energy perturbation studies have been carried out in dmso and indicate that for 1, the selectivity follows the order Rb(+) approximately K(+) > Cs(+) > Na(+), which is partially in agreement with the experimental results. The energy differences are small and indeed the ratio between stability constants found for Cs(+) and K(+) complexes is only 0.60, showing that has only a slight

Doppler-free satellites of resonances of electromagnetically induced transparency and absorption on the D 2 lines of alkali metals

NASA Astrophysics Data System (ADS)

Sargsyan, A.; Sarkisyan, D.; Staedter, D.; Akulshin, A. M.

2006-11-01

The peculiarities of intra-Doppler structures that are observed in the atomic absorption spectrum of alkali metals with the help of two independent lasers have been studied. These structures accompany ultranarrow coherent resonances of electromagnetically induced transparency and absorption. With the D 2 line of rubidium taken as an example, it is shown that, in the scheme of unidirectional waves, the maximum number of satellite resonances caused by optical pumping selective with respect to the atomic velocity is equal to seven, while only six resonances are observed in the traditional scheme of saturated absorption with counterpropagating waves of the same frequency. The spectral position of the resonances and their polarity depend on the frequency of the saturating radiation, while their number and relative amplitude depend also on the experimental geometry. These features are of general character and should show themselves in the absorption spectrum on the D 2 lines of all alkali metals. An explanation of these features is given. The calculated spectral separations between the resonances are compared to the experimental ones, and their possible application is discussed.

Response Mechanisms in Serratia marcescens IBBPo15 During Organic Solvents Exposure.

PubMed

Stancu, Mihaela Marilena

2016-12-01

Serratia marcescens strain IBB Po15 (KT315653) which possesses serratiopeptidase (ser) gene (KT894207) exhibited good solvent tolerance. During the exposure of S. marcescens IBB Po15 cells to 5 % organic solvents, n-decane was less toxic for this bacterium, compared with n-hexane, cyclohexane, ethylbenzene, toluene, and styrene. The exposure of the S. marcescens IBB Po15 cells to n-hexane, cyclohexane, ethylbenzene, toluene, and styrene induced the formation of large clusters, while in control and n-decane-exposed cells, only organization into small clusters was observed. The data obtained suggested that S. marcescens IBB Po15 cells produced some secondary metabolites (i.e., surfactant serrawettin, red pigment prodigiosin) which are well known as valuable molecules due to their large applications. The exposure of the bacterial cells to organic solvents induced secondary metabolites profile modifications. However, S. marcescens IBB Po15 possesses only alkB1, todM, rhlAB, pswP, mpr, and ser genes, the unspecific amplification of other fragments being acquired also when the primers for alkM1, xylM, ndoM, and C23DO genes were used. Modifications of DNA patterns were not depicted in S. marcescens IBB Po15 cells exposed to organic solvents.

Assessment of time to pregnancy and spontaneous abortion status following occupational exposure to organic solvents mixture.

PubMed

Attarchi, Mir Saeed; Ashouri, Monir; Labbafinejad, Yasser; Mohammadi, Saber

2012-04-01

Due to increasing usage of chemicals in various industries, occupational exposure of women with these materials is unavoidable. Nowadays, some studies indicate adverse effects of exposure to these chemicals, especially organic solvents on the reproductive system of females. This study aimed to assess the relationship between spontaneous abortion and occupational exposure to organic solvents mixture in pharmaceutical industry. This study was carried out in a pharmaceutical factory located in the suburb of Tehran in 2010. During the study, married women who were working in the factory laboratory units and had exposure to mixed organic solvents were compared with married women who were working in the packing units of the factory without occupational exposure to organic solvents in terms of spontaneous abortion frequency and duration of pregnancy using statistical methods. In this study, the frequency of spontaneous abortion in employees with and without exposure to organic solvents mixture was 10.7 and 2.9% respectively. This study showed that even after adjustment for confounding factors, there was a significant correlation between spontaneous abortion and occupational exposure to organic solvents mixture and this correlation increased with increasing levels of exposure to organic solvents. Also, a significant correlation was observed between occupational exposure to mixed organic solvents and waiting time to become pregnant (TTP). Furthermore, this study showed that even after adjustment for confounding variables, shift workers were significantly more affected by spontaneous abortion compared to daytime workers (P < 0.001). Also, in our study, synergistic effect between shift working and occupational exposure to organic solvents mixture on spontaneous abortion was seen. According to the results of this study, since there is probability of spontaneous abortion resulting from occupational exposure to various chemicals including organic solvents, recommendation to

Enhanced performance of ferroelectric-based all organic transistors and capacitors through choice of solvent

NASA Astrophysics Data System (ADS)

Knotts, Grant; Bhaumik, Anagh; Ghosh, Kartik; Guha, Suchismita

2014-03-01

We examine the role of solvents in the performance of pentacene devices using the ferroelectric copolymer poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFe) as a gate insulating layer. High dipole moment solvents such as dimethyl sulfoxide used to dissolve the copolymer for spin casting increase the charge carrier mobility in field-effect transistors by nearly an order of magnitude as compared to lower dipole moment solvents. The polarization in Al/PVDF-TrFe/Au metal-ferroelectric-metal devices is also investigated. An increase in remnant polarization of ~ 20% is observed in the sample using dimethyl sulfoxide as the ferroelectric solvent. Interestingly, at low applied electric fields of ~ 100 MV/m a remnant polarization is seen in the high dipole moment device that is nearly 3.5 times larger than the value observed in the lower dipole moment samples, suggesting that the degree of dipolar order is higher at low operating voltages for the high dipole moment device. Detailed analysis of the capacitance characteristics of metal-insulator-semiconductor structure is performed. The density of interface trap states is nearly an order of magnitude lower for the high dipole moment device. This work was supported by National Science Foundation under Grant No. ECCS-1305642.

Automated process for solvent separation of organic/inorganic substance

DOEpatents

Schweighardt, F.K.

1986-07-29

There is described an automated process for the solvent separation of organic/inorganic substances that operates continuously and unattended and eliminates potential errors resulting from subjectivity and the aging of the sample during analysis. In the process, metered amounts of one or more solvents are passed sequentially through a filter containing the sample under the direction of a microprocessor control apparatus. The mixture in the filter is agitated by ultrasonic cavitation for a timed period and the filtrate is collected. The filtrate of each solvent extraction is collected individually and the residue on the filter element is collected to complete the extraction process. 4 figs.

Dramatic enhancement of enzymatic activity in organic solvents by lyoprotectants

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

Dabulis, K.; Klibanov, A.M.

1993-03-05

When seven different hydrolytic enzymes (four proteases and three lipases) were lyophilized from aqueous solution containing a ligand, N-Ac-L-Phe-NH[sub 2], their catalytic activity in anhydrous solvents was far greater (one to two orders of magnitude) than that of the enzymes lyophilized without the ligand. This ligand-induced activation was expressed regardless of whether the substrate employed in organic solvents structurally resembled the ligand. Furthermore, nonligand lyoprotectants [sorbitol, other sugars, and poly(ethylene glycol)] also dramatically enhanced enzymatic activity in anhydrous solvents when present in enzyme aqueous solution prior to lyophilization. The effects of the ligand and of the lyoprotectants were nonadditive, suggestingmore » the same mechanism of action. Excipient-activated and nonactivated enzymes exhibited identical activities in water. Also, addition of the excipients directly to suspensions of nonactivated enzymes in organic solvents had no appreciable effect on catalytic activity. These observations indicate that the mechanism of the excipient-induced activation is based on the ability of the excipients to alleviate reversible denaturation of enzymes upon lyophilization. Activity enhancement induced by the excipients is displayed even after their removal by washing enzymes with anhydrous solvents. Subtilisin Carlsberg, lyophilized with sorbitol, was found to be a much more efficient practical catalyst than its regular' counterpart.« less

Deliberate and Accidental Gas-Phase Alkali Doping of Chalcogenide Semiconductors: Cu(In,Ga)Se2

PubMed Central

Colombara, Diego; Berner, Ulrich; Ciccioli, Andrea; Malaquias, João C.; Bertram, Tobias; Crossay, Alexandre; Schöneich, Michael; Meadows, Helene J.; Regesch, David; Delsante, Simona; Gigli, Guido; Valle, Nathalie; Guillot, Jérome; El Adib, Brahime; Grysan, Patrick; Dale, Phillip J.

2017-01-01

Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu2ZnSnS4) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source. PMID:28233864

Deliberate and Accidental Gas-Phase Alkali Doping of Chalcogenide Semiconductors: Cu(In,Ga)Se2.

PubMed

Colombara, Diego; Berner, Ulrich; Ciccioli, Andrea; Malaquias, João C; Bertram, Tobias; Crossay, Alexandre; Schöneich, Michael; Meadows, Helene J; Regesch, David; Delsante, Simona; Gigli, Guido; Valle, Nathalie; Guillot, Jérome; El Adib, Brahime; Grysan, Patrick; Dale, Phillip J

2017-02-24

Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se 2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu 2 ZnSnS 4 ) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source.

Solubility, stability, and electrochemical studies of sulfur-sulfide solutions in organic solvents

NASA Technical Reports Server (NTRS)

Fielder, W. L.; Singer, J.

1978-01-01

A preliminary study of the sulfur electrode in organic solvents suggests that the system warrants further investigation for use in a low temperature (100 deg to 120 C) Na-S secondary battery. A qualitative screening was undertaken at 120 C to determine the solubilities and stabilities of Na2S and Na2S2 in representatives of many classes of organic solvents. From the screening and quantitative studies, two classes of solvents were selected for work; amides and cyclic polyalcohols. Voltammetric and Na-S cell charge discharge studies of sulfide solutions in organic solvents (e.g., N, N-dimethylformamide) at 120 C suggested that the reversibilities of the reactions on Pt or high density graphite were moderately poor. However, the sulfur electrode was indeed reducible (and oxidizable) through the range of elemental sulfur to Na2S. Reactions and mechanisms are proposed for the oxidation reduction processes occurring at the sulfur electrode.

Solvent-Free Synthesis of Zeolites: Mechanism and Utility.

PubMed

Wu, Qinming; Meng, Xiangju; Gao, Xionghou; Xiao, Feng-Shou

2018-05-08

Zeolites have been extensively studied for years in different areas of chemical industry, such as shape selective catalysis, ion-exchange, and gas adsorption and separation. Generally, zeolites are prepared from solvothermal synthesis in the presence of a large amounts of solvents such as water and alcohols in sealed autoclaves under autogenous pressure. Water has been regarded as essential to synthesize zeolites for fast mass transfer of reactants, but it occupies a large space in autoclaves, which greatly reduces the yield of zeolite products. Furthermore, polluted wastes and relatively high pressure due to the presence of water solvent in the synthesis also leads to environmental and safety issues. Recently, inspired by great benefits of solvent-free synthesis, including the environmental concerns, energy consumption, safety, and economic cost, researchers continually challenge the rationale of the solvent and reconsider the age-old question "Do we actually need solvents at all in zeolite synthesis?" In this Account, we briefly summarize our efforts to rationally synthesize zeolites via a solvent-free route. Our research demonstrates that a series of silica, aluminosilicate, and aluminophosphate-based zeolites can be successfully prepared by mixing, grinding, and heating starting solid materials under solvent-free conditions. Combining an organotemplate-free synthesis with a solvent-free approach maximizes the advantages resulting in a more sustainable synthetic route, which avoids using toxic and costly organic templates and the formation of harmful gases by calcination of organic templates at high temperature. Furthermore, new insights into the solvent-free crystallization process of zeolites have been provided by modern techniques such as NMR and UV-Raman spectroscopy, which should be helpful in designing new zeolite structures and developing novel routes for synthesis of zeolites. The role of water and the vital intermediates during the crystallization of

Coverage dependent work function of graphene on a Cu(111) substrate with intercalated alkali metals

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

Cook, Brandon G.; Russakoff, Arthur; Varga, Kalman

2015-05-26

Using first-principles calculations, it is shown that the work function of graphene on copper can be adjusted by varying the concentration of intercalated alkali metals. Using density functional theory, we calculate the modulation of work function when Li, Na, or K are intercalated between graphene and a Cu(111) surface. Furthermore, the physical origins of the change in work function are explained in terms of phenomenological models accounting for the formation and depolarization of interfacial dipoles and the shift in the Fermi-level induced via charge transfer.

Implication of the solvent effect, metal ions and topology in the electronic structure and hydrogen bonding of human telomeric G-quadruplex DNA.

PubMed

Poudel, Lokendra; Steinmetz, Nicole F; French, Roger H; Parsegian, V Adrian; Podgornik, Rudolf; Ching, Wai-Yim

2016-08-03

We present a first-principles density functional study elucidating the effects of solvent, metal ions and topology on the electronic structure and hydrogen bonding of 12 well-designed three dimensional G-quadruplex (G4-DNA) models in different environments. Our study shows that the parallel strand structures are more stable in dry environments and aqueous solutions containing K(+) ions within the tetrad of guanine but conversely, that the anti-parallel structure is more stable in solutions containing the Na(+) ions within the tetrad of guanine. The presence of metal ions within the tetrad of the guanine channel always enhances the stability of the G4-DNA models. The parallel strand structures have larger HOMO-LUMO gaps than antiparallel structures, which are in the range of 0.98 eV to 3.11 eV. Partial charge calculations show that sugar and alkali ions are positively charged whereas nucleobases, PO4 groups and water molecules are all negatively charged. Partial charges on each functional group with different signs and magnitudes contribute differently to the electrostatic interactions involving G4-DNA and favor the parallel structure. A comparative study between specific pairs of different G4-DNA models shows that the Hoogsteen OH and NH hydrogen bonds in the guanine tetrad are significantly influenced by the presence of metal ions and water molecules, collectively affecting the structure and the stability of G4-DNA.

Compacted carbon for electrochemical cells

DOEpatents

Greinke, Ronald Alfred; Lewis, Irwin Charles

1997-01-01

This invention provides compacted carbon that is useful in the electrode of an alkali metal/carbon electrochemical cell of improved capacity selected from the group consisting of: (a) coke having the following properties: (i) an x-ray density of at least 2.00 grams per cubic centimeters, (ii) a closed porosity of no greater than 5%, and (iii) an open porosity of no greater than 47%; and (b) graphite having the following properties: (i) an x-ray density of at least 2.20 grams per cubic centimeters, (ii) a closed porosity of no greater than 5%, and (iii) an open porosity of no greater than 25%. This invention also relates to an electrode for an alkali metal/carbon electrochemical cell comprising compacted carbon as described above and a binder. This invention further provides an alkali metal/carbon electrochemical cell comprising: (a) an electrode as described above, (b) a non-aqueous electrolytic solution comprising an organic aprotic solvent and an electrolytically conductive salt and an alkali metal, and (c) a counterelectrode.

Compacted carbon for electrochemical cells

DOEpatents

Greinke, R.A.; Lewis, I.C.

1997-10-14

This invention provides compacted carbon that is useful in the electrode of an alkali metal/carbon electrochemical cell of improved capacity selected from the group consisting of: (a) coke having the following properties: (1) an x-ray density of at least 2.00 grams per cubic centimeters, (2) a closed porosity of no greater than 5%, and (3) an open porosity of no greater than 47%; and (b) graphite having the following properties: (1) an x-ray density of at least 2.20 grams per cubic centimeters, (2) a closed porosity of no greater than 5%, and (3) an open porosity of no greater than 25%. This invention also relates to an electrode for an alkali metal/carbon electrochemical cell comprising compacted carbon as described above and a binder. This invention further provides an alkali metal/carbon electrochemical cell comprising: (a) an electrode as described above, (b) a non-aqueous electrolytic solution comprising an organic aprotic solvent and an electrolytically conductive salt and an alkali metal, and (c) a counter electrode. 10 figs.

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

PubMed

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.

Organic photovoltaic devices comprising solution-processed substituted metal-phthalocyanines and exhibiting near-IR photo-sensitivity

DOEpatents

McGrath, Dominic V.; Mayukh, Mayank; Placencia, Diogenes; Armstrong, Neal R.

2016-11-29

Organic photovoltaic (OPV) devices are disclosed. An exemplary device has first and second electrodes and an organic, photovoltaically active zone located between the first and second electrodes. The photovoltaically active zone includes an organic electron-donor material and an organic electron-acceptor material. The electron-donor material includes one or more trivalent- or tetravalent-metal phthalocyanines with alkylchalcogenide ring substituents, and is soluble in at least one organic solvent. This solubility facilitates liquid-processability of the donor material, including formation of thin-films, on an unlimited scale to form planar and bulk heterojunctions in organic OPVs. These donor materials are photovoltaically active in both visible and near-IR wavelengths of light, enabling more of the solar spectrum, for example, to be applied to producing electricity. Also disclosed are methods for producing the metalated phthalocyanines and actual devices.

ALKYL PYROPHOSPHATE METAL SOLVENT EXTRACTANTS AND PROCESS

DOEpatents

Long, R.L.

1958-09-30

A process is presented for the recovery of uranium from aqueous mineral acidic solutions by solvent extraction. The extractant is a synmmetrical dialkyl pyrophosphate in which the alkyl substituents have a chain length of from 4 to 17 carbon atoms. Mentioned as a preferred extractant is dioctyl pyrophosphate. The uranium is precipitated irom the organic extractant phase with an agent such as HF, fluoride salts. alcohol, or ammonia.

Method of coating metal surfaces to form protective metal coating thereon

DOEpatents

Krikorian, Oscar H.; Curtis, Paul G.

1992-01-01

A process is disclosed for forming a protective metal coating on a metal surface using a flux consisting of an alkali metal fluoride, an alkaline earth metal fluoride, an alkali metal fluoaluminate, an alkali metal fluosilicate, and mixtures thereof. The flux, in particulate form, is mixed with particles of a metal coating material which may comprise aluminum, chromium, mixtures thereof, and alloys containing at least 50 wt. % aluminum and the particulate mixture is applied to the metal surface in a single step, followed by heating the coated metal surface to a temperature sufficient to cause the metal coating material to react with the metal surface to form a protective reaction product in the form of a metal coating bonded to the metal surface. The metal surface which reacts with the metal coating material to form the protective coating may comprise Fe, Co, Ni, Ti, V, Cr, Mn, Zr, Nb, Mo, Tc, Hf, Ta, W, Re and alloys thereof.

Method of coating metal surfaces to form protective metal coating thereon

DOEpatents

Krikorian, O.H.; Curtis, P.G.

1992-03-31

A process is disclosed for forming a protective metal coating on a metal surface using a flux consisting of an alkali metal fluoride, an alkaline earth metal fluoride, an alkali metal fluoaluminate, an alkali metal fluosilicate, and mixtures thereof. The flux, in particulate form, is mixed with particles of a metal coating material which may comprise aluminum, chromium, mixtures thereof, and alloys containing at least 50 wt. % aluminum and the particulate mixture is applied to the metal surface in a single step, followed by heating the coated metal surface to a temperature sufficient to cause the metal coating material to react with the metal surface to form a protective reaction product in the form of a metal coating bonded to the metal surface. The metal surface which reacts with the metal coating material to form the protective coating may comprise Fe, Co, Ni, Ti, V, Cr, Mn, Zr, Nb, Mo, Tc, Hf, Ta, W, Re and alloys thereof. 1 figure.

The concept of mixed organic ligands in metal-organic frameworks: design, tuning and functions.

PubMed

Yin, Zheng; Zhou, Yan-Ling; Zeng, Ming-Hua; Kurmoo, Mohamedally

2015-03-28

The research on metal-organic frameworks (MOFs) has been developing at an extraordinary pace in its two decades of existence, as judged by the exponential growth of novel structures and the constant expansion of its applicability and research scope. A major part of the research and its success are due to the vital role of the concept of mixed organic ligands in the design, tuning and functions. This perspective, therefore, reviews the recent advances in MOFs based on this concept, which is generally based on employing a small polydentate ligand (here labelled as "nodal ligand") to form either clusters, rods or layers, which are then connected by a second ditopic linker ligand to form the framework. The structures of the materials can be grouped into the following three categories: layer-spacer (usually known as pillared-layer), rod-spacer, and cluster-spacer based MOFs. Depending on the size and geometry of the spacer ligands, interpenetrations of frameworks are occasionally found. These MOFs show a wide range of properties such as (a) crystal-to-crystal transformations upon solvent modifications, post-synthetic metal exchange or ligand reactions, (b) gas sorption, solvent selectivity and purification, (c) specific catalysis, (d) optical properties including colour change, luminescence, non-linear optic, (e) short- and long range magnetic ordering, metamagnetism and reversible ground-state modifications and (f) drug and iodine carriers with controlled release. In the following, we will highlight the importance of the above concept in the design, tuning, and functions of a selection of existing MOFs having mixed organic ligands and their associated structures and properties. The results obtained so far using this concept look very promising for fine-tuning the pore size and shape for selective adsorption and specificity in catalytic reactions, which appears to be one way to propel the advances in the application and commercialization of MOFs.

Iodination of insulin in aqueous and organic solvents

PubMed Central

Massaglia, A.; Rosa, U.; Rialdi, G.; Rossi, C. A.

1969-01-01

1. The iodination of insulin was studied under various experimental conditions in aqueous media and in some organic solvents, by measuring separately the uptake of iodine by the four tyrosyl groups and the relative amounts of monoiodotyrosine and di-iodotyrosine that are formed. In aqueous media from pH1 to pH9 the iodination occurs predominantly on the tyrosyl groups of the A chain. Some organic solvents increase the iodine uptake of the B-chain tyrosyl groups. Their efficacy in promoting iodination of Tyr-B-16 and Tyr-B-26 is in the order: ethylene glycol and propylene glycol≃methanol and ethanol>dioxan>8m-urea. 2. It is suggested that each of the four tyrosyl groups in insulin has a different environment: Tyr-A-14 is fully exposed to the solvent; Tyr-A-19 is sterically influenced by the environmental structure, possibly by the vicinity of a disulphide interchain bond; Tyr-B-16 is embedded into a non-polar area whose stability is virtually independent of the molecular conformation; Tyr-B-26 is probably in a situation similar to Tyr-B-16 with the difference that its non-polar environment depends on the preservation of the native structure. PMID:5346365

Recurrent Acute Liver Failure Because of Acute Hepatitis Induced by Organic Solvents: A Case Report.

PubMed

Ito, Daisuke; Tanaka, Tomohiro; Akamatsu, Nobuhisa; Ito, Kyoji; Hasegawa, Kiyoshi; Sakamoto, Yoshihiro; Nakagawa, Hayato; Fujinaga, Hidetaka; Kokudo, Norihiro

2016-01-01

The authors present a case of recurrent acute liver failure because of occupational exposure to organic solvents. A 35-year-old man with a 3-week history of worsening jaundice and flu-like symptoms was admitted to our hospital. Viral hepatitis serology and autoimmune factors were negative. The authors considered liver transplantation, but the patient's liver function spontaneously recovered. Liver biopsy revealed massive infiltration of neutrophils, but the cause of the acute hepatitis was not identified. Four months after discharge, the patient's liver function worsened again. The authors considered the possibility of antinuclear antibody-negative autoimmune hepatitis and initiated steroid treatment, which was effective. Four months after discharge, the patient was admitted for repeated liver injury. The authors started him on steroid pulse therapy, but this time it was not effective. Just before the first admission, he had started his own construction company where he was highly exposed to organic solvents, and thus the authors considered organic solvent-induced hepatitis. Although urine test results for organic solvents were negative, a second liver biopsy revealed severe infiltration of neutrophils, compatible with toxic hepatitis. Again, his liver function spontaneously improved. Based on the pathology and detailed clinical course, including the patient's high exposure to organic solvents since just before the first admission, and the spontaneous recovery of his liver damage in the absence of the exposure, he was diagnosed with toxic hepatitis. The authors strongly advised him to avoid organic solvents. Since then, he has been in good health without recurrence. This is the first report of recurrent acute liver failure because of exposure to organic solvents, which was eventually diagnosed through a meticulous medical history and successfully recovered by avoiding the causative agents. In acute liver failure with an undetermined etiology, clinicians should rule

High-temperature, high-pressure hydrothermal synthesis, characterization, and structural relationships of mixed-alkali metals uranyl silicates

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

Chen, Yi-Hsin; Liu, Hsin-Kuan; Chang, Wen-Jung

2016-04-15

Three mixed-alkali metals uranyl silicates, Na{sub 3}K{sub 3}[(UO{sub 2}){sub 3}(Si{sub 2}O{sub 7}){sub 2}]·2H{sub 2}O (1), Na{sub 3}Rb{sub 3}[(UO{sub 2}){sub 3}(Si{sub 2}O{sub 7}){sub 2}] (2), and Na{sub 6}Rb{sub 4}[(UO{sub 2}){sub 4}Si{sub 12}O{sub 33}] (3), have been synthesized by high-temperature, high-pressure hydrothermal reactions at 550 °C and 1440 bar, and characterized by single-crystal X-ray diffraction, photoluminescence, and thermogravimetric analysis. Compound 1 and 2 are isostructural and contain layers of uranyl disilicate. The smaller cation, Na{sup +}, is located in the intralayer channels, whereas the larger cations, K{sup +} and Rb{sup +}, and water molecule are located in the interlayer region. The absencemore » of lattice water in 2 can be understood according to the valence-matching principle. The structure is related to that of a previously reported mixed-valence uranium(V,VI) silicate. Compound 3 adopts a 3D framework structure and contains a unique unbranched dreier fourfold silicate chain with the structural formula {uB,4"1_∞}[{sup 3}Si{sub 12}O{sub 33}] formed of Q{sup 2}, Q{sup 3}, and Q{sup 4} Si. The connectivity of the Si atoms in the Si{sub 12}O{sub 33}{sup 18−} anion can be interpreted on the basis of Zintl–Klemm concept. Crystal data for compound 1: triclinic, P-1, a=5.7981(2) Å, b=7.5875(3) Å, c=12.8068(5) Å, α=103.593(2)°, β=102.879(2)°, γ=90.064(2)°, V=533.00(3) Å{sup 3}, Z=1, R1=0.0278; compound 2: triclinic, P-1, a=5.7993(3) Å, b=7.5745(3) Å, c=12.9369(6) Å, α=78.265(2)°, β=79.137(2)°, γ=89.936(2)°, V=546.02(4) Å{sup 3}, Z=1, R1=0.0287; compound 3: monoclinic, C2/m, a=23.748(1) Å, b=7.3301(3) Å, c=15.2556(7) Å, β=129.116(2)°, V=2060.4(2) Å{sup 3}, Z=2, R1=0.0304. - Graphical abstract: Three mixed-alkali metals uranyl silicates were synthesized under hydrothermal conditions at 550 °C and 1400 bar and structurally characterized by single-crystal X-ray diffraction. Two of them have a layer

Batch extracting process using magneticparticle held solvents

DOEpatents

Nunez, Luis; Vandergrift, George F.

1995-01-01

A process for selectively removing metal values which may include catalytic values from a mixture containing same, wherein a magnetic particle is contacted with a liquid solvent which selectively dissolves the metal values to absorb the liquid solvent onto the magnetic particle. Thereafter the solvent-containing magnetic particles are contacted with a mixture containing the heavy metal values to transfer metal values into the solvent carried by the magnetic particles, and then magnetically separating the magnetic particles. Ion exchange resins may be used for selective solvents.

Manipulating Light with Transition Metal Clusters, Organic Dyes, and Metal Organic Frameworks

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

Ogut, Serdar

The primary goals of our research program is to develop and apply state-of-the-art first-principles methods to predict electronic and optical properties of three systems of significant scientific and technological interest: transition metal clusters, organic dyes, and metal-organic frameworks. These systems offer great opportunities to manipulate light for a wide ranging list of energy-related scientific problems and applications. During this grant period, we focused our investigations on the development, implementation, and benchmarking of many-body Green’s function methods (GW approximation and the Bethe-Salpeter equation) to examine excited-state properties of transition metal/transition-metal-oxide clusters and organic molecules that comprise the building blocks of dyesmore » and metal-organic frameworks.« less

Heteroatom incorporated coke for electrochemical cell electrode

DOEpatents

Lewis, I.C.; Greinke, R.A.

1997-06-17

This invention relates to an electrode for a coke/alkali metal electrochemical cell comprising: (a) calcined coke particles: (1) that contain at least 0.5 weight percent of nitrogen heteroatoms and at least 1.0 weight percent sulfur heteroatoms, and (2) that have an average particle size from 2 microns to 40 microns with essentially no particles being greater than 50 microns and (b) a binder. This invention also relates to a coke/alkali metal electrochemical cell comprising: (a) an electrode as described above, (b) a non-aqueous electrolytic solution comprising an organic aprotic solvent and an electrically conductive salt, and (c) a counterelectrode. 5 figs.

Organic solvents, electrolytes, and lithium ion cells with good low temperature performance

NASA Technical Reports Server (NTRS)

Huang, Chen-Kuo (Inventor); Smart, Marshall C. (Inventor); Surampudi, Subbarao (Inventor); Bugga, Ratnakumar V. (Inventor)

2002-01-01

Multi-component organic solvent systems, electrolytes and electrochemical cells characterized by good low temperature performance are provided. In one embodiment, an improved organic solvent system contains a ternary mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate. In other embodiments, quaternary systems include a fourth component, i.e, an aliphatic ester, an asymmetric alkyl carbonate or a compound of the formula LiOX, where X is R, COOR, or COR, where R is alkyl or fluoroalkyl. Electrolytes based on such organic solvent systems are also provided and contain therein a lithium salt of high ionic mobility, such as LiPF.sub.6. Reversible electrochemical cells, particularly lithium ion cells, are constructed with the improved electrolytes, and preferably include a carbonaceous anode, an insertion type cathode, and an electrolyte interspersed therebetween.

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

PubMed Central

Kalinowska, Monika; Bajko, Ewelina; Matejczyk, Marzena; Kaczyński, Piotr; Łozowicka, Bożena; Lewandowski, Włodzimierz

2018-01-01

Lithium, sodium, potassium, rubidium and caesium salts of 5-O-caffeoylquinic acid (chlorogenic acid, 5-CQA) were synthesized and described by FT-IR (infrared spectroscopy), FT-Raman (Raman spectroscopy), UV (UV absorption spectroscopy), 1H (400.15 MHz), 13C (100.63 MHz) NMR (nuclear magnetic resonance spectroscopy). The quantum–chemical calculations at the B3LYP/6-311++G** level were done in order to obtain the optimal structures, IR spectra, NBO (natural bond orbital) atomic charges, HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) orbitals and chemical reactivity parameters for 5-CQA and Li, Na and K 5-CQAs (chlorogenates). The DPPH (α, α-diphenyl-β-picrylhydrazyl) and FRAP (ferric reducing antioxidant power) assays were used for the preliminary estimation of the antioxidant properties of alkali metal chlorogenates and chlorogenic acid. In the DPPH assay the EC50 parameter were equal to 7.39 μM for 5-CQA and was in the range of 4.50–5.89 μM for salts. The FRAP values for two different concentrations (5 and 2.5 μM) of the studied compounds were respectively 114.22 and 72.53 μM Fe2+ for 5-CQA, whereas for salts they were 106.92–141.13 and 78.93–132.00 μM Fe2+. The 5-CQA and its alkali metal salts possess higher antioxidant properties than commonly applied antioxidants (BHA, BHT, l-ascorbic acid). The pro-oxidant action of these compounds on trolox oxidation was studied in the range of their concentration 0.05–0.35 μM. The lipophilicity (logkw) of chlorogenates and chlorogenic acid was determined by RP-HPLC (reverse phase—high performance liquid chromatography) using five different columns (C8, PHE (phenyl), CN (cyano), C18, IAM (immobilized artificial membrane)). The compounds were screened for their in vitro antibacterial activity against E. coli, Bacillus sp., Staphylococcus sp., Streptococcus pyogenes and antifungal activity against Candida sp. The 5-CQA possessed lower antibacterial (minimal

Comparative metabolic responses and adaptive strategies of wheat (Triticum aestivum) to salt and alkali stress.

PubMed

Guo, Rui; Yang, Zongze; Li, Feng; Yan, Changrong; Zhong, Xiuli; Liu, Qi; Xia, Xu; Li, Haoru; Zhao, Long

2015-07-07

It is well known that salinization (high-pH) has been considered as a major environmental threat to agricultural systems. The aim of this study was to investigate the differences between salt stress and alkali stress in metabolic profiles and nutrient accumulation of wheat; these parameters were also evaluated to determine the physiological adaptive mechanisms by which wheat tolerates alkali stress. The harmful effect of alkali stress on the growth and photosynthesis of wheat were stronger than those of salt stress. High-pH of alkali stress induced the most of phosphate and metal ions to precipitate; as a result, the availability of nutrients significantly declined. Under alkali stress, Ca sharply increased in roots, however, it decreased under salt stress. In addition, we detected the 75 metabolites that were different among the treatments according to GC-MS analysis, including organic acids, amino acids, sugars/polyols and others. The metabolic data showed salt stress and alkali stress caused different metabolic shifts; alkali stress has a stronger injurious effect on the distribution and accumulation of metabolites than salt stress. These outcomes correspond to specific detrimental effects of a highly pH environment. Ca had a significant positive correlation with alkali tolerates, and increasing Ca concentration can immediately trigger SOS Na exclusion system and reduce the Na injury. Salt stress caused metabolic shifts toward gluconeogenesis with increased sugars to avoid osmotic stress; energy in roots and active synthesis in leaves were needed by wheat to develop salt tolerance. Alkali stress (at high pH) significantly inhibited photosynthetic rate; thus, sugar production was reduced, N metabolism was limited, amino acid production was reduced, and glycolysis was inhibited.