National Library of Energy BETA

Sample records for aqueous electrolyte solutions

  1. Implementation of equilibrium aqueous speciation and solubility (EQ3 type) calculations into Cantera for electrolyte solutions.

    SciTech Connect (OSTI)

    Moffat, Harry K.; Jove-Colon, Carlos F.

    2009-06-01

    In this report, we summarize our work on developing a production level capability for modeling brine thermodynamic properties using the open-source code Cantera. This implementation into Cantera allows for the application of chemical thermodynamics to describe the interactions between a solid and an electrolyte solution at chemical equilibrium. The formulations to evaluate the thermodynamic properties of electrolytes are based on Pitzer's model to calculate molality-based activity coefficients using a real equation-of-state (EoS) for water. In addition, the thermodynamic properties of solutes at elevated temperature and pressures are computed using the revised Helgeson-Kirkham-Flowers (HKF) EoS for ionic and neutral aqueous species. The thermodynamic data parameters for the Pitzer formulation and HKF EoS are from the thermodynamic database compilation developed for the Yucca Mountain Project (YMP) used with the computer code EQ3/6. We describe the adopted equations and their implementation within Cantera and also provide several validated examples relevant to the calculations of extensive properties of electrolyte solutions.

  2. Excellent stability of a lithium-ion-conducting solid electrolyte upon reversible Li+/H+ exchange in aqueous solutions

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Ma, Cheng; Rangasamy, Ezhiylmurugan; Liang, Chengdu; Sakamoto, Jeffrey; More, Karren Leslie; Chi, Miaofang

    2014-10-21

    Batteries with an aqueous catholyte and a Li metal anode have attracted interest owing to their exceptional energy density and high charge/discharge rate. The long-term operation of such batteries requires that the solid electrolyte separator between the anode and aqueous solutions must be compatible with Li and stable over a wide pH range. Unfortunately, no such compound has yet been reported. In this study, an excellent stability in neutral and strongly basic solutions was observed when using the cubic Li7La3Zr2O12 garnet as a Li-stable solid electrolyte. The material underwent a Li+/H+ exchange in aqueous solutions. Nevertheless, its structure remained unchangedmore » even under a high exchange rate of 63.6%. When treated with a 2 M LiOH solution, the Li+/H+ exchange was reversed without any structural change. Furthermore, these observations suggest that cubic Li7La3Zr2O12 is a promising candidate for the separator in aqueous lithium batteries.« less

  3. Excellent stability of a lithium-ion-conducting solid electrolyte upon reversible Li+/H+ exchange in aqueous solutions

    SciTech Connect (OSTI)

    Ma, Cheng; Rangasamy, Ezhiylmurugan; Liang, Chengdu; Sakamoto, Jeffrey; More, Karren Leslie; Chi, Miaofang

    2014-10-21

    Batteries with an aqueous catholyte and a Li metal anode have attracted interest owing to their exceptional energy density and high charge/discharge rate. The long-term operation of such batteries requires that the solid electrolyte separator between the anode and aqueous solutions must be compatible with Li and stable over a wide pH range. Unfortunately, no such compound has yet been reported. In this study, an excellent stability in neutral and strongly basic solutions was observed when using the cubic Li7La3Zr2O12 garnet as a Li-stable solid electrolyte. The material underwent a Li+/H+ exchange in aqueous solutions. Nevertheless, its structure remained unchanged even under a high exchange rate of 63.6%. When treated with a 2 M LiOH solution, the Li+/H+ exchange was reversed without any structural change. Furthermore, these observations suggest that cubic Li7La3Zr2O12 is a promising candidate for the separator in aqueous lithium batteries.

  4. Non-aqueous electrolytes for lithium ion batteries

    DOE Patents [OSTI]

    Chen, Zonghai; Amine, Khalil

    2015-11-12

    The present invention is generally related to electrolytes containing anion receptor additives to enhance the power capability of lithium-ion batteries. The anion receptor of the present invention is a Lewis acid that can help to dissolve LiF in the passivation films of lithium-ion batteries. Accordingly, one aspect the invention provides electrolytes comprising a lithium salt; a polar aprotic solvent; and an anion receptor additive; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

  5. Non-aqueous electrolyte for lithium-ion battery

    SciTech Connect (OSTI)

    Zhang, Lu; Zhang, Zhengcheng; Amine, Khalil

    2015-12-22

    An electrolyte including an alkali metal salt; a polar aprotic solvent; and a triazinane trione; wherein the electrolyte is substantially non-aqueous.

  6. Highly Quantitative Electrochemical Characterization of Non-Aqueous Electrolytes & Solid Electrolyte Interphases

    SciTech Connect (OSTI)

    Sergiy V. Sazhin; Kevin L. Gering; Mason K. Harrup; Harry W. Rollins

    2012-10-01

    The methods to measure solid electrolyte interphase (SEI) electrochemical properties and SEI formation capability of non-aqueous electrolyte solutions are not adequately addressed in the literature. And yet, there is a strong demand in new electrolyte generations that promote stabilized SEIs and have an influence to resolve safety, calendar life and other limitations of Li-ion batteries. To fill this gap, in situ electrochemical approach with new descriptive criteria for highly quantitative characterization of SEI and electrolytes is proposed. These criteria are: SEI formation capacity, SEI corrosion rate, SEI maintenance rate, and SEI kinetic stability. These criteria are associated with battery parameters like irreversible capacity, self-discharge, shelf-life, power, etc. Therefore, they are especially useful for electrolyte development and standard fast screening, allowing a skillful approach to narrow down the search for the best electrolyte. The characterization protocol also allows retrieving information on interfacial resistance for SEI layers and the electrochemical window of electrolytes, the other important metrics of characterization. The method validation was done on electrolyte blends containing phosphazenes, developed at Idaho National Laboratory, as 1.2M LiPF6 [80 % EC-MEC (2:8) (v/v) + 20% Phosphazene variety] (v/v), which were targeted for safer electrolyte variations.

  7. Separation of metal ions from aqueous solutions

    DOE Patents [OSTI]

    Almon, Amy C.

    1994-01-01

    A process and apparatus for quantitatively and selectively separating metal ions from mixtures thereof in aqueous solution. The apparatus includes, in combination, a horizontal electrochemical flow cell containing flow bulk electrolyte solution and an aqueous, metal ion-containing solution, the cell containing a metal mesh working electrode, a counter electrode positioned downstream from the working electrode, an independent variable power supply/potentiostat positioned outside of the flow cell and connected to the electrodes, and optionally a detector such as a chromatographic detector, positioned outside the flow cell. This apparatus and its operation has significant application where trace amounts of metal ions are to be separated.

  8. High conductivity electrolyte solutions and rechargeable cells incorporating such solutions

    DOE Patents [OSTI]

    Angell, C.A.; Zhang, S.S.; Xu, K.

    1998-10-20

    This invention relates generally to electrolyte solvents for use in liquid or rubbery polymer electrolyte solutions as are used, for example, in electrochemical devices. More specifically, this invention relates to sulfonyl/phospho-compound electrolyte solvents and sulfonyl/phospho-compound electrolyte solutions incorporating such solvents. 9 figs.

  9. High conductivity electrolyte solutions and rechargeable cells incorporating such solutions

    DOE Patents [OSTI]

    Angell, Charles Austen (Mesa, AZ); Zhang, Sheng-Shui (Tucson, AZ); Xu, Kang (Tempe, AZ)

    1998-01-01

    This invention relates generally to electrolyte solvents for use in liquid or rubbery polymer electrolyte solutions as are used, for example, in electrochemical devices. More specifically, this invention relates to sulfonyl/phospho-compound electrolyte solvents and sulfonyl/phospho-compound electrolyte solutions incorporating such solvents.

  10. Basic energy properties of electrolytic solutions database. ...

    Office of Scientific and Technical Information (OSTI)

    Basic energy properties of electrolytic solutions database. Viscosity, thermal conductivity, density, enthalpy Citation Details In-Document Search Title: Basic energy properties ...

  11. Non-aqueous electrolytes for electrochemical cells

    DOE Patents [OSTI]

    Zhang, Zhengcheng; Dong, Jian; Amine, Khalil

    2016-06-14

    An electrolyte electrochemical device includes an anodic material and an electrolyte, the electrolyte including an organosilicon solvent, a salt, and a hybrid additiving having a first and a second compound, the hybrid additive configured to form a solid electrolyte interphase film on the anodic material upon application of a potential to the electrochemical device.

  12. Non-aqueous electrolytes for lithium-air batteries

    DOE Patents [OSTI]

    Amine, Khalil; Chen, Zonghai; Zhang, Zhengcheng

    2016-06-07

    A lithium-air cell includes a negative electrode; an air positive electrode; and a non-aqueous electrolyte which includes an anion receptor that may be represented by one or more of the formulas. ##STR00001##

  13. Non-aqueous electrolyte for lithium-ion battery

    DOE Patents [OSTI]

    Amine, Khalil; Zhang, Lu; Zhang, Zhengcheng

    2016-01-26

    A substantially non-aqueous electrolyte solution includes an alkali metal salt, a polar aprotic solvent, and an organophosphorus compound of Formula IA, IB, or IC: ##STR00001## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each independently hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkoxy, alkenoxy, alkynoxy, cycloalkoxy, aryloxy, heterocyclyloxy, heteroaryloxy, siloxyl, silyl, or organophosphatyl; R.sup.5 and R.sup.6 are each independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl; R.sup.7 is ##STR00002## and R.sup.8, R.sup.9 and R.sup.10 are each independently alkyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl; provided that if the organophosphorus compound is of Formula IB, then at least one of R.sup.5, and R.sup.6 are other than hydrogen, alkyl, or alkenyl; and if the organophosphorus compound is of Formula IC, then the electrolyte solution does not include 4-methylene-1,3-dioxolan-2-one or 4,5-dimethylene-1,3-dioxolan-2-one.

  14. Anion receptor compounds for non-aqueous electrolytes

    DOE Patents [OSTI]

    Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

    2000-09-19

    A new family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

  15. Cesium recovery from aqueous solutions

    DOE Patents [OSTI]

    Goodhall, C. A.

    1960-09-13

    A process for recovering cesium from aqueous solutions is given in which precipitation on zinc ferricyanide is used. The precipitation is preferably carried out in solutions containing at least 0.0004M zinc ferricyanide, an acidity ranging from 0.2N mineral acid to 0.61N acid deficiency, and 1 to 2.5M aluminum nitrate. (D.L.C.)

  16. Phenyl boron-based compounds as anion receptors for non-aqueous battery electrolytes

    DOE Patents [OSTI]

    Lee, Hung Sui; Yang, Xiao-Qing; McBreen, James; Sun, Xuehui

    2002-01-01

    Novel fluorinated boronate-based compounds which act as anion receptors in non-aqueous battery electrolytes are provided. When added to non-aqueous battery electrolytes, the fluorinated boronate-based compounds of the invention enhance ionic conductivity and cation transference number of non-aqueous electrolytes. The fluorinated boronate-based anion receptors include different fluorinated alkyl and aryl groups.

  17. Control Of Screening Of A Charged Particle In Electrolytic Aqueous Paul Trap

    SciTech Connect (OSTI)

    Park, Jae Hyun; Krstic, Predrag S.

    2011-06-01

    Individual charged particles could be trapped and confined by the combined radio-frequency and DC quadrupole electric field of an aqueous Paul trap. Viscosity of water improves confinement and extends the range of the trap parameters which characterize the stability of the trap. Electrolyte, if present in aqueous solution, may screen the charged particle and thus partially or fully suppress electrophoretic interaction with the applied filed, possibly reducing it to a generally much weaker dielectrophoretic interaction with an induced dipole. Applying molecular dynamics simulation we show that the quadrupole field has a different effect at the electrolyte ions and at much heavier charged particle, effectively eliminating the screening by electrolyte ions and reinstating the electrophoretic confinement.

  18. Non-aqueous electrolytes for electrochemical cells

    DOE Patents [OSTI]

    Dong, Jian; Zhang, Zhengcheng; Amine, Khalil

    2016-07-12

    A electrolyte for a lithium battery includes a silane/siloxane compound represented by SiR.sub.4-x-yR'.sub.xR''.sub.y, by Formula II, or Formula III: ##STR00001## where each R is individually an alkenyl, alkynyl, alk(poly)enyl, alk(poly)ynyl, aryl; each R' is represented by; ##STR00002## each R'' is represented by Formula I-B; ##STR00003## R.sup.1 is an organic spacer; R.sup.2 is a bond or an organic spacer; R.sup.3 is alkyl or aryl; k is 1-15; m is 1-15; n is 1 or 2; p is 1-3; x' is 1-2; and y' is 0-2.

  19. Non-aqueous solution preparation of doped and undoped lixmnyoz

    DOE Patents [OSTI]

    Boyle, Timothy J.; Voigt, James A.

    1997-01-01

    A method for generation of phase-pure doped and undoped Li.sub.x Mn.sub.y O.sub.z precursors. The method of this invention uses organic solutions instead of aqueous solutions or nonsolution ball milling of dry powders to produce phase-pure precursors. These precursors can be used as cathodes for lithium-polymer electrolyte batteries. Dopants may be homogeneously incorporated to alter the characteristics of the powder.

  20. Three dimensional electrode for the electrolytic removal of contaminants from aqueous waste streams

    DOE Patents [OSTI]

    Spiegel, Ella F.; Sammells, Anthony F.

    2001-01-01

    Efficient and cost-effective electrochemical devices and processes for the remediation of aqueous waste streams. The invention provides electrolytic cells having a high surface area spouted electrode for removal of heavy metals and oxidation of organics from aqueous environments. Heavy metal ions are reduced, deposited on cathode particles of a spouted bed cathode and removed from solution. Organics are efficiently oxidized at anode particles of a spouted bed anode and removed from solution. The method of this inventions employs an electrochemical cell having an anolyte compartment and a catholyte compartment, separated by a microporous membrane, in and through which compartments anolyte and catholyte, respectively, are circulated. A spouted-bed electrode is employed as the cathode for metal deposition from contaminated aqueous media introduced as catholyte and as the anode for oxidation of organics from contaminated aqueous media introduced as anolyte.

  1. REMOVAL OF CHLORIDE FROM AQUEOUS SOLUTIONS

    DOE Patents [OSTI]

    Schulz, W.W.

    1959-08-01

    The removal of chlorides from aqueons solutions is described. The process involves contacting the aqueous chloride containing solution with a benzene solution about 0.005 M in phenyl mercuric acetate whereby the chloride anions are taken up by the organic phase and separating the organic phase from the aqueous solutions.

  2. Simulation of Osmotic Pressure in Concentrated Aqueous Salt Solutions |

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Argonne Leadership Computing Facility Simulation of Osmotic Pressure in Concentrated Aqueous Salt Solutions Authors: Luo, Y., Roux, B. Accurate force fields are critical for meaningful simulation studies of highly concentrated electrolytes. The ion models that are widely used in biomolecular simulations do not necessarily reproduce the correct behavior at finite concentrations. In principle, the osmotic pressure is a key thermodynamic property that could be used to test and refine force

  3. SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

    DOE Patents [OSTI]

    Beederman, M.; Vogler, S.; Hyman, H.H.

    1959-07-14

    The separation of rathenium from a rathenium containing aqueous solution is described. The separation is accomplished by adding sodium nitrite, silver nitrate and ozone to the ruthenium containing aqueous solution to form ruthenium tetroxide and ihen volatilizing off the ruthenium tetroxide.

  4. Wide electrochemical window solvents for use in electrochemical devices and electrolyte solutions incorporating such solvents

    DOE Patents [OSTI]

    Angell, Charles Austen; Zhang, Sheng-Shui; Xu, Kang

    1998-01-01

    The present invention relates to electrolyte solvents for use in liquid or rubbery electrolyte solutions. Specifically, this invention is directed to boron-containing electrolyte solvents and boron-containing electrolyte solutions.

  5. RECOVERY OF TETRAVALENT CATIONS FROM AQUEOUS SOLUTIONS

    DOE Patents [OSTI]

    Moore, R.L.

    1958-05-01

    The recovery of plutonium, zirconium, and tetravalent cerium values from aqueous solutions is described. It consists of adding an alkyl phosphate to a nnineral acid aqueous solution containing the metal to be recovered, whereby a precipitate forms with the tetravalent values, and separating the precipitate from the solution. All alkyl phosphates, if water-soluble, are suitable for the process; however, monobutyl phosphate has been found best.

  6. Non-aqueous electrolytes for lithium ion batteries (Patent) ...

    Office of Scientific and Technical Information (OSTI)

    Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte. Inventors: Chen, Zonghai ; Amine, Khalil Issue Date: 2015-11-12 ...

  7. Calculation of chemical equilibrium between aqueous solution...

    Office of Scientific and Technical Information (OSTI)

    natural water compositions; EQ6 uses the results of EQ3 to predict the consequences of heating and cooling aqueous solutions and of irreversible reaction in rock--water systems. ...

  8. Interactions of Spores with Planar Surfaces in Aqueous Solutions...

    Office of Scientific and Technical Information (OSTI)

    Interactions of Spores with Planar Surfaces in Aqueous Solutions Citation Details In-Document Search Title: Interactions of Spores with Planar Surfaces in Aqueous Solutions ...

  9. SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

    DOE Patents [OSTI]

    Callis, C.F.; Moore, R.L.

    1959-09-01

    >The separation of ruthenium from aqueous solutions containing uranium plutonium, ruthenium, and fission products is described. The separation is accomplished by providing a nitric acid solution of plutonium, uranium, ruthenium, and fission products, oxidizing plutonium to the hexavalent state with sodium dichromate, contacting the solution with a water-immiscible organic solvent, such as hexone, to extract plutonyl, uranyl, ruthenium, and fission products, reducing with sodium ferrite the plutonyl in the solvent phase to trivalent plutonium, reextracting from the solvent phase the trivalent plutonium, ruthenium, and some fission products with an aqueous solution containing a salting out agent, introducing ozone into the aqueous acid solution to oxidize plutonium to the hexavalent state and ruthenium to ruthenium tetraoxide, and volatizing off the ruthenium tetraoxide.

  10. Extracting alcohols from aqueous solutions

    DOE Patents [OSTI]

    Compere, Alicia L.; Googin, John M.; Griffith, William L.

    1984-01-01

    Hydrocarbon and surfactants are contacted with a solution of alcohol and water to extract the alcohol into the hydrocarbon-surfactant mixture.

  11. ADSORPTION OF CERIUM VALUES FROM AQUEOUS SOLUTIONS

    DOE Patents [OSTI]

    Roberts, F.P.

    1963-08-13

    Cerium can be removed from aqueous nitric acid (2 to 13 M) solutions by passing the latter over a PbO/sub 2/-containing anion exchange resin. The cerium is taken up by the resin, while any lanthanides, yttrium, and strontium present remain in the solution. (AEC)

  12. Rotating Disk-Electrode Aqueous Electrolyte Accelerated Stress Tests for PGM Electrocatalyst/Support Durability Evaluation

    Broader source: Energy.gov [DOE]

    Rotating disk-electrode aqueous electrolyte accelerated stress test protocols developed by the DOE Durability Working Group for platinum group metal (PGM) electrocatalyst/support durability evaluation, October 4, 2011.

  13. Ambipolar zinc-polyiodide electrolyte for a high-energy density aqueous redox flow battery

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Li, Bin; Nie, Zimin; Vijayakumar, M.; Li, Guosheng; Liu, Jun; Sprenkle, Vincent L.; Wang, Wei

    2015-02-24

    Large-scale energy storage systems are crucial for substantial deployment of renewable energy sources. Energy storage systems with high energy density, high safety, and low cost and environmental friendliness are desired. To overcome the major limitations of the current aqueous redox flow battery systems, namely lower energy density (~25 Wh L-1) and presence of strong acids and/or other hazardous, a high energy density aqueous zinc/polyiodide flow battery (ZIB) is designed with near neutral ZnI2 solutions as catholytes. The energy density of ZIB could reach 322 Wh L-1 at the solubility limit of ZnI2 in water (~7 M). We demonstrate charge andmore » discharge energy densities of 245.9 Wh/L and 166.7 Wh L-1 with ZnI2 electrolyte at 5.0 M, respectively. The addition of ethanol (EtOH) in ZnI2 electrolyte can effectively mitigate the growth of zinc dendrite at the anode and improve the stability of catholytes with wider temperature window (-20 to 50°C), which enable ZIB system to be a promising alternative as a high-energy and high- safety stationary energy storage system.« less

  14. Ambipolar zinc-polyiodide electrolyte for a high-energy density aqueous redox flow battery

    SciTech Connect (OSTI)

    Li, Bin; Nie, Zimin; Vijayakumar, M.; Li, Guosheng; Liu, Jun; Sprenkle, Vincent L.; Wang, Wei

    2015-02-24

    Large-scale energy storage systems are crucial for substantial deployment of renewable energy sources. Energy storage systems with high energy density, high safety, and low cost and environmental friendliness are desired. To overcome the major limitations of the current aqueous redox flow battery systems, namely lower energy density (~25 Wh L-1) and presence of strong acids and/or other hazardous, a high energy density aqueous zinc/polyiodide flow battery (ZIB) is designed with near neutral ZnI2 solutions as catholytes. The energy density of ZIB could reach 322 Wh L-1 at the solubility limit of ZnI2 in water (~7 M). We demonstrate charge and discharge energy densities of 245.9 Wh/L and 166.7 Wh L-1 with ZnI2 electrolyte at 5.0 M, respectively. The addition of ethanol (EtOH) in ZnI2 electrolyte can effectively mitigate the growth of zinc dendrite at the anode and improve the stability of catholytes with wider temperature window (-20 to 50°C), which enable ZIB system to be a promising alternative as a high-energy and high- safety stationary energy storage system.

  15. Ambipolar zinc-polyiodide electrolyte for a high-energy density aqueous redox flow battery

    SciTech Connect (OSTI)

    Li, Bin; Nie, Zimin; Vijayakumar, M.; Li, Guosheng; Liu, Jun; Sprenkle, Vincent L.; Wang, Wei

    2015-02-24

    Large-scale energy storage systems are crucial for substantial deployment of renewable energy sources. Energy storage systems with high energy density, high safety, and low cost and environmental friendliness are desired. To overcome the major limitations of the current aqueous redox flow battery systems, namely lower energy density (~25 Wh L-1) and presence of strong acids and/or other hazardous, a high energy density aqueous zinc/polyiodide flow battery (ZIB) is designed with near neutral ZnI2 solutions as catholytes. The energy density of ZIB could reach 322 Wh L-1 at the solubility limit of ZnI2 in water (~7 M). We demonstrate charge and discharge energy densities of 245.9 Wh/L and 166.7 Wh L-1 with ZnI2 electrolyte at 5.0 M, respectively. The addition of ethanol (EtOH) in ZnI2 electrolyte can effectively mitigate the growth of zinc dendrite at the anode and improve the stability of catholytes with wider temperature window (-20 to 50°C), which enable ZIB system to be a promising alternative as a high-energy and high- safety stationary energy storage system.

  16. Removal of uranium from aqueous HF solutions

    DOE Patents [OSTI]

    Pulley, Howard; Seltzer, Steven F.

    1980-01-01

    This invention is a simple and effective method for removing uranium from aqueous HF solutions containing trace quantities of the same. The method comprises contacting the solution with particulate calcium fluoride to form uranium-bearing particulates, permitting the particulates to settle, and separting the solution from the settled particulates. The CaF.sub.2 is selected to have a nitrogen surface area in a selected range and is employed in an amount providing a calcium fluoride/uranium weight ratio in a selected range. As applied to dilute HF solutions containing 120 ppm uranium, the method removes at least 92% of the uranium, without introducing contaminants to the product solution.

  17. Non-aqueous electrolyte for high voltage rechargeable magnesium batteries

    DOE Patents [OSTI]

    Doe, Robert Ellis; Lane, George Hamilton; Jilek, Robert E; Hwang, Jaehee

    2015-02-10

    An electrolyte for use in electrochemical cells is provided. The properties of the electrolyte include high conductivity, high Coulombic efficiency, and an electrochemical window that can exceed 3.5 V vs. Mg/Mg.sup.+2. The use of the electrolyte promotes the electrochemical deposition and dissolution of Mg without the use of any Grignard reagents, other organometallic materials, tetraphenyl borate, or tetrachloroaluminate derived anions. Other Mg-containing electrolyte systems that are expected to be suitable for use in secondary batteries are also described.

  18. High voltage rechargeable magnesium batteries having a non-aqueous electrolyte

    DOE Patents [OSTI]

    Doe, Robert Ellis; Lane, George Hamilton; Jilek, Robert E.; Hwang, Jaehee

    2016-03-22

    A rechargable magnesium battery having an non-aqueous electrolyte is provided. The properties of the electrolyte include high conductivity, high Coulombic efficiency, and an electrochemical window that can exceed 3.5 V vs. Mg/Mg.sup.+2. The use of the electrolyte promotes the electrochemical deposition and dissolution of Mg without the use of any Grignard reagents, other organometallic materials, tetraphenyl borate, or tetrachloroaluminate derived anions. Other Mg-containing electrolyte systems that are expected to be suitable for use in secondary batteries are also described.

  19. Removal of metal ions from aqueous solution

    DOE Patents [OSTI]

    Jackson, Paul J.; Delhaize, Emmanuel; Robinson, Nigel J.; Unkefer, Clifford J.; Furlong, Clement

    1990-01-01

    A method of removing heavy metals from aqueous solution, a composition of matter used in effecting said removal, and apparatus used in effecting said removal. One or more of the polypeptides, poly (.gamma.-glutamylcysteinyl)glycines, is immobilized on an inert material in particulate form. Upon contact with an aqueous solution containing heavy metals, the polypeptides sequester the metals, removing them from the solution. There is selectivity of poly (.gamma.-glutamylcysteinyl)glycines having a particular number of monomer repeat units for particular metals. The polypeptides are easily regenerated by contact with a small amount of an organic acid, so that they can be used again to remove heavy metals from solution. This also results in the removal of the metals from the column in a concentrated form.

  20. Removal of metal ions from aqueous solution

    DOE Patents [OSTI]

    Jackson, Paul J.; Delhaize, Emmanuel; Robinson, Nigel J.; Unkefer, Clifford J.; Furlong, Clement

    1990-11-13

    A method of removing heavy metals from aqueous solution, a composition of matter used in effecting said removal, and apparatus used in effecting said removal. One or more of the polypeptides, poly (.gamma.-glutamylcysteinyl)glycines, is immobilized on an inert material in particulate form. Upon contact with an aqueous solution containing heavy metals, the polypeptides sequester the metals, removing them from the solution. There is selectivity of poly (.gamma.-glutamylcysteinyl)glycines having a particular number of monomer repeat unit for particular metals. The polypeptides are easily regenerated by contact with a small amount of an organic acid, so that they can be used again to remove heayv metals from solution. This also results in the removal of the metals from the column in a concentrated form.

  1. RECOVERY OF PLUTONIUM FROM AQUEOUS SOLUTIONS

    DOE Patents [OSTI]

    Reber, E.J.

    1959-09-01

    A process is described for recovering plutonium values from aqueous solutions by precipitation on bismuth phosphate. The plutonium is secured in its tetravalent state. bismuth salt is added to the solution, and ant excess of phosphoric acid anions is added to the solution in two approximately equal installments. The rate of addition of the first installment is about two to three times as high as the rate of addition of the second installment, whereby a precipitate of bismuth phosphate forms, the precipitate carrying the plutonium values. The precipitate is separated from the solution.

  2. SEPARATION OF SCANDIUM FROM AQUEOUS SOLUTIONS

    DOE Patents [OSTI]

    Peppard, D.F.; Nachtman, E.S.

    1958-02-25

    This patent relates to a process for the separation of scandium from yttrium, thorium, and trivalent rare earths and with their separation from each other. It has been found that scandium and yttrium can be separated from trivalent rare earths in acidic solution, for example, a solution 6 M in HCl, by contacting with tributyl phosphate, whereupon the scandum is preferentially extracted into the organic phase, leaving the yttrium and trivalent rare earths in the aqueous phase.

  3. Toward the understanding of hydration phenomena in aqueous electrolytes from the interplay of theory, molecular simulation, and experiment

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Chialvo, Ariel A.; Vlcek, Lukas

    2015-05-22

    We confront the microstructural analysis of aqueous electrolytes and present a detailed account of the fundamentals underlying the neutron scattering with isotopic substitution (NDIS) approach for the experimental determination of ion coordination numbers in systems involving both halides anions and oxyanions. We place particular emphasis on the frequently overlooked ion-pairing phenomenon, identify its microstructural signature in the neutron-weighted distribution functions, and suggest novel techniques to deal with either the estimation of the ion-pairing magnitude or the correction of its effects on the experimentally measured coordination numbers. We illustrate the underlying ideas by applying these new developments to the interpretation ofmore » four NDIS test-cases via molecular simulation, as convenient dry runs for the actual scattering experiments, for representative aqueous electrolyte solutions at ambient conditions involving metal halides and nitrates.« less

  4. Toward the understanding of hydration phenomena in aqueous electrolytes from the interplay of theory, molecular simulation, and experiment

    SciTech Connect (OSTI)

    Chialvo, Ariel A.; Vlcek, Lukas

    2015-05-22

    We confront the microstructural analysis of aqueous electrolytes and present a detailed account of the fundamentals underlying the neutron scattering with isotopic substitution (NDIS) approach for the experimental determination of ion coordination numbers in systems involving both halides anions and oxyanions. We place particular emphasis on the frequently overlooked ion-pairing phenomenon, identify its microstructural signature in the neutron-weighted distribution functions, and suggest novel techniques to deal with either the estimation of the ion-pairing magnitude or the correction of its effects on the experimentally measured coordination numbers. We illustrate the underlying ideas by applying these new developments to the interpretation of four NDIS test-cases via molecular simulation, as convenient dry runs for the actual scattering experiments, for representative aqueous electrolyte solutions at ambient conditions involving metal halides and nitrates.

  5. Microscopic Insights into the Electrochemical Behavior of Non-aqueous Electrolytes in Supercapacitors

    SciTech Connect (OSTI)

    Jiang, Deen; Wu, Jianzhong

    2013-01-01

    Electric double-layer capacitors (EDLC) are electrical devices that store energy by adsorption of ionic species at the inner surface of porous electrodes. Compared with aqueous electrolytes, ionic liquid and organic electrolytes have the advantage of larger potential windows, making them attractive for the next generation of EDLC with superior energy and power densities. The performance of both ionic liquid and organic electrolyte EDLC hinges on the judicious selection of the electrode pore size and the electrolyte composition that requires a comprehension of the charging behavior from a microscopic view. In this perspective, we discuss predictions from the classical density functional theory (CDFT) on the dependence of the capacitance on the pore size for ionic-liquid and organic-electrolyte EDLC. CDFT is applicable to electrodes with the pore size ranging from that below the ionic dimensionality to mesoscopic scales, thus unique for investigating the electrochemical behavior of the confined electrolytes for EDLC applications.

  6. ELECTROLYTIC REDUCTION OF NITRIC ACID SOLUTIONS

    DOE Patents [OSTI]

    Alter, H.W.; Barney, D.L.

    1958-09-30

    A process is presented for the treatment of radioactivc waste nitric acid solutions. The nitric acid solution is neutralized with an alkali metal hydroxide in an amount sufficient to precipitate insoluble hydroxides, and after separation of the precipitate the solution is electrolyzed to convert the alkali nitrate formed, to alkali hydroxide, gaseous ammonla and oxygen. The solution is then reusable after reducing the volume by evaporating the water and dissolved ammonia.

  7. Basic energy properties of electrolytic solutions database. ...

    Office of Scientific and Technical Information (OSTI)

    THERMAL CONDUCTIVITY; VISCOSITY; ALKALI METAL COMPOUNDS; CHLORIDES; CHLORINE COMPOUNDS; DISPERSIONS; HALIDES; HALOGEN COMPOUNDS; MIXTURES; SODIUM COMPOUNDS; SOLUTIONS; ...

  8. Non-aqueous electrolyte for lithium-ion battery

    DOE Patents [OSTI]

    Zhang, Lu; Zhang, Zhengcheng; Amine, Khalil

    2014-04-15

    The present technology relates to stabilizing additives and electrolytes containing the same for use in electrochemical devices such as lithium ion batteries and capacitors. The stabilizing additives include triazinane triones and bicyclic compounds comprising succinic anhydride, such as compounds of Formulas I and II described herein.

  9. Aqueous Solution Vessel Thermal Model Development II

    SciTech Connect (OSTI)

    Buechler, Cynthia Eileen

    2015-10-28

    The work presented in this report is a continuation of the work described in the May 2015 report, “Aqueous Solution Vessel Thermal Model Development”. This computational fluid dynamics (CFD) model aims to predict the temperature and bubble volume fraction in an aqueous solution of uranium. These values affect the reactivity of the fissile solution, so it is important to be able to calculate them and determine their effects on the reaction. Part A of this report describes some of the parameter comparisons performed on the CFD model using Fluent. Part B describes the coupling of the Fluent model with a Monte-Carlo N-Particle (MCNP) neutron transport model. The fuel tank geometry is the same as it was in the May 2015 report, annular with a thickness-to-height ratio of 0.16. An accelerator-driven neutron source provides the excitation for the reaction, and internal and external water cooling channels remove the heat. The model used in this work incorporates the Eulerian multiphase model with lift, wall lubrication, turbulent dispersion and turbulence interaction. The buoyancy-driven flow is modeled using the Boussinesq approximation, and the flow turbulence is determined using the k-ω Shear-Stress-Transport (SST) model. The dispersed turbulence multiphase model is employed to capture the multiphase turbulence effects.

  10. RECOVERY OF ACTINIDES FROM AQUEOUS NITRIC ACID SOLUTIONS

    DOE Patents [OSTI]

    Ader, M.

    1963-11-19

    A process of recovering actinides is presented. Tetravalent actinides are extracted from rare earths in an aqueous nitric acid solution with a ketone and back-extracted from the ketone into an aqueous medium. The aqueous actinide solution thus obtained, prior to concentration by boiling, is sparged with steam to reduce its ketone to a maximum content of 3 grams per liter. (AEC)

  11. Electrical pulse fabrication of graphene nanopores in electrolyte solution

    SciTech Connect (OSTI)

    Kuan, Aaron T.; Szalay, Tamas; Lu, Bo; Xie, Ping; Golovchenko, Jene A.

    2015-05-18

    Nanopores in graphene membranes can potentially offer unprecedented spatial resolution for single molecule sensing, but their fabrication has thus far been difficult, poorly scalable, and prone to contamination. We demonstrate an in-situ fabrication method that nucleates and controllably enlarges nanopores in electrolyte solution by applying ultra-short, high-voltage pulses across the graphene membrane. This method can be used to rapidly produce graphene nanopores with subnanometer size accuracy in an apparatus free of nanoscale beams or tips.

  12. Aqueous solutions database to high temperatures and pressures...

    Office of Scientific and Technical Information (OSTI)

    Title: Aqueous solutions database to high temperatures and pressures: NaCl solutions A survey is made of available experimental data on sodium chloride solutions which are used in ...

  13. Functionalized polymers for binding to solutes in aqueous solutions

    DOE Patents [OSTI]

    Smith, Barbara F.; Robison, Thomas W.

    2006-11-21

    A functionalized polymer for binding a dissolved molecule in an aqueous solution is presented. The polymer has a backbone polymer to which one or more functional groups are covalently linked. The backbone polymer can be such polymers as polyethylenimine, polyvinylamine, polyallylamine, and polypropylamine. These polymers are generally water-soluble, but can be insoluble when cross-linked. The functional group can be for example diol derivatives, polyol derivatives, thiol and dithiol derivatives, guest-host groups, affinity groups, beta-diphosphonic acids, and beta-diamides

  14. Process for decomposing nitrates in aqueous solution

    DOE Patents [OSTI]

    Haas, Paul A.

    1980-01-01

    This invention is a process for decomposing ammonium nitrate and/or selected metal nitrates in an aqueous solution at an elevated temperature and pressure. Where the compound to be decomposed is a metal nitrate (e.g., a nuclear-fuel metal nitrate), a hydroxylated organic reducing agent therefor is provided in the solution. In accordance with the invention, an effective proportion of both nitromethane and nitric acid is incorporated in the solution to accelerate decomposition of the ammonium nitrate and/or selected metal nitrate. As a result, decomposition can be effected at significantly lower temperatures and pressures, permitting the use of system components composed of off-the-shelf materials, such as stainless steel, rather than more costly materials of construction. Preferably, the process is conducted on a continuous basis. Fluid can be automatically vented from the reaction zone as required to maintain the operating temperature at a moderate value--e.g., at a value in the range of from about 130.degree.-200.degree. C.

  15. Direct observation of contact ion-pairing in aqueous solution...

    Office of Scientific and Technical Information (OSTI)

    Sponsoring Org: USDOE Country of Publication: United States Language: English Subject: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AQUEOUS SOLUTIONS; ION PAIRS; ...

  16. Uranyl-Peroxide Nanocapsules in Aqueous Solution: Force Field...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Uranyl-Peroxide Nanocapsules in Aqueous Solution: Force Field Development and First Applications Previous Next List Pere Mir, Bess Vlaisavljevich, Allison L. Dzubak, Shuxian Hu,...

  17. Excitation Energies of Zinc Porphyrin in Aqueous Solution Using...

    Office of Scientific and Technical Information (OSTI)

    Theory Citation Details In-Document Search Title: Excitation Energies of Zinc Porphyrin in Aqueous Solution Using Long-Range Corrected Time-Dependent Density Functional Theory ...

  18. A Comparative Study of Anodized Titania Nanotube Architectures in Aqueous and Nonaqueous Solutions

    SciTech Connect (OSTI)

    Sturgeon, Matthew R; Lai, Peng; Hu, Michael Z.

    2011-01-01

    The unique and highly utilized properties of TiO2 nanotubes are a direct result of nanotube architecture. In order to create different engineered architectures, the effects of electrolyte solution, time, and temperature on the anodization of titanium foil were studied along with the resultant anodized titanium oxide (ATO) nanotube architectures encompassing nanotube length, pore diameter, wall thickness, smoothness, and ordered array structure. Titanium foil was anodized in three different electrolyte solutions: one aqueous (consisting of NH4F and (NH4)2SO4)) and two nonaqueous (glycerin or ethylene glycol, both containing NH4F) at varying temperatures and anodization times. Variation in anodization applied voltage, initial current, and effect of F- ion concentration on ATO nanotube architecture were also studied. Anodization in the aqueous electrolyte produced short, rough nanotube arrays, whereas anodization in organic electrolytes produced long, smooth nanotube arrays greater than 10 m in length. Anodization in glycerin at elevated temperatures for several hours presents the possibility of producing freely dispersed individual nanotubes.

  19. Electrodeposited Manganese Oxides on Three-Dimensional Carbon Nanotube Substrate: Supercapacitive Behaviour in Aqueous and Organic Electrolytes

    SciTech Connect (OSTI)

    Nam,K.W.; Yang,X.

    2009-03-01

    Thin amorphous manganese oxide layers with a thickness of 3-5nm are electrodeposited on a carbon nanotube (CNT) film substrate that has a three-dimensional nanoporous structure (denoted asMnO2/CNT electrode). For the purpose of comparison, manganese oxide films are also electrodeposited on a flat Pt-coated Si wafer substrate (denoted as MnO2 film electrode). The pseudocapacitive properties of the MnO2 film and MnO2/CNT electrodes are examined in both aqueous electrolyte (1.0M KCl) and nonaqueousorganic electrolyte (1.0M LiClO4 in propylene carbonate). While both types of electrode showpseudocapacitive behaviour in the aqueous electrolyte, only the MnO2/CNT electrode does so in the organic electrolyte, due to its high oxide/electrolyte interfacial area and improved electron conduction through the CNT substrate. Compared with the MnO2 film electrode, the MnO2/CNT electrode shows a much higher specific capacitance and better high-rate capability, regardless of the electrolyte used.Use of the organic electrolyte results in a ?6 times higher specific energy compared with that obtained with the aqueous electrolyte, while maintaining a similar specific power. The construction of a threedimensional nanoporous network structure consisting of a thin oxide layer on a CNT film substrate at the nm scale and the use of an organic electrolyte are promising approaches to improving the specific energyof supercapacitors.

  20. Hydroxyl radical production in plasma electrolysis with KOH electrolyte solution

    SciTech Connect (OSTI)

    Saksono, Nelson; Febiyanti, Irine Ayu Utami, Nissa; Ibrahim

    2015-12-29

    Plasma electrolysis is an effective technology for producing hydroxyl radical (•OH). This method can be used for waste degradation process. This study was conducted to obtain the influence of applied voltage, electrolyte concentration, and anode depth in the plasma electrolysis system for producing hydroxyl radical. The materials of anode and cathode, respectively, were made from tungsten and stainless steel. KOH solution was used as the solution. Determination of hydroxyl radical production was done by measuring H{sub 2}O{sub 2} amount formed in plasma system using an iodometric titration method, while the electrical energy consumed was obtained by measuring the electrical current throughout the process. The highest hydroxyl radical production was 3.51 mmol reached with 237 kJ energy consumption in the power supply voltage 600 V, 0.02 M KOH, and 0.5 cm depth of anode.

  1. SEPARATION OF PLUTONIUM FROM AQUEOUS SOLUTIONS BY ION-EXCHANGE

    DOE Patents [OSTI]

    Schubert, J.

    1958-06-01

    A process is described for the separation of plutonium from an aqueous solution of a plutonium salt, which comprises adding to the solution an acid of the group consisting of sulfuric acid, phosphoric acid, and oxalic acid, and mixtures thereof to provide an acid concentration between 0.0001 and 1 M, contacting the resultant solution with a synthetic organic anion exchange resin, and separating the aqueous phase and the resin which contains the plutonium.

  2. Excellent Stability of a Lithium-Ion-Conducting Solid Electrolyte...

    Office of Scientific and Technical Information (OSTI)

    Excellent Stability of a Lithium-Ion-Conducting Solid Electrolyte upon Reversible Li+H+ Exchange in Aqueous Solutions Citation Details In-Document Search Title: Excellent ...

  3. Extracting alcohols from aqueous solutions. [USDOE patent application

    DOE Patents [OSTI]

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

    1981-12-02

    The objective is to provide an efficient process for extracting alcohols in aqueous solutions into hydrocarbon fuel mixtures, such as gasoline, diesel fuel and fuel oil. This is done by contacting an aqueous fermentation liquor with a hydrocarbon or hydrocarbon mixture containing carbon compounds having 5-18 carbon atoms, which may include gasoline, diesel fuel or fuel oil. The hydrocarbon-aqueous alcohol solution is then mixed with one or more of a group of polyoxyalkylene polymers to extract the alcohol into the hydrocarbon fuel-polyoxyalkylene polymer mixture.

  4. Quantitative Chromatographic Determination of Dissolved Elemental Sulfur in the Non-aqueous Electrolyte for Lithium-Sulfur Batteries

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Zheng, Dong; Yang, Xiao-Qing; Zhang, Xuran; Li, Chao; McKinnon, Meaghan E.; Sadok, Rachel G.; Qu, Deyu; Yu, Xiqian; Lee, Hung-Sui; Qu, Deyang

    2014-12-02

    A fast and reliable analytical method is reported for the quantitative determination of dissolved elemental sulfur in non-aqueous electrolytes for Li-S batteries. By using high performance liquid chromatography with a UV detector, the solubility of S in 12 different pure solvents and in 22 different electrolytes was determined. It was found that the solubility of elemental sulfur is dependent on the Lewis basicity, the polarity of solvents and the salt concentration in the electrolytes. In addition, the S content in the electrolyte recovered from a discharged Li-S battery was successfully determined by the proposed HPLC/UV method. Thus, the feasibility ofmore » the method to the online analysis for a Li-S battery is demonstrated. Interestingly, the S was found super-saturated in the electrolyte recovered from a discharged Li-S cell.« less

  5. Quantitative Chromatographic Determination of Dissolved Elemental Sulfur in the Non-aqueous Electrolyte for Lithium-Sulfur Batteries

    SciTech Connect (OSTI)

    Zheng, Dong; Yang, Xiao-Qing; Zhang, Xuran; Li, Chao; McKinnon, Meaghan E.; Sadok, Rachel G.; Qu, Deyu; Yu, Xiqian; Lee, Hung-Sui; Qu, Deyang

    2014-12-02

    A fast and reliable analytical method is reported for the quantitative determination of dissolved elemental sulfur in non-aqueous electrolytes for Li-S batteries. By using high performance liquid chromatography with a UV detector, the solubility of S in 12 different pure solvents and in 22 different electrolytes was determined. It was found that the solubility of elemental sulfur is dependent on the Lewis basicity, the polarity of solvents and the salt concentration in the electrolytes. In addition, the S content in the electrolyte recovered from a discharged Li-S battery was successfully determined by the proposed HPLC/UV method. Thus, the feasibility of the method to the online analysis for a Li-S battery is demonstrated. Interestingly, the S was found super-saturated in the electrolyte recovered from a discharged Li-S cell.

  6. SOLVENT EXTRACTION OF THORIUM VALUES FROM AQUEOUS SOLUTIONS

    DOE Patents [OSTI]

    Warf, J.C.

    1959-04-21

    The separation of thorium values from rare earth metals contained ln aqueous solutions by means of extraction with a water immiscible alkyl phosphate diluted with a hydrocarbon such as hexane is described. While the extraction according to this invention may be carried out from any aqueous salt solution, it is preferred to use solutions containing free mineral acid. Hydrochloric acid and in particular nitric acid are sultable in a concentration ranging from 0.1 to 7 normal. The higher acid concentration results in higher extraction values.

  7. REMOVAL OF CESIUM BY SORPTION FROM AQUEOUS SOLUTIONS

    DOE Patents [OSTI]

    Ames, L.L.

    1962-01-16

    ABS>A process is given for selectively removing cesium from acid aqueous solutions containing cesium in microquantities and other cations in macroquantities by absorption on clinoptilolite. The cesium can be eluted from the clinoptilolite with a solution of ammonia, potassium hydroxide, or rubidium hydroxide. (AEC)

  8. SEPARATION OF TECHNETIUM FROM AQUEOUS SOLUTIONS BY COPRECIPITATION WITH MAGNETITE

    DOE Patents [OSTI]

    Rimshaw, S.J.

    1961-10-24

    A method of separating technetium in the 4+ oxidation state from an aqueous basic solution containing products of uranium fission is described. The method consists of contacting the solution with finely divided magnetite and recovering a technetium-bearing precipitate. (AEC)

  9. An Aqueous Redox Flow Battery Based on Neutral Alkali Metal Ferri/ferrocyanide and Polysulfide Electrolytes

    SciTech Connect (OSTI)

    Wei, Xiaoliang; Xia, Gordon; Kirby, Brent W.; Thomsen, Edwin C.; Li, Bin; Nie, Zimin; Graff, Gordon L.; Liu, Jun; Sprenkle, Vincent L.; Wang, Wei

    2015-11-13

    Aiming to explore low-cost redox flow battery systems, a novel iron-polysulfide (Fe/S) flow battery has been demonstrated in a laboratory cell. This system employs alkali metal ferri/ferrocyanide and alkali metal polysulfides as the redox electrolytes. When proper electrodes, such as pretreated graphite felts, are used, 78% energy efficiency and 99% columbic efficiency are achieved. The remarkable advantages of this system over current state-of-the-art redox flow batteries include: 1) less corrosive and relatively environmentally benign redox solutions used; 2) excellent energy and utilization efficiencies; 3) low cost for redox electrolytes and cell components. These attributes can lead to significantly reduced capital cost and make the Fe/S flow battery system a promising low-cost energy storage technology. The major drawbacks of the present cell design are relatively low power density and possible sulfur species crossover. Further work is underway to address these concerns.

  10. Separation and concentration of lower alcohols from dilute aqueous solutions

    DOE Patents [OSTI]

    Moore, Raymond H.; Eakin, David E.; Baker, Eddie G.; Hallen, Richard T.

    1991-01-01

    A process for producing, from a dilute aqueous solution of a lower (C.sub.1 -C.sub.5) alcohol, a concentrated liquid solution of the alcohol in an aromatic organic solvent is disclosed. Most of the water is removed from the dilute aqueous solution of alcohol by chilling sufficiently to form ice crystals. Simultaneously, the remaining liquid is extracted at substantially the same low temperature with a liquid organic solvent that is substantially immiscible in aqueous liquids and has an affinity for the alcohol at that temperature, causing the alcohol to transfer to the organic phase. After separating the organic liquid from the ice crystals, the organic liquid can be distilled to enrich the concentration of alcohol therein. Ethanol so separated from water and concentrated in an organic solvent such as toluene is useful as an anti-knock additive for gasoline.

  11. Method for removing organic liquids from aqueous solutions and mixtures

    DOE Patents [OSTI]

    Hrubesh, Lawrence W.; Coronado, Paul R.; Dow, Jerome P.

    2004-03-23

    A method for removing organic liquids from aqueous solutions and mixtures. The method employs any porous material preferably in granular form and having small pores and a large specific surface area, that is hydrophobic so that liquid water does not readily wet its surface. In this method, organics, especially organic solvents that mix with and are more volatile than water, are separated from aqueous solution by preferentially evaporating across the liquid/solid boundary formed at the surfaces of the hydrophobic porous materials. Also, organic solvents that are immiscible with water, preferentially wet the surfaces of the hydrophobic material and are drawn within the porous materials by capillary action.

  12. Dissolution of lead paint in aqueous solutions

    SciTech Connect (OSTI)

    Barnes, G.L.; Davis, A.P.

    1996-07-01

    An analysis of the rate and extent of lead leaching from a lead-based paint was completed. At low-solution pH, dissolution was rapid and approached 80% of the total lead. Residual lead can be estimated based on the predicted solubility of lead carbonate and basic lead carbonate. Release of lead from the paint was slower than that from pure basic lead carbonate due to inhibition by the paint matrix. Although the dissolved concentration of lead in solution at neutral/high pH was low, the paint binder was apparently destroyed at these pH values, releasing colloidal lead pigment particles. The presence of ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) enhanced both the rate and degree of lead dissolution, while benzoic acid had a minimal effect.

  13. RECOVERY OF URANIUM FROM AQUEOUS PHOSPHATE-CONTAINING SOLUTIONS

    DOE Patents [OSTI]

    Igelsrud, I.; Stephen, E.F.

    1959-08-11

    ABS>A method is presented for recovering hexavalent uranium from an acidic phosphaie solution. A high molecular weight amine, such as a mixture of cccoanut oil amines, is added to the solution in such amount as to give a ratio of about 2000 parts by weight of amine to 1 part by weight of uranium. The uranium is precipitated with the amines and the whole filtered from the solution. The uranium is leached from the amine mass by washing with aqueous sodium carbonate solution; and the amine mixture is available for reuse.

  14. REMOVAL OF CESIUM FROM AQUEOUS SOLUTIONS BY ADSORPTION

    DOE Patents [OSTI]

    Knoll, K.C.

    1963-07-16

    A process of removing microquantities of cesium from aqueous solutions also containing macroquantities of other ions by adsorption on clinoptilolite is described. The invention resides in the pretreatment of the clinoptilolite by heating at 400 deg C and cooling prior to use. (AEC)

  15. RECOVERY OF METAL VALUES FROM AQUEOUS SOLUTIONS BY SOLVENT EXTRACTION

    DOE Patents [OSTI]

    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.

  16. Understanding Aqueous Electrolyte Stability through Combined Computational and Magnetic Resonance Spectroscopy: A Case Study on Vanadium Redox Flow Battery Electrolytes

    SciTech Connect (OSTI)

    Vijayakumar, M.; Nie, Zimin; Walter, Eric D.; Hu, Jian Z.; Liu, Jun; Sprenkle, Vincent L.; Wang, Wei

    2015-02-01

    Redox flow battery (RFB) is a promising candidate for energy storage component in designing resilient grid scale power supply due to the advantage of the separation of power and energy. However, poorly understood chemical and thermal stability issues of electrolytes currently limit the performance of RFB. Designing of high performance stable electrolytes requires comprehensive knowledge about the molecular level solvation structure and dynamics of their redox active species. The molecular level understanding of detrimental V2O5 precipitation process led to successful designing of mixed acid based electrolytes for vanadium redox flow batteries (VRFB). The higher stability of mixed acid based electrolytes is attributed to the choice of hydrochloric acid as optimal co-solvent, which provides chloride anions for ligand exchange process in vanadium solvation structure. The role of chloride counter anion on solvation structure and dynamics of vanadium species were studied using combined magnetic resonance spectroscopy and DFT based theoretical methods. Finally, the solvation phenomenon of multiple vanadium species and their impact on VRFB electrolyte chemical stability were discussed.

  17. Ewald Summation Approach to Potential Models of Aqueous Electrolytes Involving Gaussian Charges and Induced Dipoles: Formal and Simulation Results

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Chialvo, Ariel A.; Vlcek, Lukas

    2014-11-01

    We present a detailed derivation of the complete set of expressions required for the implementation of an Ewald summation approach to handle the long-range electrostatic interactions of polar and ionic model systems involving Gaussian charges and induced dipole moments with a particular application to the isobaricisothermal molecular dynamics simulation of our Gaussian Charge Polarizable (GCP) water model and its extension to aqueous electrolytes solutions. The set comprises the individual components of the potential energy, electrostatic potential, electrostatic field and gradient, the electrostatic force and the corresponding virial. Moreover, we show how the derived expressions converge to known point-based electrostatic counterpartsmore » when the parameters, defining the Gaussian charge and induced-dipole distributions, are extrapolated to their limiting point values. Finally, we illustrate the Ewald implementation against the current reaction field approach by isothermal-isobaric molecular dynamics of ambient GCP water for which we compared the outcomes of the thermodynamic, microstructural, and polarization behavior.« less

  18. Process of concentrating ethanol from dilute aqueous solutions thereof

    DOE Patents [OSTI]

    Oulman, Charles S. [Ames, IA; Chriswell, Colin D. [Slater, IA

    1981-07-07

    Relatively dilute aqueous solutions of ethanol are concentrated by passage through a bed of a crystalline silica polymorph, such as silicalite, to adsorb the ethanol with residual dilute feed in contact with the bed, which is displaced by passing concentrated aqueous ethanol through the bed without displacing the adsorbed ethanol. A product concentrate is then obtained by removing the adsorbed ethanol from the bed together with at least a portion of the concentrated aqueous ethanol used as the displacer liquid. This process permits ethanol to be concentrated from dilute fermentation beers, which may contain from 6 to 10% ethanol, to obtain a concentrate product at very low energy cost having an ethanol concentration in excess of 95%, such as a concentration of from 98 to 99.5%.

  19. Process of concentrating ethanol from dilute aqueous solutions thereof

    DOE Patents [OSTI]

    Oulman, C.S.; Chriswell, C.D.

    1981-07-07

    Relatively dilute aqueous solutions of ethanol are concentrated by passage through a bed of a crystalline silica polymorph, such as silicalite, to adsorb the ethanol with residual dilute feed in contact with the bed, which is displaced by passing concentrated aqueous ethanol through the bed without displacing the adsorbed ethanol. A product concentrate is then obtained by removing the adsorbed ethanol from the bed together with at least a portion of the concentrated aqueous ethanol used as the displacer liquid. This process permits ethanol to be concentrated from dilute fermentation beers, which may contain from 6 to 10% ethanol, to obtain a concentrate product at very low energy cost having an ethanol concentration in excess of 95%, such as a concentration of from 98 to 99.5%. 5 figs.

  20. Adsorption analysis of ammonia in an aqueous solution

    SciTech Connect (OSTI)

    Arman, B.; Panchal, C.B.

    1993-08-01

    An analysis is carried out to determine the effects of the diffusional resistance on the rate of the adsorption of ammonia in an aqueous solution. A performance prediction model is developed to calculate the local rate of heat and mass transfer, including physical and thermodynamic property calculations of the mixture. An algorithm is developed for calculating the interfacial conditions. The local heat- and mass-transfer calculation is then incorporated into the performance prediction method for adsorption for a given geometry.

  1. Preparation of thin ceramic films via an aqueous solution route

    DOE Patents [OSTI]

    Pederson, Larry R.; Chick, Lawrence A.; Exarhos, Gregory J.

    1989-01-01

    A new chemical method of forming thin ceramic films has been developed. An aqueous solution of metal nitrates or other soluble metal salts and a low molecular weight amino acid is coated onto a substrate and pyrolyzed. The amino acid serves to prevent precipitation of individual solution components, forming a very viscous, glass-like material as excess water is evaporated. Using metal nitrates and glycine, the method has been demonstrated for zirconia with various levels of yttria stabilization, for lanthanum-strontium chromites, and for yttrium-barium-copper oxide superconductors on various substrates.

  2. Non-aqueous solution preparation of doped and undoped Li{sub x}Mn{sub y}O{sub z}

    DOE Patents [OSTI]

    Boyle, T.J.; Voigt, J.A.

    1997-05-20

    A method is described for generation of phase-pure doped and undoped Li{sub x}Mn{sub y}O{sub z} precursors. The method of this invention uses organic solutions instead of aqueous solutions or nonsolution ball milling of dry powders to produce phase-pure precursors. These precursors can be used as cathodes for lithium-polymer electrolyte batteries. Dopants may be homogeneously incorporated to alter the characteristics of the powder. 1 fig.

  3. Electrolyte pore/solution partitioning by expanded grand canonical...

    Office of Scientific and Technical Information (OSTI)

    Because of simultaneous rise in the solution surface tension, which increases the ... Resource Type: Journal Article Resource Relation: Journal Name: Journal of Chemical Physics; ...

  4. X-ray studies of concentrated aqueous solutions

    SciTech Connect (OSTI)

    Ludwig, K.F. Jr.; Warburton, W.K.; Fontaine, A.

    1987-07-01

    Concentrated aqueous solutions of three transition metal bromides (ZnBr/sub 2/, CuBr/sub 2/, and NiBr/sub 2/) and an alkali bromide (RbBr) have been studied with differential anomalous scattering (DAS) and extended x-ray absorption fine structure (EXAFS). The aq-ZnBr/sub 2/ solutions exhibit considerable inner-shell ion complexing with the formation of tetrahedral complexes about the Zn/sup 2 +/. In aq-CuBr/sub 2/, the Cu/sup 2 +/ has an octahedral coordination shell. Most of the anions are bound directly to the cations in both solutions. In contrast, there are only a few Ni--Br nearest neighbors in aq-NiBr/sub 2/. Instead, cations and anions share hydrating water molecules. Preliminary data show that any ion complexing in aq-RbBr must be weak. These results are in good agreement with published thermodynamic studies.

  5. Process for disposal of aqueous solutions containing radioactive isotopes

    DOE Patents [OSTI]

    Colombo, Peter; Neilson, Jr., Robert M.; Becker, Walter W.

    1979-01-01

    A process for disposing of radioactive aqueous waste solutions whereby the waste solution is utilized as the water of hydration to hydrate densified powdered portland cement in a leakproof container; said waste solution being dispersed without mechanical inter-mixing in situ in said bulk cement, thereafter the hydrated cement body is impregnated with a mixture of a monomer and polymerization catalyst to form polymer throughout the cement body. The entire process being carried out while maintaining the temperature of the components during the process at a temperature below 99.degree. C. The container containing the solid polymer-impregnated body is thereafter stored at a radioactive waste storage dump such as an underground storage dump.

  6. Standard Electrode Potentials Involving Radicals in Aqueous Solution: Inorganic Radicals

    SciTech Connect (OSTI)

    Armstrong, David A.; Huie, Robert E.; Koppenol, Willem H.; Lymar, Sergei V.; Merenyi, Gabor; Neta, Pedatsur; Ruscic, Branko; Stanbury, David M.; Steenken, Steen; Wardman, Peter

    2015-12-01

    Recommendations are made for standard potentials involving select inorganic radicals in aqueous solution at 25 °C. These recommendations are based on a critical and thorough literature review and also by performing derivations from various literature reports. The recommended data are summarized in tables of standard potentials, Gibbs energies of formation, radical pKa’s, and hemicolligation equilibrium constants. In all cases, current best estimates of the uncertainties are provided. An extensive set of Data Sheets is appended that provide original literature references, summarize the experimental results, and describe the decisions and procedures leading to each of the recommendations

  7. Preparation of metallic nanoparticles by irradiation in starch aqueous solution

    SciTech Connect (OSTI)

    Nemţanu, Monica R. Braşoveanu, Mirela Iacob, Nicuşor

    2014-11-24

    Colloidal silver nanoparticles (AgNPs) were synthesized in a single step by electron beam irradiation reduction of silver ions in aqueous solution containing starch. The nanoparticles were characterized by spectrophotocolorimetry and compared with those obtained by chemical (thermal) reduction method. The results showed that the smaller sizes of AgNPs were prepared with higher yields as the irradiation dose increased. The broadening of particle size distribution occurred by increasing of irradiation dose and dose rate. Chromatic parameters such as b* (yellow-blue coordinate), C* (chroma) and ΔE{sub ab} (total color difference) could characterize the nanoparticles with respect of their concentration. Hue angle h{sup o} was correlated to the particle size distribution. Experimental data of the irradiated samples were also subjected to factor analysis using principal component extraction and varimax rotation in order to reveal the relation between dependent variables and independent variables and to reduce their number. The radiation-based method provided silver nanoparticles with higher concentration and narrower size distribution than those produced by chemical reduction method. Therefore, the electron beam irradiation is effective for preparation of silver nanoparticles using starch aqueous solution as dispersion medium.

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

    SciTech Connect (OSTI)

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

    2013-08-20

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

  9. Origin of electrochemical, structural and transport properties in non-aqueous zinc electrolytes

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Han, Sang -Don; Rajput, Nav Nidhi; Qu, Xiaohui; Pan, Baofei; He, Meinan; Ferrandon, Magali S.; Liao, Chen; Persson, Kristin A.; Burrell, Anthony K.

    2016-01-14

    Through coupled experimental analysis and computational techniques, we uncover the origin of anodic stability for a range of nonaqueous zinc electrolytes. By examination of electrochemical, structural, and transport properties of nonaqueous zinc electrolytes with varying concentrations, it is demonstrated that the acetonitrile Zn(TFSI)2, acetonitrile Zn(CF3SO3)2, and propylene carbonate Zn(TFSI)2 electrolytes can not only support highly reversible Zn deposition behavior on a Zn metal anode (≥99% of Coulombic efficiency), but also provide high anodic stability (up to ~3.8 V). The predicted anodic stability from DFT calculations is well in accordance with experimental results, and elucidates that the solvents play an importantmore » role in anodic stability of most electrolytes. Molecular dynamics (MD) simulations were used to understand the solvation structure (e.g., ion solvation and ionic association) and its effect on dynamics and transport properties (e.g., diffusion coefficient and ionic conductivity) of the electrolytes. Lastly, the combination of these techniques provides unprecedented insight into the origin of the electrochemical, structural, and transport properties in nonaqueous zinc electrolytes« less

  10. Electrolytes - Advanced Electrolyte and Electrolyte Additives...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    More Documents & Publications Electrolytes - Advanced Electrolyte and Electrolyte Additives Electrolytes - Advanced Electrolyte and Electrolyte Additives Develop & Evaluate ...

  11. Study of the nanobubble phase of aqueous NaCl solutions by dynamic light scattering

    SciTech Connect (OSTI)

    Bunkin, N F; Shkirin, A V [A M Prokhorov General Physics Institute, Russian Academy of Sciences, Moscow (Russian Federation); Burkhanov, I S; Chaikov, L L [P N Lebedev Physics Institute, Russian Academy of Sciences, Moscow (Russian Federation); Lomkova, A K [N.E. Bauman Moscow State Technical University, Moscow (Russian Federation)

    2014-11-30

    Aqueous NaCl solutions with different concentrations have been investigated by dynamic scattering of laser radiation. It is experimentally shown that these solutions contain scattering particles with a wide size distribution in a range of ?10 100 nm. The experimental results indirectly confirm the existence of quasi-stable gas nanobubbles in the bulk of aqueous ionic solutions. (light scattering)

  12. Study on the photophysical characteristics of R6G-. beta. cyclodextrin aqueous solution

    SciTech Connect (OSTI)

    Xingkang Zhang; Jianxin Chen; Guangzhi Xu

    1987-02-01

    Photophysical characteristics of R6G-..beta.. cyclodextrin system in aqueous solution have been studied by examining the steady and time-resolved fluorescence. Results are discussed.

  13. Enantiopure, Octadentate Ligands as Sensitizers for Europium andTerbium Circularly Polarized Luminescence in Aqueous Solution

    SciTech Connect (OSTI)

    Seitz, Michael; Moore, Evan G.; Ingram, Andrew J.; Muller,Gilles; Raymond, Kenneth N.

    2007-08-09

    Tb and Eu complexes of enantiopure ligands with a new modular design show strong overall luminescence and CPL activity in aqueous solution.

  14. A Pentafluorophenylboron Oxalate Additive in Non-aqueous Electrolytes 3 for Lithium Batteries

    SciTech Connect (OSTI)

    Yang, X.Q.; Li, L.F.; Lee, H.S.; Li, H.; Huang, X.J.

    2009-12-01

    A novel compound named pentafluorophenylboron oxalate (PFPBO) has been synthesized. PFPBO has a unique molecular structure containing a boron atom center with electron deficiency and an oxalate group. It is found that when PFPBO is used as additive, the solubility of lithium fluoride (LiF) or lithium oxide (Li{sub 2}O, Li{sub 2}O{sub 2}) in propylene carbonate (PC) and dimethyl carbonate (DMC) solvents can be increased dramatically. The new electrolytes show high ionic conductivity, high lithium ion transference number and good compatibility with LiMn{sub 2}O{sub 4} cathode and MCMB anode. PFPBO was synthesized with the designed structure to act as a bi-functional additive: boron-based anion receptor (BBAR) additive and stable solid electrolyte interphase (SEI) formation additive in PC-based electrolytes. The results show it does possess these two desired functionalities.

  15. Ionic liquids, electrolyte solutions including the ionic liquids, and energy storage devices including the ionic liquids

    SciTech Connect (OSTI)

    Gering, Kevin L.; Harrup, Mason K.; Rollins, Harry W.

    2015-12-08

    An ionic liquid including a phosphazene compound that has a plurality of phosphorus-nitrogen units and at least one pendant group bonded to each phosphorus atom of the plurality of phosphorus-nitrogen units. One pendant group of the at least one pendant group comprises a positively charged pendant group. Additional embodiments of ionic liquids are disclosed, as are electrolyte solutions and energy storage devices including the embodiments of the ionic liquid.

  16. Excellent Stability of a Lithium-Ion-Conducting Solid Electrolyte...

    Office of Scientific and Technical Information (OSTI)

    Excellent Stability of a Lithium-Ion-Conducting Solid Electrolyte upon Reversible Li+H+ Exchange in Aqueous Solutions Title: Excellent Stability of a Lithium-Ion-Conducting Solid ...

  17. Characterization of Chitin and Chitosan Molecular Structure in Aqueous Solution

    SciTech Connect (OSTI)

    Franca, Eduardo D.; Lins, Roberto D.; Freitas, Luiz C.; Straatsma, t. P.

    2008-11-08

    Molecular dynamics simulations have been used to characterize the structure of chitin and chitosan fibers in aqueous solutions. Chitin fibers, whether isolated or in the form of a β-chitin nanoparticle, adopt the so-called 2-fold helix with Φ and φ values similar to its crystalline state. In solution, the intramolecular hydrogen bond HO3(n)•••O5(n+1) responsible for the 2-fold helical motif is stabilized by hydrogen bonds with water molecules in a well-defined orientation. On the other hand, chitosan can adopt five distinct helical motifs and its conformational equilibrium is highly dependent on pH. The hydrogen bond pattern and solvation around the O3 atom of insoluble chitosan (basic pH) are nearly identical to these quantities in chitin. Our findings suggest that the solubility and conformation of these polysaccharides are related to the stability of the intrachain HO3(n)•••O5(n+1) hydrogen bond, which is affect by the water exchange around the O3-HO3 hydroxyl group.

  18. Investigation of the Rechargeability of Li-O2 Batteries in Non-aqueous Electrolyte

    SciTech Connect (OSTI)

    Xiao, Jie; Hu, Jian Z.; Wang, Deyu; Hu, Dehong; Xu, Wu; Graff, Gordon L.; Nie, Zimin; Liu, Jun; Zhang, Jiguang

    2011-07-01

    In order to understand the nature of the limited cycle life and poor energy efficiency associated with the secondary Li-O2 batteries the discharge products of primary Li-O2 cells at different depth of discharge (DOD) are systematically analyzed in this work. It is revealed that if discharged to 2.0 V a small amount of Li2O2 coexist with Li2CO3 and RO-(C=O)-OLi) in alkyl carbonate-based electrolyte. Further discharging the air electrodes to below 2.0 V the amount of Li2CO3 and LiRCO3 increases significantly due to the severe electrolyte decomposition. There is no Li2O detected in this alkyl carbonate electrolyte regardless of DOD. It is also found that the alkyl carbonate based electrolyte begins to decompose at 4.0 V during charging under the combined influences from the high surface area carbon, the nickel metal current collector and the oxygen atmosphere. Accordingly the impedance of the Li-O2 cell continues to increase after each discharge and recharge process indicating a repeated plating of insoluble lithium salts on the carbon surface. Therefore the whole carbon electrode becomes completely insulated only after a few cycles and loses the function of providing active tri-phase regions for the Li-oxygen batteries.

  19. Process for separating and recovering an anionic dye from an aqueous solution

    DOE Patents [OSTI]

    Rogers, R.; Horwitz, E.P.; Bond, A.H.

    1998-01-13

    A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution. 7 figs.

  20. Process for separating and recovering an anionic dye from an aqueous solution

    DOE Patents [OSTI]

    Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

    1998-01-01

    A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution.

  1. Synthesis and studies of boron based anion receptors and their use in non-aqueous electrolytes for lithium batteries

    SciTech Connect (OSTI)

    Sun, X.; Yang, X.Q.; Lee, H.S.; McBreen, J.; Choi, L.S.

    1998-12-31

    A new family of anion receptors based on boron compounds has been synthesized. These compounds can be used as anion receptors in lithium battery electrolytes and can greatly increase solubility and ionic conductivities of various lithium salts, such as LiF, LiCl, CF{sub 3}COOLi and C{sub 2}F{sub 5}COOLi, in DME solutions. Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy studies show that Cl{sup {minus}} anions of LiCl are complexed with these compounds in DME solutions. The electrochemical stability of lithium salts and one of the boron compounds in deferent solvents was studied. For the first time, LiF has been successfully used as conducting salt in a novel electrolyte with this boron compound as an additive in DME. A rechargeable Li/LiMn{sub 2}O{sub 4} cell using this electrolyte was successfully cycled 51 times. However, the capacity fades with cycling due to decomposition of the solvent. The cycling performance of the battery was greatly improved by replacing DME with PC-EC-DMC as the solvent.

  2. Direct Photolysis of Chlorophenols In Aqueous Solution By Ultraviolet Excilamps

    SciTech Connect (OSTI)

    Matafonova, Galina; Philippova, Natalya; Batoev, Valeriy

    2011-08-25

    The direct photolysis of 2-chlorophenol (2-CP), 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP) in model aqueous solution was studied using UV XeBr (282 nm) and KrCl (222 nm) excilamps. The highest pseudo-first order rate constants and quantum yields were found for molecular form of 4-CP (at pH 2 and 5.7) and anionic forms of 2-CP and 2,4-DCP (at pH 11) when irradiated by XeBr excilamp. The maximum removal efficiency of molecular form of 2-CP and 2,4-DCP with the lowest UV dose of absorbed energy was observed using KrCl excilamp. On the contrary, the XeBr excilamp required the lowest dose ({approx}2 J{center_dot}cm{sup -2}) for complete degradation of molecular 4-CP and anionic 2-CP. The highest removal efficiency of anionic form of 4-CP (65%) was achieved when using KrCl excilamp.

  3. Structure and dynamics of aqueous solution of uranyl ions

    SciTech Connect (OSTI)

    Chopra, Manish; Choudhury, Niharendu

    2014-04-24

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

  4. Electrolytes - Advanced Electrolyte and Electrolyte Additives...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    More Documents & Publications Development of Advanced Electrolytes and Electrolyte Additives Electrolytes - Advanced Electrolyte and Electrolyte Additives Develop & evaluate ...

  5. Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Non-Aqueous Electrolytes

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Canepa, Pieremanuele; Gautam, Gopalakrishnan Sai; Malik, Rahul; Jayaraman, Saivenkataraman; Rong, Ziqin; Zavadil, Kevin R.; Persson, Kristin; Ceder, Gerbrand

    2015-04-08

    Multivalent (MV) battery architectures based on pairing a Mg metal anode with a high-voltage (~3 V) intercalation cathode offer a realistic design pathway toward significantly surpassing the energy storage performance of traditional Li-ion-based batteries, but there are currently only few electrolyte systems that support reversible Mg deposition. Using both static first-principles calculations and ab initio molecular dynamics, we perform a comprehensive adsorption study of several salt and solvent species at the interface of Mg metal with an electrolyte of Mg2+ and Cl–dissolved in liquid tetrahydrofuran (THF). Our findings not only provide a picture of the stable species at the interfacemore » but also explain how this system can support reversible Mg deposition, and as such, we provide insights in how to design other electrolytes for Mg plating and stripping. Furthermore, the active depositing species are identified to be (MgCl)+ monomers coordinated by THF, which exhibit preferential adsorption on Mg compared to possible passivating species (such as THF solvent or neutral MgCl2 complexes). We found that upon deposition, the energy to desolvate these adsorbed complexes and facilitate charge transfer is shown to be small (~61–46.2 kJ mol–1 to remove three THF from the strongest adsorbing complex), and the stable orientations of the adsorbed but desolvated (MgCl)+ complexes appear to be favorable for charge transfer. Finally, observations of Mg–Cl dissociation at the Mg surface at very low THF coordinations (0 and 1) suggest that deleterious Cl incorporation in the anode may occur upon plating. In the stripping process, this is beneficial by further facilitating the Mg removal reaction.« less

  6. Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Non-Aqueous Electrolytes

    SciTech Connect (OSTI)

    Canepa, Pieremanuele; Gautam, Gopalakrishnan Sai; Malik, Rahul; Jayaraman, Saivenkataraman; Rong, Ziqin; Zavadil, Kevin R.; Persson, Kristin; Ceder, Gerbrand

    2015-04-08

    Multivalent (MV) battery architectures based on pairing a Mg metal anode with a high-voltage (~3 V) intercalation cathode offer a realistic design pathway toward significantly surpassing the energy storage performance of traditional Li-ion-based batteries, but there are currently only few electrolyte systems that support reversible Mg deposition. Using both static first-principles calculations and ab initio molecular dynamics, we perform a comprehensive adsorption study of several salt and solvent species at the interface of Mg metal with an electrolyte of Mg2+ and Cldissolved in liquid tetrahydrofuran (THF). Our findings not only provide a picture of the stable species at the interface but also explain how this system can support reversible Mg deposition, and as such, we provide insights in how to design other electrolytes for Mg plating and stripping. Furthermore, the active depositing species are identified to be (MgCl)+ monomers coordinated by THF, which exhibit preferential adsorption on Mg compared to possible passivating species (such as THF solvent or neutral MgCl2 complexes). We found that upon deposition, the energy to desolvate these adsorbed complexes and facilitate charge transfer is shown to be small (~6146.2 kJ mol1 to remove three THF from the strongest adsorbing complex), and the stable orientations of the adsorbed but desolvated (MgCl)+ complexes appear to be favorable for charge transfer. Finally, observations of MgCl dissociation at the Mg surface at very low THF coordinations (0 and 1) suggest that deleterious Cl incorporation in the anode may occur upon plating. In the stripping process, this is beneficial by further facilitating the Mg removal reaction.

  7. Aqueous Binary Lanthanide(III) Nitrate Ln(NO3)3 Electrolytes Revisited: Extended Pitzer and Bromley Treatments

    SciTech Connect (OSTI)

    Chatterjee, Sayandev; Campbell, Emily L.; Neiner, Doinita; Pence, Natasha; Robinson, Troy; Levitskaia, Tatiana G.

    2015-09-11

    To date, only limited thermodynamic models describing activity coefficients of the aqueous solutions of lanthanide ions are available. This work expands the existing experimental osmotic coefficient data obtained by classical isopiestic technique for the aqueous binary trivalent lanthanide nitrate Ln(NO3)3 solutions using a combination of water activity and vapor pressure osmometry measurements. The combined osmotic coefficient database for each aqueous lanthanide nitrate at 25°C, consisting of literature available data as well as data obtained in this work, was used to test the validity of Pitzer and Bromley thermodynamic models for the accurate prediction of mean molal activity coefficients of the Ln(NO3)3 solutions in wide concentration ranges. The new and improved Pitzer and Bromley parameters were calculated. It was established that the Ln(NO3)3 activity coefficients in the solutions with ionic strength up to 12 mol kg-1 can be estimated by both Pitzer and single-parameter Bromley models, even though the latter provides for more accurate prediction, particularly in the lower ionic strength regime (up to 6 mol kg-1). On the other hand for the concentrated solutions, the extended three-parameter Bromley model can be employed to predict the Ln(NO3)3 activity coefficients with remarkable accuracy. The accuracy of the extended Bromley model in predicting the activity coefficients was greater than ~95% and ~90% for all solutions with the ionic strength up to 12 mol kg-1 and and 20 mol kg-1, respectively. This is the first time that the activity coefficients for concentrated lanthanide solutions have been predicted with such a remarkable accuracy.

  8. Ion aggregation in high salt solutions. III. Computational vibrational spectroscopy of HDO in aqueous salt solutions

    SciTech Connect (OSTI)

    Choi, Jun-Ho; Lim, Sohee; Chon, Bonghwan; Cho, Minhaeng; Kim, Heejae; Kim, Seongheun

    2015-05-28

    The vibrational frequency, frequency fluctuation dynamics, and transition dipole moment of the OD stretch mode of HDO molecule in aqueous solutions are strongly dependent on its local electrostatic environment and hydrogen-bond network structure. Therefore, the time-resolved vibrational spectroscopy the OD stretch mode has been particularly used to investigate specific ion effects on water structure. Despite prolonged efforts to understand the interplay of OD vibrational dynamics with local water hydrogen-bond network and ion aggregate structures in high salt solutions, still there exists a gap between theory and experiment due to a lack of quantitative model for accurately describing OD stretch frequency in high salt solutions. To fill this gap, we have performed numerical simulations of Raman scattering and IR absorption spectra of the OD stretch mode of HDO in highly concentrated NaCl and KSCN solutions and compared them with experimental results. Carrying out extensive quantum chemistry calculations on not only water clusters but also ion-water clusters, we first developed a distributed vibrational solvatochromic charge model for the OD stretch mode in aqueous salt solutions. Furthermore, the non-Condon effect on the vibrational transition dipole moment of the OD stretch mode was fully taken into consideration with the charge response kernel that is non-local polarizability density. From the fluctuating OD stretch mode frequencies and transition dipole vectors obtained from the molecular dynamics simulations, the OD stretch Raman scattering and IR absorption spectra of HDO in salt solutions could be calculated. The polarization effect on the transition dipole vector of the OD stretch mode is shown to be important and the asymmetric line shapes of the OD stretch Raman scattering and IR absorption spectra of HDO especially in highly concentrated NaCl and KSCN solutions are in quantitative agreement with experimental results. We anticipate that this

  9. Fe sub 3 Al-type iron aluminides: Aqueous corrosion properties in a range of electrolytes and slow-strain-rate ductilities during aqueous corrosion

    SciTech Connect (OSTI)

    Buchanan, R.A.; Kim, J.G. . Dept. of Materials Science and Engineering)

    1992-08-01

    The Fe{sub 3}Al-type iron aluminides have undergone continued development at the Oak Ridge National Laboratory for enhancement of mechanical and corrosion properties. Improved alloys and thermomechanical processing methods have evolved. The overall purpose of the project herein described was to evaluate the aqueous corrosion properties of the most recent alloy compositions in a wide range of possibly-aggressive solutions and under several different types of corrosion-test conditions. The work supplements previous aqueous-corrosion studies on iron aluminides by the present authors. Four stages of this one-year aqueous-corrosion investigation are described. First the corrosion properties of selected iron aluminides were evaluated by means of electrochemical tests and longer-time immersion tests in a range of acidic, basic and chloride solutions. Theses tests were performed under non-crevice conditions, i.e. the specimens were not designed to contain crevice geometries. Second, the iron-aluminide alloy that proved most resistance to chloride-induced localized corrosion under non-crevice conditions was further evaluated under more-severe crevice conditions by electrochemical and immersion testing. Third, in order to study the relative roles of Fe, Al, Cr and Mo in the formation of passive films, the chemical compositions of passive films were determined by X-ray photoelectron spectroscopy (XPS). And fourth, in order to study aqueous-corrosion effects on the ductilities of iron aluminides as related to hydrogen embrittlement and/or stress-corrosion cracking, slow-strain-rate corrosion (SSRC) tests were conducted over a range of electrochemical potentials.

  10. Fe{sub 3}Al-type iron aluminides: Aqueous corrosion properties in a range of electrolytes and slow-strain-rate ductilities during aqueous corrosion

    SciTech Connect (OSTI)

    Buchanan, R.A.; Kim, J.G.

    1992-08-01

    The Fe{sub 3}Al-type iron aluminides have undergone continued development at the Oak Ridge National Laboratory for enhancement of mechanical and corrosion properties. Improved alloys and thermomechanical processing methods have evolved. The overall purpose of the project herein described was to evaluate the aqueous corrosion properties of the most recent alloy compositions in a wide range of possibly-aggressive solutions and under several different types of corrosion-test conditions. The work supplements previous aqueous-corrosion studies on iron aluminides by the present authors. Four stages of this one-year aqueous-corrosion investigation are described. First the corrosion properties of selected iron aluminides were evaluated by means of electrochemical tests and longer-time immersion tests in a range of acidic, basic and chloride solutions. Theses tests were performed under non-crevice conditions, i.e. the specimens were not designed to contain crevice geometries. Second, the iron-aluminide alloy that proved most resistance to chloride-induced localized corrosion under non-crevice conditions was further evaluated under more-severe crevice conditions by electrochemical and immersion testing. Third, in order to study the relative roles of Fe, Al, Cr and Mo in the formation of passive films, the chemical compositions of passive films were determined by X-ray photoelectron spectroscopy (XPS). And fourth, in order to study aqueous-corrosion effects on the ductilities of iron aluminides as related to hydrogen embrittlement and/or stress-corrosion cracking, slow-strain-rate corrosion (SSRC) tests were conducted over a range of electrochemical potentials.

  11. Process for recovering chaotropic anions from an aqueous solution also containing other ions

    DOE Patents [OSTI]

    Rogers, R.; Horwitz, E.P.; Bond, A.H.

    1999-03-30

    A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 19 figs.

  12. Process for recovering chaotropic anions from an aqueous solution also containing other ions

    DOE Patents [OSTI]

    Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

    1999-01-01

    A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

  13. ELECTROLYTIC PRODUCTION OF URANIUM TETRAFLUORIDE

    DOE Patents [OSTI]

    Lofthouse, E.

    1954-08-31

    This patent relates to electrolytic methods for the production of uranium tetrafluoride. According to the present invention a process for the production of uranium tetrafluoride comprises submitting to electrolysis an aqueous solution of uranyl fluoride containing free hydrofluoric acid. Advantageously the aqueous solution of uranyl fluoride is obtained by dissolving uranium hexafluoride in water. On electrolysis, the uranyl ions are reduced to uranous tons at the cathode and immediately combine with the fluoride ions in solution to form the insoluble uranium tetrafluoride which is precipitated.

  14. EXTRACTION OF TETRAVALENT PLUTONIUM VALUES FROM AQUEOUS ACID SOLUTIONS BY 2($beta$-ETHYLBUTOXY) ETHANOL

    DOE Patents [OSTI]

    Seaborg, G.T.

    1961-08-15

    A process of extracting tetnavalent plutonium from aqueous inonganic acid solutions (acidity between 1 N and pH of 2.5) with 2( beta -ethylbutoxy) ethanol is described. (AEC)

  15. Method and apparatus for measuring volatile compounds in an aqueous solution

    DOE Patents [OSTI]

    Gilmore, Tyler J [Pasco, WA; Cantrell, Kirk J [West Richland, WA

    2002-07-16

    The present invention is an improvement to the method and apparatus for measuring volatile compounds in an aqueous solution. The apparatus is a chamber with sides and two ends, where the first end is closed. The chamber contains a solution volume of the aqueous solution and a gas that is trapped within the first end of the chamber above the solution volume. The gas defines a head space within the chamber above the solution volume. The chamber may also be a cup with the second end. open and facing down and submerged in the aqueous solution so that the gas defines the head space within the cup above the solution volume. The cup can also be entirely submerged in the aqueous solution. The second end of the. chamber may be closed such that the chamber can be used while resting on a flat surface such as a bench. The improvement is a sparger for mixing the gas with the solution volume. The sparger can be a rotating element such as a propeller on a shaft or a cavitating impeller. The sparger can also be a pump and nozzle where the pump is a liquid pump and the nozzle is a liquid spray nozzle open, to the head space for spraying the solution volume into the head space of gas. The pump could also be a gas pump and the nozzle a gas nozzle submerged in the solution volume for spraying the head space gas into the solution volume.

  16. Ceramic electrolyte coating methods

    DOE Patents [OSTI]

    Seabaugh, Matthew M.; Swartz, Scott L.; Dawson, William J.; McCormick, Buddy E.

    2004-10-12

    Processes for preparing aqueous suspensions of a nanoscale ceramic electrolyte material such as yttrium-stabilized zirconia. The invention also includes a process for preparing an aqueous coating slurry of a nanoscale ceramic electrolyte material. The invention further includes a process for depositing an aqueous spray coating slurry including a ceramic electrolyte material on pre-sintered, partially sintered, and unsintered ceramic substrates and products made by this process.

  17. Dynamics of Magnesite Formation at Low-Temperature and High pCO2 in Aqueous Solution

    SciTech Connect (OSTI)

    Qafoku, Odeta; Dixon, David A.; Rosso, Kevin M.; Schaef, Herbert T.; Bowden, Mark E.; Arey, Bruce W.; Felmy, Andrew R.

    2015-09-17

    Like many metal carbonate minerals, despite conditions of supersaturation, precipitation of magnesite from aqueous solution is kinetically hindered at low temperatures, for reasons that remain poorly understood. The present study examines precipitation products from reaction of Mg(OH)2 in aqueous solutions saturated with supercritical CO2 at high pressures (90 atm and 110 atm) and low temperatures (35 C and 50 C). Traditional bulk characterization (X-ray diffraction) of the initial solid formed indicated the presence of hydrated magnesium carbonates (hydromagnesite and nesquehonite), thermodynamically metastable phases that were found to slowly react during ageing to the more stable anhydrous form, magnesite, at temperatures as low as 35 C (135-140 days) and at a faster rate at 50 C (56 days). Undetected by bulk measurements, detailed examination of the precipitates by scanning electron microscopy (SEM) showed that magnesite is present as a minor component at relatively early reaction times (7 days) at 50 C. In addition to magnesite dominating the solid phases over time, we find that mangesite nucleation and growth occurs more quickly with increasing partial pressure of CO2, and in electrolyte solutions with high bicarbonate content. Furthermore, formation of magnesite was found to be enhanced in sulfate-rich solutions, compared to chloride-rich solutions. We speculate that much of this behavior is possibly due to sulfate serving as sink of protons generated during carbonation reactions. These results support the importance of integrating magnesite as an equilibrium phase in reactive transport calculations of the effects of carbon dioxide sequestration on subsurface formations at long time scales.

  18. Electrolytic dissolver

    DOE Patents [OSTI]

    Wheelwright, E.J.; Fox, R.D.

    1975-08-26

    This patent related to an electrolytic dissolver wherein dissolution occurs by solution contact including a vessel of electrically insulative material, a fixed first electrode, a movable second electrode, means for insulating the electrodes from the material to be dissolved while permitting a free flow of electrolyte therebetween, means for passing a direct current between the electrodes and means for circulating electrolyte through the dissolver. (auth)

  19. RECOVERY OF URANIUM AND THORIUM FROM AQUEOUS SOLUTIONS

    DOE Patents [OSTI]

    Calkins, G.D.

    1958-06-10

    >A process is described for the recovery of uranium and thorium from monazite sand, which is frequently processed by treating it with a hot sodium hydroxide solution whereby a precipitate forms consisting mainly of oxides or hydroxides of the rare earths, thorium and uranium. The precipitate is dissolved in mineral acid, and the acid solution is then neutralized to a pH value of between 5.2 and 6.2 whereby both the uranium and thorium precipitate as the hydroxides, while substantially all the rare earth metal values present remain in the solution. The uranium and thoriunn can then be separated by dissolving the precipitate in a solution containing a mixture of alkali carbonate and alkali bicarbonate: and contacting the carbonate solution with a strong-base anion exchange resin whereby the uranium values are adsorbed on the resin while the thorium remains in solution.

  20. SEPARATION OF POLONIUM, PROTACTINIUM OR MIXTURES THEREOF IN AQUEOUS SOLUTION FROM BISMUTH, LEAD, ZIRCONIUM AND/OR COLUMBIUM VALUES

    DOE Patents [OSTI]

    Van Winkle, Q.; Kraus, K.A.

    1959-10-27

    A process is presented for separating polonium, protactinium, or mixtures thereof in aqueous solution from bismuth, zirconium, lead, and niobium values contained in the solution. The method comprises providing hydrochloric acid in the solution in a concentration of at least 5N. contacting the aqueous solution with a substantially waterimmiscible organic solvent such as diisopropyl ketone, and separating the aqueous phase containing the bismuth, zirconium, lead, and niobium from the organic extract phase containing the polonium, protactinium, or mixture thereof.

  1. Menu Driven Program Determining Properties of Aqueous Lithium Bromide Solutions

    Energy Science and Technology Software Center (OSTI)

    1992-12-09

    LIMENU is a menu driven program written to compute seven physical properties of a lithium bromide-water solution and three physical properties of water, and to display two plots.

  2. Electrolyte pore/solution partitioning by expanded grand canonical ensemble Monte Carlo simulation

    SciTech Connect (OSTI)

    Moucka, Filip; Bratko, Dusan Luzar, Alenka

    2015-03-28

    Using a newly developed grand canonical Monte Carlo approach based on fractional exchanges of dissolved ions and water molecules, we studied equilibrium partitioning of both components between laterally extended apolar confinements and surrounding electrolyte solution. Accurate calculations of the Hamiltonian and tensorial pressure components at anisotropic conditions in the pore required the development of a novel algorithm for a self-consistent correction of nonelectrostatic cut-off effects. At pore widths above the kinetic threshold to capillary evaporation, the molality of the salt inside the confinement grows in parallel with that of the bulk phase, but presents a nonuniform width-dependence, being depleted at some and elevated at other separations. The presence of the salt enhances the layered structure in the slit and lengthens the range of inter-wall pressure exerted by the metastable liquid. Solvation pressure becomes increasingly repulsive with growing salt molality in the surrounding bath. Depending on the sign of the excess molality in the pore, the wetting free energy of pore walls is either increased or decreased by the presence of the salt. Because of simultaneous rise in the solution surface tension, which increases the free-energy cost of vapor nucleation, the rise in the apparent hydrophobicity of the walls has not been shown to enhance the volatility of the metastable liquid in the pores.

  3. SEPARATION OF PLUTONIUM VALUES FROM OTHER METAL VALUES IN AQUEOUS SOLUTIONS BY SELECTIVE COMPLEXING AND ADSORPTION

    DOE Patents [OSTI]

    Beaton, R.H.

    1960-06-28

    A process is given for separating tri- or tetravalent plutonium from fission products in an aqueous solution by complexing the fission products with oxalate, tannate, citrate, or tartrate anions at a pH value of at least 2.4 (preferably between 2.4 and 4), and contacting a cation exchange resin with the solution whereby the plutonium is adsorbed while the complexed fission products remain in solution.

  4. RECOVERY OF THORIUM AND URANIUM VALUES FROM AQUEOUS SOLUTIONS

    DOE Patents [OSTI]

    Calkins, G.D.

    1958-02-18

    This patent deals with the separation and recovery of uranium from monazite sand. After initial treatment of the sand with sodium hydroxide, a precipitate is obtuined which contains the uranium, thorium, rare earths and some phosphorus. This precipitate is then dissolved in nitric acid. The bulk of the rare earths are removed from thls soiution by adding aa excess of alkali carbonate, causing precipitation of the rare earths together with part of the thorium present. The solution still contains a considerable amount of thorium, some rare earths, and practically all of the uranium originally present. Thorium and rare earth values are readily precipitated from such solution, and the uranium values thus isolated, by the addition of an excess hydrogen peroxide. The pH value of the solution is preferably adjusted to at least 9 prior to the addition of the peroxide.

  5. Process for recovering pertechnetate ions from an aqueous solution also containing other ions

    DOE Patents [OSTI]

    Rogers, R.; Horwitz, E.P.; Bond, A.H.

    1997-02-18

    A solid/liquid process for the separation and recovery of TcO{sub 4}{sup {minus}1} ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO{sub 4}{sup {minus}1} ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO{sub 4}{sup {minus}1} ions in such an aqueous solution that is free from MoO{sub 4}{sup {minus}2} ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 15 figs.

  6. Process for recovering pertechnetate ions from an aqueous solution also containing other ions

    DOE Patents [OSTI]

    Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

    1997-01-01

    A solid/liquid process for the separation and recovery of TcO.sub.4.sup.-1 ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO.sub.4.sup.-1 ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO.sub.4.sup.-1 ions in such an aqueous solution that is free from MoO.sub.4.sup.-2 ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

  7. PRECIPITATION OF ZIRCONIUM, NIOBIUM, AND RUTHENIUM FROM AQUEOUS SOLUTIONS

    DOE Patents [OSTI]

    Wilson, A.S.

    1958-08-12

    An improvement on the"head end process" for decontaminating dissolver solutions of their Zr, Ni. and Ru values. The process consists in adding a water soluble symmetrical dialkyl ketone. e.g. acetone, before the formation of the manganese dioxide precipitate. The effect is that upon digestion, the ruthenium oxide does not volatilize, but is carried on the manganese dioxide precipitate.

  8. THERMAL CONDUCTIVITY OF AQUEOUS NaCl SOLUTIONS

    Office of Scientific and Technical Information (OSTI)

    ... to 25C or 50C for 30 minutes. solution was measured by a differential thermocouple. ... Equations ( 4 ) and ( 5 ) were used i n this work t o reproduce and i n t e r p o l a t e ...

  9. Time-resolved fluorometric determination of terbium in aqueous solution

    SciTech Connect (OSTI)

    Hemmilae, I.

    1985-07-01

    The fluorescent properties of water-soluble binary and ternary complexes of terbium(III) were studied and their applications in time-resolved fluorometric analysis were tested. Solutions composed of different ..beta..-diketones, tri-n-octylphosphine oxide as the synergistic agent, and Triton X-100 as the detergent were optimized to maximize fluorescence emission in Tb measurement. The results were then compared with seven published methods which included the use of the following respective solutions, ethylenediamine-N,N'-bis((o-hydroxy-phenyl)acetic acid), dipicolinic acid, iminodiacetic acid with Tiron, EDTA with Tiron, EDTA with 2,3-dihydroxynaphthalene, EDTA with sulfosalicylic acid, and EDTA with salicylate. Fluorinated aliphatic ..beta..-diketones showed the most promising properties in acidic solution. They were especially suitable for use in time-resolved fluorometric analyses where Tb was used as the label after being conjugated to the analyte via bifunctional complexones. An acidic pH is required for Tb release before conversion into a fluorescent chelate. The applicability of the developed measurement solutions to the measurement of Eu was also tested. 22 references, 3 figures, 7 tables.

  10. Photochemical method for generating superoxide radicals (O.sub.2.sup.-) in aqueous solutions

    DOE Patents [OSTI]

    Holroyd, Richard A.; Bielski, Benon H. J.

    1980-01-01

    A photochemical method and apparatus for generating superoxide radicals (ub.2.sup.-) in an aqueous solution by means of a vacuum-ultraviolet lamp of simple design. The lamp is a microwave powered rare gas device that emits far-ultraviolet light. The lamp includes an inner loop of high purity quartz tubing through which flows an oxygen-saturated sodium formate solution. The inner loop is designed so that the solution is subjected to an intense flux of far-ultraviolet light. This causes the solution to photodecompose and form the product radical (O.sub.2.sup.-).

  11. Sorption of metal ions from multicomponent aqueous solutions by activated carbons produced from waste

    SciTech Connect (OSTI)

    Tikhonova, L.P.; Goba, V.E.; Kovtun, M.F.; Tarasenko, Y.A.; Khavryuchenko, V.D.; Lyubchik, S.B.; Boiko, A.N.

    2008-08-15

    Activated carbons produced by thermal treatment of a mixture of sunflower husks, low-grade coal, and refinery waste were studied as adsorbents of transition ion metals from aqueous solutions of various compositions. The optimal conditions and the mechanism of sorption, as well as the structure of the sorbents, were studied.

  12. Electrolytes - Advanced Electrolyte and Electrolyte Additives...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    More Documents & Publications Electrolytes - Advanced Electrolyte and Electrolyte Additives Develop & evaluate materials & additives that enhance thermal & overcharge abuse ...

  13. The chemistry of plutonium(VI) in aqueous carbonate solutions

    SciTech Connect (OSTI)

    Stout, B.E.; Choppin, G.R. . Dept. of Chemistry); Sullivan, J.C. )

    1990-01-01

    The dynamic behavior of carbonate ion as a ligand that interacts with the hexavalent actinyl ions of U, Np, and Pu has been examined by {sup 13}C NMR. The first order rate parameter that describes the exchange between bulk solution and bound carbonate decreases with increasing pH. At a pH of 10.0, 25{degree}C, the respective values of k for the U(VI), Np(VI) and Pu(VI) complexes are 27.1 {plus minus} 0.3, 64.7 {plus minus} 3.3 and 706 {plus minus} 29. The variation of k with temperature was used to calculate the values of {Delta}H{sup +} = 53 and 42 kJ/M; and {Delta}S{sup +} = {minus}40 and {minus}71 J/M-K for the uranyl and neptunyl systems, respectively. A plausible reaction scheme for the exchange reaction is considered. The influence of these slow carbonate exchange reactions on selected electron transfer reactions is noted. 19 refs., 4 figs., 2 tabs.

  14. Electrolyte additive for lithium rechargeable organic electrolyte battery

    DOE Patents [OSTI]

    Behl, Wishvender K.; Chin, Der-Tau

    1989-01-01

    A large excess of lithium iodide in solution is used as an electrolyte adive to provide overcharge protection for a lithium rechargeable organic electrolyte battery.

  15. Electrolyte additive for lithium rechargeable organic electrolyte battery

    DOE Patents [OSTI]

    Behl, Wishvender K.; Chin, Der-Tau

    1989-02-07

    A large excess of lithium iodide in solution is used as an electrolyte adive to provide overcharge protection for a lithium rechargeable organic electrolyte battery.

  16. Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

    DOE Patents [OSTI]

    Dietz, Mark L.; Horwitz, E. Philip; Bartsch, Richard A.; Barrans, Jr., Richard E.; Rausch, David

    1999-01-01

    A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution.

  17. Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

    DOE Patents [OSTI]

    Dietz, M.L.; Horwitz, E.P.; Bartsch, R.A.; Barrans, R.E. Jr.; Rausch, D.

    1999-03-30

    A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution. 4 figs.

  18. METHOD OF RECOVERING PLUTONIUM VALUES FROM AQUEOUS SOLUTIONS BY CARRIER PRECIPITATION

    DOE Patents [OSTI]

    James, R.A.; Thompson, S.G.

    1959-11-01

    A process is presented for pretreating aqueous nitric acid- plutonium solutions containing a small quantity of hydrazine that has formed as a decomposition product during the dissolution of neutron-bombarded uranium in nitric acid and that impairs the precipitation of plutonium on bismuth phosphate. The solution is digested with alkali metal dichromate or potassium permanganate at between 75 and 100 deg C; sulfuric acid at approximately 75 deg C and sodium nitrate, oxaiic acid plus manganous nitrate, or hydroxylamine are added to the solution to secure the plutonium in the tetravalent state and make it suitable for precipitation on BiPO/sub 4/.

  19. Adsorption of organic acids from dilute aqueous solution onto activated carbon

    SciTech Connect (OSTI)

    Wang, S.W.

    1980-06-01

    The radioisotope technique was used to study the removal of organic acid contaminants from dilute aqueous solutions onto activated carbon. Acetic acid, propionic acid, n-butyric acid, n-hexanoic acid and n-heptanoic acid were studied at 278, 298, and 313/sup 0/K. Three bi-solute acid mixtures (acetic and propionic acids, acetic and butanoic acids, and propionic and butanoic acids) were studied at 278 and 298/sup 0/K. Isotherms of the single-solute systems were obtained at three different temperatures in the very dilute concentration region (less than 1% by weight). These data are very important in the prediction of bi-solute equilibrium data. A Polanyi-based competitive adsorption potential theory was used to predict the bi-solute equilibrium uptakes. Average errors between calculated and experimental data ranges from 4% to 14%. It was found that the competitive adsorption potential theory gives slightly better results than the ideal adsorbed solution theory.

  20. Ceramic electrolyte coating and methods

    DOE Patents [OSTI]

    Seabaugh, Matthew M.; Swartz, Scott L.; Dawson, William J.; McCormick, Buddy E.

    2007-08-28

    Aqueous coating slurries useful in depositing a dense coating of a ceramic electrolyte material (e.g., yttrium-stabilized zirconia) onto a porous substrate of a ceramic electrode material (e.g., lanthanum strontium manganite or nickel/zirconia) and processes for preparing an aqueous suspension of a ceramic electrolyte material and an aqueous spray coating slurry including a ceramic electrolyte material. The invention also includes processes for depositing an aqueous spray coating slurry including a ceramic electrolyte material onto pre-sintered, partially sintered, and unsintered ceramic substrates and products made by this process.

  1. Effect of temperature on the complexation of Uranium(VI) with fluoride in aqueous solutions

    SciTech Connect (OSTI)

    Tian, Guoxin; Rao, Linfeng

    2009-05-18

    Complexation of U(VI) with fluoride at elevated temperatures in aqueous solutions was studied by spectrophotometry. Four successive complexes, UO{sub 2}F{sup +}, UO{sub 2}F{sub 2}(aq), UO{sub 2}F{sub 3}{sup -}, and UO{sub 2}F{sub 4}{sup 2-}, were identified, and the stability constants at 25, 40, 55, and 70 C were calculated. The stability of the complexes increased as the temperature was elevated. The enthalpies of complexation at 25 C were determined by microcalorimetry. Thermodynamic parameters indicate that the complexation of U(VI) with fluoride in aqueous solutions at 25 to 70 C is slightly endothermic and entropy-driven. The Specific Ion Interaction (SIT) approach was used to obtain the thermodynamic parameters of complexation at infinite dilution. Structural information on the U(VI)/fluoride complexes was obtained by extended X-ray absorption fine structure spectroscopy.

  2. Aggregation of heteropolyanions in aqueous solutions exhibiting short-range attractions and long-range repulsions

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Bera, Mrinal K.; Qiao, Baofu; Seifert, Soenke; Burton-Pye, Benjamin P.; Monica Olvera de la Cruz; Antonio, Mark R.

    2015-12-15

    Charged colloids and proteins in aqueous solutions interact via short-range attractions and long-range repulsions (SALR) and exhibit complex structural phases. These include homogeneously dispersed monomers, percolated monomers, clusters, and percolated clusters. We report the structural architectures of simple charged systems in the form of spherical, Keggin-type heteropolyanions (HPAs) by small-angle X-ray scattering (SAXS) and molecular dynamics (MD) simulations. Structure factors obtained from the SAXS measurements show that the HPAs interact via SALR. Concentration and temperature dependences of the structure factors for HPAs with –3e (e is the charge of an electron) charge are consistent with a mixture of nonassociated monomersmore » and associated randomly percolated monomers, whereas those for HPAs with –4e and –5e charges exhibit only nonassociated monomers in aqueous solutions. Our experiments show that the increase in magnitude of the charge of the HPAs increases their repulsive interactions and inhibits their aggregation in aqueous solutions. MD simulations were done to reveal the atomistic scale origins of SALR between HPAs. As a result, the short-range attractions result from water or proton-mediated hydrogen bonds between neighboring HPAs, whereas the long-range repulsions are due to the distributions of ions surrounding the HPAs.« less

  3. Method for removal of explosives from aqueous solution using suspended plant cells

    DOE Patents [OSTI]

    Jackson, Paul J.; Torres, deceased, Agapito P.; Delhaize, Emmanuel

    1994-01-01

    The use of plant suspension cultures to remove ionic metallic species and TNT-based explosives and their oxidation products from aqueous solution is described. Several plant strains were investigated including D. innoxia, Citrus citrus, and Black Mexican Sweet Corn. All showed significant ability to remove metal ions. Ions removed to sub-ppm levels include barium, iron, and plutonium. D. innoxia cells growing in media containing weapons effluent contaminated with Ba.sup.2+ also remove TNT, other explosives and oxidation products thereof from solution. The use of dead, dehydrated cells was also found to be of use in treating waste directly.

  4. Method for removal of metal atoms from aqueous solution using suspended plant cells

    DOE Patents [OSTI]

    Jackson, Paul J.; Torres, deceased, Agapito P.; Delhaize, Emmanuel

    1992-01-01

    The use of plant suspension cultures to remove ionic metallic species and TNT-based explosives and their oxidation products from aqueous solution is described. Several plant strains were investigated including D. innoxia, Citrus citrus, and Black Mexican Sweet Corn. All showed significant ability to remove metal ions. Ions removed to sub-ppm levels include barium, iron, and plutonium. D. innoxia cells growing in media containing weapons effluent contaminated with Ba.sup.2+ also remove TNT, other explosives and oxidation products thereof from solution. The use of dead, dehydrated cells were also found to be of use in treating waste directly.

  5. Role of pH in metal adsorption from aqueous solutions containing chelating agents on chitosan

    SciTech Connect (OSTI)

    Wu, F.C.; Tseng, R.L.; Juang, R.S.

    1999-01-01

    The role of pH in adsorption of Cu(II) from aqueous solutions containing chelating agents on chitosan was emphasized. Four chelating agents including ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, and sodium gluconate were used. It was shown that the adsorption ability of Cu(II) on chitosan from its chelated solutions varied significantly with pH variations. The competition between coordination of Cu(II) with unprotonated chitosan and electrostatic interaction of the Cu(II) chelates with protonated chitosan took place because of the change in solution pH during adsorption. The maximum adsorption capacity was obtained within each optimal pH range determined from titration curves of the chelated solutions. Coordination of Cu(II) with the unprotonated chitosan was found to dominate at pH below such an optimal pH value.

  6. Cr(VI) reduction in aqueous solutions by using copper smelter slag

    SciTech Connect (OSTI)

    Kiyak, B.; Oezer, A.; Altundogan, H.S.; Erdem, M.; Tuemen, F. )

    1999-01-01

    The ability of Copper Smelter Slag (CSS) to reduce Cr(VI) in aqueous solutions has been investigated. The extent of reduction if dependent on the amounts of acid and reductant, contact time, Cr(VI) concentration, temperature of the solution and particle size of CSS. The amount of acid is the most important variable affecting the reduction process. When twice the amount of acid required with respect to Cr(VI) was used, Cr(VI) in 100 ml solution (100 mg/l) was completely reduced in a contact period less than 5 min by a 10 g/l dosage of CSS. Reduction efficiency increased with increase in temperature of solution, showing that the process is endothermic. Reduced chromium, and iron and other metals dissolved from CSS were effectively precipitated by using NaOH or calcinated carbonation sludge from sugar plant.

  7. Cr(VI) reduction in aqueous solutions by using copper smelter slag

    SciTech Connect (OSTI)

    Kiyak, B.; Oezer, A.; Altundogan, H.S.; Erdem, M.; Tuemen, F.

    1999-11-01

    The ability of Copper Smelter Slag (CSS) to reduce Cr(VI) in aqueous solutions has been investigated. The extent of reduction if dependent on the amounts of acid and reductant, contact time, Cr(VI) concentration, temperature of the solution and particle size of CSS. The amount of acid is the most important variable affecting the reduction process. When twice the amount of acid required with respect to Cr(VI) was used, Cr(VI) in 100 ml solution (100 mg/l) was completely reduced in a contact period less than 5 min by a 10 g/l dosage of CSS. Reduction efficiency increased with increase in temperature of solution, showing that the process is endothermic. Reduced chromium, and iron and other metals dissolved from CSS were effectively precipitated by using NaOH or calcinated carbonation sludge from sugar plant.

  8. Compatibility of Lithium Salts with Solvent of the Non-Aqueous Electrolyte in LiO2 Batteries

    SciTech Connect (OSTI)

    Du, Peng; Lu, Jun; Lau, Kah Chun; Luo, Xiangyi; Bareno, Javier; Zhang, Xiaoyi; Ren, Yang; Zhang, Zhengcheng; Curtiss, Larry A.; Sun, Yang-Kook; Amine, Khalil

    2013-02-20

    The stability of lithium salts, especially in the presence of reduced oxygen species, O2 and H2O (even in a small amount), plays an important role in the cyclability and capacity of LiO2 cells. This combined experimental and computational study provides evidence that the stability of the electrolyte used in LiO2 cells strongly depends on the compatibility of lithium salts with solvent. In the case of the LiPF61NM3 electrolyte, the decomposition of LiPF6 occurs in the cell as evidenced by in situ XRD, FT-IR and XPS analysis, which triggers the decomposition of 1NM3 solvent due to formation of HF from the decomposition of LiPF6. These reactions lead to degradation of the electrolyte and cause poor cyclability of the cell. The same reactions are not observed when LiTFSI and LiCF3SO3 are used as the lithium salts in 1NM3 solvent, or LiPF6 is used in TEGDME solvent.

  9. Solubilities of ethane in aqueous solutions of sodium dodecyl sulfate at elevated pressures

    SciTech Connect (OSTI)

    Li, P.; Han, B.; Yan, H.; Liu, R.

    1995-10-01

    The solubilities of ethane in aqueous solutions of sodium dodecyl sulfate (SDS) were measured at 313.15 K and at pressures up to 3 MPa. The molalities of SDS (m{sub SDS}) in the aqueous solution were 0.0000, 0.0020, 0.0040, 0.0060, 0.0070, 0.0080, 0.0090, 0.0100, 0.0126, 0.0150, 0.0200, and 0.0300. The effect of SDS on the gas solubility in both concentration regions below and above the critical micelle concentration (cmc) was studied. The existence of the micelles of SDS in the solution is favorable to the dissolution of ethane due to the hydrocarbon-like interior of the micelles. The solubilities of ethane in each micelle at different pressures were evaluated based on some assumptions. It was found that the intramicellar solubility of ethane is less than that of the gas in n-dodecane. It was also found that the solubility of ethane in the micelles increases linearly with the partial pressure of ethane. The cmc of SDS was evaluated based on the solubility vs m{sub SDS} curves and the effect of dissolved ethane on the cmc was studied. It was observed that the cmc shifts toward a higher value with the increase in dissolved ethane.

  10. Sulfate Separation from Aqueous Alkaline Solutions by Selective Crystallization of Alkali Metal Coordination Capsules

    SciTech Connect (OSTI)

    Rajbanshi, Arbin; Moyer, Bruce A; Custelcean, Radu

    2011-01-01

    Self-assembly of a tris(urea) anion receptor with Na{sub 2}SO{sub 4} or K{sub 2}SO{sub 4} yields crystalline capsules held together by coordinating Na{sup +} or K{sup +} cations and hydrogen-bonding water bridges, with the sulfate anions encapsulated inside urea-lined cavities. The sodium-based capsules can be selectively crystallized in excellent yield from highly competitive aqueous alkaline solutions ({approx}6 M Na{sup +}, pH 14), thereby providing for the first time a viable approach to sulfate separation from nuclear wastes.

  11. Process for preparing chemically modified micas for removal of cesium salts from aqueous solution

    DOE Patents [OSTI]

    Yates, Stephen Frederic; DeFilippi, Irene; Gaita, Romulus; Clearfield, Abraham; Bortun, Lyudmila; Bortun, Anatoly

    2000-09-05

    A chemically modified mica composite formed by heating a trioctahedral mica in an aqueous solution of sodium chloride having a concentration of at least 1 mole/liter at a temperature greater than 180 degrees Centigrade for at least 20 hours, thereby replacing exchangeable ions in the mica with sodium. Formation is accomplished at temperatures and pressures which are easily accessed by industrial equipment. The reagent employed is inexpensive and non-hazardous, and generates a precipitate which is readily separated from the modified mica.

  12. Testing of stripping columns for the removal of benzene from aqueous radioactive salt solution

    SciTech Connect (OSTI)

    Georgeton, G.K.; Taylor, G.A.; Gaughan, T.P.

    1995-06-27

    Radioactive high level wastes (HLW) generated from production of special nuclear materials at the Savannah River Site (SRS) are held in interim storage in 51 underground, million gallon tanks. Radioactive cesium ({sup 137}Cs) is segregated by evaporation of aqueous waste solution for interim storage in a salt matrix comprised of Na and K salts or in concentrated salt solution. The saltcake will be dissolved and {sup 137}Cs will be separated from the nonradioactive salts in solution in the In-Tank Precipitation (ITP) Process. The cesium will be combined with other radioactive species and glass formers to be melted and poured into stainless steel canisters in the Defense Waste Processing Facility (DWPF). The salt solution remaining after decontamination in the ITP process will be incorporated into grout for disposal at the site`s Saltstone facility. In the ITP facility, sodium tetraphenylborate (STPB) will be added to precipitate the cesium. Potassium in the waste solution also reacts with STPB and precipitates. Due to radiolytic and chemical degradation of the tetraphenylborate (TPB) precipitate, benzene is generated. The benzene dissolves into the decontaminated salt solution (DSS) and into water (WW) used to {open_quotes}wash{close_quotes} the precipitate to lower the soluble salt content of the slurry. Safety and processing requirements for disposal of the DSS and for temporary storage of the WW dictate that the benzene concentration be reduced.

  13. Kinetic investigation of catalytic disproportionation of superoxide ions in the non-aqueous electrolyte used in Li-air batteries

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Wang, Qiang; Yang, Xiao -Qing; Zheng, Doug; McKinnon, Meaghan E.; Qu, Deyang

    2014-10-28

    Superoxide reacts with carbonate solvents in Liair batteries. Tris(pentafluorophenyl)borane is found to catalyze a more rapid superoxide (O2-) disproportionation reaction than the reaction between superoxide and propylene carbonate (PC). With this catalysis, the negative impact of the reaction between the electrolyte and O2-produced by the O2 reduction can be minimized. A simple kinetic study using ESR spectroscopy was reported to determine reaction orders and rate constants for the reaction between PC and superoxide, and the disproportionation of superoxide catalyzed by Tris(pentafluorophenyl)borane and Li ions. The reactions are found to be first order and the rate constants are 0.033 s-1 M-1,more0.020 s-1 M-1and 0.67 s-1M-1 for reactions with PC, Li ion and Tris(pentafluorophenyl)borane, respectively.less

  14. Kinetic investigation of catalytic disproportionation of superoxide ions in the non-aqueous electrolyte used in Li–air batteries

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Wang, Qiang; Zheng, Dong; McKinnon, Meaghan E.; Yang, Xiao -Qing; Qu, Deyang

    2014-10-28

    Superoxide reacts with carbonate solvents in Li–air batteries. Tris(pentafluorophenyl)borane is found to catalyze a more rapid superoxide (O2-) disproportionation reaction than the reaction between superoxide and propylene carbonate (PC). With this catalysis, the negative impact of the reaction between the electrolyte and O2-produced by the O2 reduction can be minimized. A simple kinetic study using ESR spectroscopy was reported to determine reaction orders and rate constants for the reaction between PC and superoxide, and the disproportionation of superoxide catalyzed by Tris(pentafluorophenyl)borane and Li ions. As a result, the reactions are found to be first order and the rate constants aremore » 0.033 s-1 M-1, 0.020 s-1 M-1and 0.67 s-1M-1 for reactions with PC, Li ion and Tris(pentafluorophenyl)borane, respectively.« less

  15. Mean ionic activity coefficients in aqueous NaCl solutions from molecular dynamics simulations

    SciTech Connect (OSTI)

    Mester, Zoltan; Panagiotopoulos, Athanassios Z.

    2015-01-28

    The mean ionic activity coefficients of aqueous NaCl solutions of varying concentrations at 298.15 K and 1 bar have been obtained from molecular dynamics simulations by gradually turning on the interactions of an ion pair inserted into the solution. Several common non-polarizable water and ion models have been used in the simulations. Gibbs-Duhem equation calculations of the thermodynamic activity of water are used to confirm the thermodynamic consistency of the mean ionic activity coefficients. While the majority of model combinations predict the correct trends in mean ionic activity coefficients, they overestimate their values at high salt concentrations. The solubility predictions also suffer from inaccuracies, with all models underpredicting the experimental values, some by large factors. These results point to the need for further ion and water model development.

  16. Free radicals induced in aqueous solution by non-contact atmospheric-pressure cold plasma

    SciTech Connect (OSTI)

    Tani, Atsushi; Fukui, Satoshi; Ono, Yusuke; Kitano, Katsuhisa; Ikawa, Satoshi

    2012-06-18

    To understand plasma-induced chemical processing in liquids, we investigated the formation of free radicals in aqueous solution exposed to different types of non-contact atmospheric-pressure helium plasma using the spin-trapping technique. Both hydroxyl radical (OH{center_dot}) and superoxide anion radical (O{sub 2}{sup -}{center_dot}) adducts were observed when neutral oxygen gas was additionally supplied to the plasma. In particular, O{sub 2}{sup -}{center_dot} can be dominantly induced in the solution via oxygen flow into the afterglow gas of helium plasma. This type of plasma treatment can potentially be used in medical applications to control infectious diseases, because the O{sub 2}{sup -}{center_dot} is crucial for sterilization of liquids via atmospheric-pressure plasma.

  17. Magnetic separation of Dy(III) ions from homogeneous aqueous solutions

    SciTech Connect (OSTI)

    Pulko, B. Yang, X.; Lei, Z.; Odenbach, S.; Eckert, K.

    2014-12-08

    The possibility to enrich paramagnetic dysprosium(III) ions in a magnetic field gradient is proved by means of interferometry, which may open the route for a magnetic separation of rare earth ions from aqueous solutions. The separation dynamics are studied for three different concentrations of DyCl{sub 3} and compared with those found recently in a sulphate solution of the 3d ion Mn(II). In view of the similar-sized hydration spheres for Dy(III) and Mn(II), the slower separation dynamics in DyCl{sub 3} is attributed to both a higher densification coefficient and the strong impact of Brownian motion due to the absence of ion-pair clusters.

  18. Separation of glycols from dilute aqueous solutions via complexation with boronic acids

    SciTech Connect (OSTI)

    Randel, L.A.; King, C.J.

    1991-07-01

    This work examines methods of separating low molecular weight glycols from dilute aqueous solution. Extraction into conventional solvents is generally not economical, since, in the literature reviewed, distribution ratios for the two- to four-carbon glycols are all less than one. Distribution ratios can be increased, however, by incorporating into the organic phase an extracting agent that will complex with the solute of interest. The extracting agent investigated in this work is 3-nitrophenylboronic acid (NPBA). NPBA, a boric acid derivative, reversibly complexes with many glycols. The literature on complexation of borate and related compounds with glycols, including mechanistic data, measurement techniques, and applications to separation processes, provides information valuable for designing experiments with NPBA and is reviewed herein. 88 refs., 15 figs., 24 tabs.

  19. Sonochemical preparation of copper sulfides with different phases in aqueous solutions

    SciTech Connect (OSTI)

    Kristl, Matjaž; Hojnik, Nuša; Gyergyek, Sašo; Drofenik, Miha

    2013-03-15

    Highlights: ► Sonochemical preparation of copper sulfides in aqueous solutions is reported. ► CuS and Cu{sub 2}S nanoparticles with crystallite sizes between 7 and 18 nm were obtained. ► Crystallite size can be changed using different complexing agents. ► Thermal behavior was studied by TG and XRD measurements. - Abstract: There is a growing interest in the synthesis of nanostructured copper sulfides due to their ability to form compounds with various stoichiometries. We report a sonochemical route for the preparation of copper sulfides with different compositions in aqueous solutions, using different, general and convenient copper sources such as copper acetate, copper hydroxide or basic copper carbonate and thiourea or thioacetamide as sulfur precursors under ambient air. Phase analysis, purity and morphology of the products were studied by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The results revealed that nanoparticles of covellite, CuS, with crystallite sizes between 7 and 18 nm can be obtained by using different precursors and complexing agents and that chalcocite, Cu{sub 2}S, can also be prepared sonochemically.

  20. Electrolyte additive for improved battery performance

    DOE Patents [OSTI]

    Bellows, Richard J. (Hampton, NJ); Kantner, Edward (E. Brunswick, NJ)

    1989-04-04

    In one embodiment of the present invention, there is provided an electrochemical cell having a metal bromine couple. The cell includes an electrode structure on which to deposit the metal of the couple and a counterelectrode at which to generate bromine. A microporous membrane separates the electrode and counterelectrode. Importantly, the aqueous electrolyte comprises an aqueous metal bromide solution containing a water soluble bromine complexing agent capable of forming a water immiscible complex with bromine and an additive capable of decreasing the wettability of the microporous separators employed in such cells by such water immiscible bromine complexes.

  1. Kinetic investigation of catalytic disproportionation of superoxide ions in the non-aqueous electrolyte used in Liair batteries

    SciTech Connect (OSTI)

    Wang, Qiang; Zheng, Dong; McKinnon, Meaghan E.; Yang, Xiao -Qing; Qu, Deyang

    2014-10-28

    Superoxide reacts with carbonate solvents in Liair batteries. Tris(pentafluorophenyl)borane is found to catalyze a more rapid superoxide (O2-) disproportionation reaction than the reaction between superoxide and propylene carbonate (PC). With this catalysis, the negative impact of the reaction between the electrolyte and O2-produced by the O2 reduction can be minimized. A simple kinetic study using ESR spectroscopy was reported to determine reaction orders and rate constants for the reaction between PC and superoxide, and the disproportionation of superoxide catalyzed by Tris(pentafluorophenyl)borane and Li ions. As a result, the reactions are found to be first order and the rate constants are 0.033 s-1 M-1, 0.020 s-1 M-1and 0.67 s-1M-1 for reactions with PC, Li ion and Tris(pentafluorophenyl)borane, respectively.

  2. Kinetic investigation of catalytic disproportionation of superoxide ions in the non-aqueous electrolyte used in Li-air batteries

    SciTech Connect (OSTI)

    Wang, Qiang; Yang, Xiao -Qing; Zheng, Doug; McKinnon, Meaghan E.; Qu, Deyang

    2014-10-28

    Superoxide reacts with carbonate solvents in Liair batteries. Tris(pentafluorophenyl)borane is found to catalyze a more rapid superoxide (O2-) disproportionation reaction than the reaction between superoxide and propylene carbonate (PC). With this catalysis, the negative impact of the reaction between the electrolyte and O2-produced by the O2 reduction can be minimized. A simple kinetic study using ESR spectroscopy was reported to determine reaction orders and rate constants for the reaction between PC and superoxide, and the disproportionation of superoxide catalyzed by Tris(pentafluorophenyl)borane and Li ions. The reactions are found to be first order and the rate constants are 0.033 s-1 M-1, 0.020 s-1 M-1and 0.67 s-1M-1 for reactions with PC, Li ion and Tris(pentafluorophenyl)borane, respectively.

  3. Note: A novel technique for analysis of aqueous solutions by laser-induced breakdown spectroscopy

    SciTech Connect (OSTI)

    Rusak, D. A.; Bell, Z. T.; Anthony, T. P.

    2015-11-15

    Surface-enhanced Raman spectroscopy (SERS) substrates typically consist of gold or silver nanoparticles deposited on a non-conductive substrate. In Raman spectroscopy, the nanoparticles produce an enhancement of the electromagnetic field which, in turn, leads to greater electronic excitation of molecules in the local environment. Here, we show that these same surfaces can be used to enhance the signal-to-noise ratio obtained in laser-induced breakdown spectroscopy of aqueous solutions. In this case, the SERS substrates not only lower breakdown thresholds and lead to more efficient plasma initiation but also provide an appropriately wettable surface for the deposition of the liquid. We refer to this technique as surface-enhanced laser-induced breakdown spectroscopy.

  4. Oxidative processes occurring when pulsed high voltage discharges degrade phenol in aqueous solution

    SciTech Connect (OSTI)

    Sun, B.; Sato, Masayuki; Clements, J.S.

    2000-02-01

    In this investigation, results obtained using a pulsed discharge for organic compound removal are presented. The degradation of phenol by a streamer corona discharge and spark discharge, the effects of hydrogen peroxide additive on removal efficiency, and photochemical oxidation by ultraviolet light from the discharge plasma channel were investigated. The intermediate products and final byproducts formed by the spark discharge were also studied. A preliminary study of the degradation mechanism inside and outside the plasma channel was carried out. It was found that the removal efficiency of organic contaminants in the aqueous solution was higher for the spark discharge than for the streamer corona discharge and was greatly influenced by the discharge type and additive. The energy efficiency was the highest for the case with hydrogen peroxide injection and spark discharge. The main intermediate products produced by the spark discharge during the treatment process were hydroquinone, pyrocatechol, and p-benzoquinone. These intermediate products disappeared when the treatment time was increased.

  5. Rate-based process modeling study of CO{sub 2} capture with aqueous monoethanolamine solution

    SciTech Connect (OSTI)

    Zhang, Y.; Chen, H.; Chen, C.C.; Plaza, J.M.; Dugas, R.; Rochelle, G.T.

    2009-10-15

    Rate-based process modeling technology has matured and is increasingly gaining acceptance over traditional equilibrium-stage modeling approaches. Recently comprehensive pilot plant data for carbon dioxide (CO{sub 2}) capture with aqueous monoethanolamine (MEA) solution have become available from the University of Texas at Austin. The pilot plant data cover key process variables including CO{sub 2} concentration in the gas stream, CO{sub 2} loading in lean MEA solution, liquid to gas ratio, and packing type. In this study, we model the pilot plant operation with Aspen RateSep, a second generation rate-based multistage separation unit operation model in Aspen Plus. After a brief review of rate-based modeling, thermodynamic and kinetic models for CO{sub 2} absorption with the MEA solution, and transport property models, we show excellent match of the rate-based model predictions against the comprehensive pilot plant data and we validate the superiority of the rate-based models over the traditional equilibrium-stage models. We further examine the impacts of key rate-based modeling options, i.e., film discretization options and flow model options. The rate-based model provides excellent predictive capability, and it should be very useful for design and scale-up of CO{sub 2} capture processes.

  6. Crystallization Temperature of Aqueous Lithium Bromide Solutions at Low Evaporation Temperature

    SciTech Connect (OSTI)

    Kisari, Padmaja; Wang, Kai; Abdelaziz, Omar; Vineyard, Edward Allan

    2010-01-01

    Water- aqueous Lithium Bromide (LiBr) solutions have shown superior performance as working fluid pairs for absorption refrigeration cycles. Most of the available literature (e.g. ASHRAE Handbook of Fundamentals, etc.) provide crystallization behavior down to only 10 C. The typical evaporating temperature for an absorption chiller system is usually lower than 10 C. Hence, it is essential to have an accurate prediction of the crystallization temperature in this range in order to avoid crystallization during the design phase. We have therefore conducted a systematic study to explore the crystallization temperatures of LiBr/Water solutions that fall below an evaporating temperature of 10 C. Our preliminary studies revealed that the rate of cooling of the sample solution influences the crystallization temperature; therefore we have performed a quasi steady test where the sample was cooled gradually by reducing the sample temperature in small steps. Results from this study are reported in this paper and can be used to extend the data available in open literature.

  7. Novel, electrolyte solutions comprising fully inorganic salts with high anodic stability for rechargeable magnesium batteries

    SciTech Connect (OSTI)

    Doe, RE; Han, R; Hwang, J; Gmitter, AJ; Shterenberg, I; Yoo, HD; Pour, N; Aurbach, D

    2014-01-01

    Herein the first inorganic magnesium salt solution capable of highly reversible magnesium electrodeposition is presented. Synthesized by acid-base reaction of MgCl2 and Lewis acidic compounds such as AlCl3, this salt class demonstrates upwards of 99% Coulombic efficiency, deposition overpotential of <200 mV, and anodic stability of 3.1 V.

  8. ELECTROLYTIC MEMBRANE DIALYSIS FOR TREATING WASTEWATER STREAMS

    SciTech Connect (OSTI)

    Ronald C. Timpe

    2000-04-01

    This project will determine whether electrolytic dialysis has promise in the separation of charged particles in an aqueous solution. The ability to selectively move ions from one aqueous solution to another through a semipermeable membrane will be studied as a function of emf, amperage, and particle electrical charge. The ions selected for the study are Cl{sup -} and SO{sub 4}{sup 2-}. These ions are of particular interest because of their electrical conduction properties in aqueous solution resulting with their association with the corrosive action of metals. The studies will be performed with commercial membranes on solutions prepared in the laboratory from reagent salts. pH adjustments will be made with dilute reagent acid and base. Specific objectives of the project include testing a selected membrane currently available for electrolytic dialysis, membrane resistance to extreme pH conditions, the effectiveness of separating a mixture of two ions selected on the basis of size, the efficiency of the membranes in separating chloride (Cl{sup 1-}) from sulfate (SO{sub 4}{sup 2-}), and separation efficiency as a function of electromotive force (emf).

  9. Pseudo-hydroxide extraction in the separation of sodium hydroxide from aqueous solutions using alkyl phenols

    SciTech Connect (OSTI)

    Kang, Hyun Ah; Moyer, Bruce A

    2006-01-01

    Pseudo-hydroxide extraction of sodium hydroxide from aqueous solution using four alkyl phenols of nearly identical molecular weight in 1-octanol at 25 degrees C was examined to understand the effect of alkyl substituents. The order of extraction strength among the four alkyl phenols tested was 4-tert-octylphenol. 3,5-di-tertbutylphenol. 2,4-di-tert-butylphenol. 2,6-di-tert-butyl-4-methylphenol. A good correlation with phenol pK(a) was observed, indicating that extraction strength is determined by phenol acidity, as modified by steric effects in proximity to the phenol - OH group. The effective partition ratios (P-eff) of two phenols from 1 M NaOH solution were determined, showing that the phenols remain predominantly in the 1-octanol phase even when converted to their sodium salts. However, the hydrophobicity of the tested phenols may not be sufficient for process purposes. The equilibrium constants for the governing extraction equilibria were determined by modeling the data using the program SXLSQI, supporting the cation-exchange extraction mechanism. The proposed mechanism consists of two simple sets of equilibria for a. Ion-pair extraction to give Na+OH- ion pairs and corresponding free ions in 1-octanol the phase and b. Cation exchange by monomeric phenol molecules (HAs) to form monomeric organic-phase Na(+)A(-) ion pairs and corresponding free organic-phase ions.

  10. Stress corrosion cracking of alloy 600 in high temperature aqueous solutions: Influencing factors, mechanisms and models

    SciTech Connect (OSTI)

    Szklarska-Smialowska, Z.; Rebak, R.B.

    1996-12-31

    A detailed critical review of the multiple variables affecting stress corrosion cracking (SCC) of in high temperature (deaerated) aqueous solutions is given. Most of the data in the literature deals with the cracking susceptibility in the primary side; however, it is clear that similar factors and to a similar extent influence the SCC susceptibility in both primary and secondary sides. Some factors such as alkalinity of the solution or presence of lead (Pb) may be more in the secondary side and others such as partial pressure of hydrogen (H{sub 2}) in the primary side. Even though the effect of the variables on SCC susceptibility is more or less established, in models, in most of the cases there is a lack of fundamental understanding of the mechanisms involved. The different mechanisms and models proposed to explain the SCC of alloy 600 are briefly reviewed and their validity to explain the influence of the variables and to predict the crack growth rate (CGR), is assessed. It is concluded that several of the proposed models seem to give a fair estimate of the CGR values under certain conditions; however, it appears that a single mechanism cannot explain in detail the complex case of alloy 600 SCC. 113 refs., 11 figs., 3 tabs.

  11. Solubilities and other physical parameters of aromatic hydrocarbons in water and aqueous sodium chloride solutions as determined by headspace analysis

    SciTech Connect (OSTI)

    Lowry, M.A.H.

    1991-12-31

    The solubility, Henry`s law constant, aqueous-vapor partition coefficients, and oil-aqueous distribution coefficients of benzene, toluene, ethylbenzene, o-xylene,m-xylene and p-xylene were determined in water and aqueous sodium chloride solutions at 25C. Values are in agreement with using gas chromatography of headspace literature. The salting-out effect of sodium chloride on the solute properties measured was illustrated using the empirical relationship deduced by Setschenow (1889). The empirical relationship predicts that the logarithm of solubility will be a function of ionic strength. The solubility data obtained in this work obeys this relationship. It was also found that the logarithm of the Henry`s law constant, partition coefficient, and distribution coefficient are linear functions of ionic strength. 10 tabs, 6 figs.

  12. Materials for Use with Aqueous Redox Flow Batteries | Argonne National

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Laboratory Materials for Use with Aqueous Redox Flow Batteries The invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated

  13. Device of dispensing micro doses of aqueous solutions of substances onto a carrier and device for carrying out said method

    DOE Patents [OSTI]

    Ershow, Gennady Moiseevich; Kirillov, Evgenii Vladislavovich; Mirzabekov, Andrei Darievich

    1998-01-01

    A device for dispensing microdoses of aqueous solutions are provided, whereby the substance is transferred by the free surface end of a rodlike transferring element; the temperature of the transferring element is maintained at essentially the dew point of the ambient air during the transfer. The device may comprise a plate-like base to which are affixed a plurality of rods; the unfixed butt ends of the rods are coplanar. The device further comprises a means for maintaining the temperature of the unfixed butt ends of the rods essentially equal to the dew point of the ambient air during transfer of the aqueous substance.

  14. Efficient frequency conversion by stimulated Raman scattering in a sodium nitrate aqueous solution

    SciTech Connect (OSTI)

    Ganot, Yuval E-mail: ibar@bgu.ac.il; Bar, Ilana E-mail: ibar@bgu.ac.il

    2015-09-28

    Frequency conversion of laser beams, based on stimulated Raman scattering (SRS) is an appealing technique for generating radiation at new wavelengths. Here, we investigated experimentally the SRS due to a single pass of a collimated frequency-doubled Nd:YAG laser beam (532 nm) through a saturated aqueous solution of sodium nitrate (NaNO{sub 3}), filling a 50 cm long cell. These experiments resulted in simultaneous generation of 1st (564 nm) and 2nd (599 nm) Stokes beams, corresponding to the symmetric stretching mode of the nitrate ion, ν{sub 1}(NO{sub 3}{sup −}), with 40 and 12 mJ/pulse maximal converted energies, equivalent to 12% and 4% efficiencies, respectively, for a 340 mJ/pulse pump energy. The results indicate that the pump and SRS beams were thermally defocused and that four-wave mixing was responsible for the second order Stokes process onset.

  15. Electrophoretic Study of the SnO2/Aqueous Solution Interface up to 260 degrees C.

    SciTech Connect (OSTI)

    Rodriguez-Santiago, V; Fedkin, Mark V.; Wesolowski, David J

    2009-07-01

    An electrophoresis cell developed in our laboratory was utilized to determine the zeta potential at the SnO{sub 2} (cassiterite)/aqueous solution (10{sup -3} mol kg{sup -1} NaCl) interface over the temperature range from 25 to 260 C. Experimental techniques and methods for the calculation of zeta potential at elevated temperature are described. From the obtained zeta potential data as a function of pH, the isoelectric points (IEPs) of SnO{sub 2} were obtained for the first time. From these IEP values, the standard thermodynamic functions were calculated for the protonation-deprotonation equilibrium at the SnO{sub 2} surface, using the 1-pK surface complexation model. It was found that the IEP values for SnO{sub 2} decrease with increasing temperature, and this behavior is compared to the predicted values by the multisite complexation (MUSIC) model and other semitheoretical treatments, and were found to be in excellent agreement.

  16. Geopolymeric adsorbents from fly ash for dye removal from aqueous solution

    SciTech Connect (OSTI)

    Li, L.; Wang, S.B.; Zhu, Z.H.

    2006-08-01

    Adsorbents from coal fly ash treated by a solid-state fusion method using NaOH were prepared. It was found that amorphous aluminosilicate, geopolymers would be formed. These fly ash-derived inorganic polymers were assessed as potential adsorbents for removal of some basic dyes, methylene blue and crystal violet, from aqueous solution. It was found that the adsorption capacity of the synthesised adsorbents depends on the preparation conditions such as NaOH:fly-ash ratio and fusion temperature with the optimal conditions being at 1.2:1 weight ratio of Na:fly-ash at 250-350{sup o}C. The synthesised materials exhibit much higher adsorption capacity than fly ash itself and natural zeolite. The adsorption isotherm can be fitted by Langmuir and Freundlich models while the two-site Langmuir model produced the best results. It was also found that the fly ash derived geopolymeric adsorbents show higher adsorption capacity for crystal violet than methylene blue and the adsorption temperature influences the adsorption capacity. Kinetic studies show that the adsorption process follows the pseudo second-order kinetics.

  17. New porous titanium–niobium oxide for photocatalytic degradation of bromocresol green dye in aqueous solution

    SciTech Connect (OSTI)

    Chaleshtori, Maryam Zarei; Hosseini, Mahsa; Edalatpour, Roya; Masud, S.M. Sarif; Chianelli, Russell R.

    2013-10-15

    Graphical abstract: The photocatalytic activity of different porous titanium–niobium oxides was evaluated toward degradation of bromocresol green (BG) under UV light. A better catalytic activity was observed for all samples at lower pH. Catalysts have a stronger ability for degradation of BG in acid media than in alkaline media. - Highlights: • Different highly structured titanium–niobium oxides have been prepared using improved methods of synthesis. • Photo-degradation of bromocresol green dye (BG) with nanostructure titanium–niobium oxide catalysts was carried out under UV light. • The photo-catalytic activity of all catalysts was higher in lower pH. • Titanium–niobium oxide catalysts are considerably stable and reusable. - Abstract: In this study, high surface area semiconductors, non porous and porous titanium–niobium oxides derived from KTiNbO{sub 5} were synthesized, characterized and developed for their utility as photocatalysts for decontamination with sunlight. These materials were then used in the photocatalytic degradation of bromocresol green dye (BG) in aqueous solution using UV light and their catalytic activities were evaluated at various pHs. For all catalysts, the photocatalytic degradation of BG was most efficient in acidic solutions. Results show that the new porous oxides have large porous and high surface areas and high catalytic activity. A topotactic dehydration treatment greatly improves catalyst performance at various pHs. Stability and long term activity of porous materials (topo and non-topo) in photocatalysis reactions was also tested. These results suggest that the new materials can be used to efficiently purify contaminated water.

  18. Total reflection infrared spectroscopy of water-ice and frozen aqueous NaCl solutions

    SciTech Connect (OSTI)

    Walker, Rachel L.; Searles, Keith; Willard, Jesse A.; Michelsen, Rebecca R. H., E-mail: RMichelsen@rmc.edu [Department of Chemistry, Randolph-Macon College, P.O. Box 5005, Ashland, Virginia 23005 (United States)] [Department of Chemistry, Randolph-Macon College, P.O. Box 5005, Ashland, Virginia 23005 (United States)

    2013-12-28

    Liquid-like and liquid water at and near the surface of water-ice and frozen aqueous sodium chloride films were observed using attenuated total reflection infrared spectroscopy (ATR-IR). The concentration of NaCl ranged from 0.0001 to 0.01 M and the temperature varied from the melting point of water down to 256 K. The amount of liquid brine at the interface of the frozen films with the germanium ATR crystal increased with salt concentration and temperature. Experimental spectra are compared to reflection spectra calculated for a simplified morphology of a uniform liquid layer between the germanium crystal and the frozen film. This morphology allows for the amount of liquid observed in an experimental spectrum to be converted to the thickness of a homogenous layer with an equivalent amount of liquid. These equivalent thickness ranges from a nanometer for water-ice at 260 K to 170 nm for 0.01 M NaCl close to the melting point. The amounts of brine observed are over an order of magnitude less than the total liquid predicted by equilibrium thermodynamic models, implying that the vast majority of the liquid fraction of frozen solutions may be found in internal inclusions, grain boundaries, and the like. Thus, the amount of liquid and the solutes dissolved in them that are available to react with atmospheric gases on the surfaces of snow and ice are not well described by thermodynamic equilibrium models which assume the liquid phase is located entirely at the surface.

  19. Mechanistic studies of hydrogen evolution in aqueous solution catalyzed by a tertpyridine-amine cobalt complex

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Lewandowska-Andralojc, Anna; Baine, Teera; Zhao, Xuan; Muckerman, James T.; Fujita, Etsuko; Poyansky, Dmitry E.

    2015-04-22

    The ability of cobalt-based transition metal complexes to catalyze electrochemical proton reduction to produce molecular hydrogen has resulted in a large number of mechanistic studies involving various cobalt complexes. In addition, while the basic mechanism of proton reduction promoted by cobalt species is well understood, the reactivity of certain reaction intermediates, such as CoI and CoIII–H, is still relatively unknown owing to their transient nature, especially in aqueous media. In this work we investigate the properties of intermediates produced during catalytic proton reduction in aqueous solutions promoted by the [(DPA-Bpy)Co(OH₂)]n+ (DPA-Bpy = N,N-bis(2-pyridinylmethyl)-2,20-bipyridine-6-methanamine) complex ([Co(L)(OH₂)]n+ where L is the pentadentatemore » DPA-Bpy ligand or [Co(OH₂)]n+ as a shorthand). Experimental results based on transient pulse radiolysis and laser flash photolysis methods, together with electrochemical studies and supported by DFT calculations indicate that, while the water ligand is strongly coordinated to the metal center in the oxidation state 3+, one-electron reduction of the complex to form a CoII species results in weakening the Co–O bond. The further reduction to a CoI species leads to the loss of the aqua ligand and the formation of [CoI–VS)]⁺ (VS = vacant site). Interestingly, DFT calculations also predict the existence of a [CoI(κ⁴-L)(OH₂)]⁺ species at least transiently, and its formation is consistent with the experimental Pourbaix diagram. Both electrochemical and kinetics results indicate that the CoI species must undergo some structural change prior to accepting the proton, and this transformation represents the rate-determining step (RDS) in the overall formation of [CoIII–H]⁺. We propose that this RDS may originate from the slow removal of a solvent ligand in the intermediate [CoI(κ⁴-L)(OH₂)]⁺ in addition to the significant structural reorganization of the metal complex and

  20. Mechanistic studies of hydrogen evolution in aqueous solution catalyzed by a tertpyridine-amine cobalt complex

    SciTech Connect (OSTI)

    Lewandowska-Andralojc, Anna; Baine, Teera; Zhao, Xuan; Muckerman, James T.; Fujita, Etsuko; Poyansky, Dmitry E.

    2015-04-22

    The ability of cobalt-based transition metal complexes to catalyze electrochemical proton reduction to produce molecular hydrogen has resulted in a large number of mechanistic studies involving various cobalt complexes. In addition, while the basic mechanism of proton reduction promoted by cobalt species is well understood, the reactivity of certain reaction intermediates, such as CoI and CoIIIH, is still relatively unknown owing to their transient nature, especially in aqueous media. In this work we investigate the properties of intermediates produced during catalytic proton reduction in aqueous solutions promoted by the [(DPA-Bpy)Co(OH?)]n+ (DPA-Bpy = N,N-bis(2-pyridinylmethyl)-2,20-bipyridine-6-methanamine) complex ([Co(L)(OH?)]n+ where L is the pentadentate DPA-Bpy ligand or [Co(OH?)]n+ as a shorthand). Experimental results based on transient pulse radiolysis and laser flash photolysis methods, together with electrochemical studies and supported by DFT calculations indicate that, while the water ligand is strongly coordinated to the metal center in the oxidation state 3+, one-electron reduction of the complex to form a CoII species results in weakening the CoO bond. The further reduction to a CoI species leads to the loss of the aqua ligand and the formation of [CoIVS)]? (VS = vacant site). Interestingly, DFT calculations also predict the existence of a [CoI(??-L)(OH?)]? species at least transiently, and its formation is consistent with the experimental Pourbaix diagram. Both electrochemical and kinetics results indicate that the CoI species must undergo some structural change prior to accepting the proton, and this transformation represents the rate-determining step (RDS) in the overall formation of [CoIIIH]?. We propose that this RDS may originate from the slow removal of a solvent ligand in the intermediate [Co

  1. Zinc-bromine batteries with improved electrolyte

    SciTech Connect (OSTI)

    Kantner, E.

    1985-01-01

    The coulombic efficiency of aqueous zinc bromine batteries can be increased if, in addition to the bromide ions required to be present in the electrolyte to charge the cell to rated capacity, chloride ions are added to the electrolyte in amounts sufficient to reduce the amount of free bromine present in the electrolyte during operation of the cell.

  2. Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solution

    SciTech Connect (OSTI)

    DePaolo, D.

    2010-10-15

    A surface reaction kinetic model is developed for predicting Ca isotope fractionation and metal/Ca ratios of calcite as a function of rate of precipitation from aqueous solution. The model is based on the requirements for dynamic equilibrium; i.e. proximity to equilibrium conditions is determined by the ratio of the net precipitation rate (R{sub p}) to the gross forward precipitation rate (R{sub f}), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of R{sub p} has been experimentally measured under varying conditions, but the magnitude of R{sub f} is not generally known, and may depend on several factors. It is posited that, for systems with no trace constituents that alter the surface chemistry, R{sub f} can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (R{sub b} or k{sub b}), since at equilibrium R{sub f} = R{sub b}, and R{sub p} = 0. Hence it can be inferred that R{sub f} {approx} R{sub p} + R{sub b}. The dissolution rate of pure calcite is measureable and is known to be a function of temperature and pH. At given temperature and pH, equilibrium precipitation is approached when R{sub p} (= R{sub f} - R{sub b}) << R{sub b}. For precipitation rates high enough that R{sub p} >> R{sub b}, both isotopic and trace element partitioning are controlled by the kinetics of ion attachment to the mineral surface, which tend to favor more rapid incorporation of the light isotopes of Ca and discriminate weakly between trace metals and Ca. With varying precipitation rate, a transition region between equilibrium and kinetic control occurs near R{sub p} {approx} R{sub b} for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate R{sub f} for calcite precipitation. Mechanistic models for calcite precipitation indicate that the molecular exchange rate is not constant at constant T and pH, but rather is dependent also on solution saturation state and hence R{sub p

  3. Preparation and lithium intercalation behavior of TiO{sub 2} in aqueous solutions

    SciTech Connect (OSTI)

    Li, Yunjiao, E-mail: yunjiaoli6601@hotmail.com; Li, Lin; Chen, Lingpeng; Wang, Xuanyu; Xu, Cang

    2014-04-01

    Highlights: The poor crystalline anatase phase or amorphous TiO{sub 2} was prepared by TiCl{sub 4} hydrolysis under different pH conditions. Phase transition behavior and lithium intercalation ability of the obtained TiO{sub 2} were found to be related to TiO{sub 2} property. The results indicate that TiO{sub 2} products obtained from TiCl{sub 4} hydrolysis at lower pH are favorable for lithium intercalation. - Abstract: The low crystalline or amorphous TiO{sub 2} was prepared by TiCl{sub 4} hydrolysis in aqueous solutions under different pH conditions at 45 C. The products obtained at lower pH (1.233.10) appear to be nano-sized particles with poor crystalline anatase structure and an uniform particle size distribution, while the product prepared at pH 4.10 presents in a poor crystalline anatase structure and the regular morphology starts to disappear, and the products obtained at higher pH (>6.00) are amorphous and irregular morphology. The hydrolysis products obtained at pH 2.60 and 8.80 were heat-treated at 300, 400, 600, 700 and 800 C for 3 h, respectively, to figure out the phase transition. The differences in phase transition process were observed, which verified the properties difference. The lithium intercalation abilities of the obtained TiO{sub 2} were studied. The results indicated that the TiO{sub 2} obtained at lower pH are more favorable for lithium intercalation and are better precursors.

  4. Probing the Degradation Mechanisms in Electrolyte Solutions for Li-ion Batteries by In-Situ Transmission Electron Microscopy

    SciTech Connect (OSTI)

    Abellan Baeza, Patricia; Mehdi, Beata L.; Parent, Lucas R.; Gu, Meng; Park, Chiwoo; Xu, Wu; Zhang, Yaohui; Arslan, Ilke; Zhang, Jiguang; Wang, Chong M.; Evans, James E.; Browning, Nigel D.

    2014-02-21

    One of the goals in the development of new battery technologies is to find new electrolytes with increased electrochemical stability. In-situ (scanning) transmission electron microscopy ((S)TEM) using an electrochemical fluid cell provides the ability to rapidly and directly characterize electrode/electrolyte interfacial reactions under battery relevant electrochemical conditions. Furthermore, as the electron beam itself causes a localized electrochemical reaction when it interacts with the electrolyte, the breakdown products that occur during the first stages of battery operation can potentially be simulated and characterized using a straightforward in-situ liquid stage (without electrochemical biasing capabilities). In this paper, we have studied the breakdown of a range of inorganic/salt complexes that are used in state-of-the-art Li-ion battery systems. The results of the in-situ (S)TEM experiments matches with previous stability tests performed during battery operation and the breakdown products and mechanisms are also consistent with known mechanisms. This analysis indicates that in-situ liquid stage (S)TEM observations can be used to directly test new electrolyte designs and provide structural insights into the origin of the solid electrolyte interphase (SEI) formation mechanism.

  5. Process for electrolytic deposition of metals on zirconium materials

    DOE Patents [OSTI]

    Donaghy, Robert E.

    1979-01-30

    A process for the electrolytic deposition of a metal layer on an article comprised of zirconium or a zirconium alloy is disclosed. The article is activated in an aged aqueous solution comprising from about 10 to about 20 grams per liter ammonium bifluoride and from about 0.75 to about 2 grams per liter of sulfuric acid. The solution is aged by immersion of pickled zirconium in the solution for at least about 10 minutes. The loosely adhering film formed on the article in the activating step is removed and the article is contacted with an electrolytic plating solution containing the metal to be deposited on the article in the presence of an electrode receiving current.

  6. Development of Advanced Electrolytes and Electrolyte Additives...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Electrolytes and Electrolyte Additives Development of Advanced Electrolytes and Electrolyte Additives 2010 DOE Vehicle Technologies and Hydrogen Programs Annual Merit Review and ...

  7. Influence of liquid structure on diffusive isotope separation in molten silicates and aqueous solutions

    SciTech Connect (OSTI)

    Watkins, J.M.; DePaolo, D.J.; Ryerson, F.J.; Peterson, B.

    2011-03-01

    }. Cations diffusing in aqueous solutions display a similar relationship between isotopic separation efficiency and D{sub cation} =D{sub H 2 O} , although the efficiencies are smaller than in silicate liquids. Our empirical relationship provides a tool for predicting the magnitude of diffusive isotopic effects in many geologic environments and a basis for a more comprehensive theory of isotope separation in liquid solutions. We present a conceptual model for the relationship between diffusivity and liquid structure that is consistent with available data.

  8. Electrolyte additive for lithium rechargeable organic electrolyte battery

    SciTech Connect (OSTI)

    Behl, W.K.; Chin, D.T.

    1988-02-08

    This invention relates in general to a rechargeable lithium organic electrolyte battery and, in particular, to an electrolyte additive for such a battery that provides overcharge protection. Rechargeable lithium-organic electrolyte batteries are being developed to provide low-cost, high-energy-density power sources for communication, night vision and various other Army applications. Typically, a rechargeable lithium organic electrolyte battery includes a lithium anode, a cathode including compounds such as titanium disulfide, molybdenum oxide, molybdenum sulfide, vanadium oxide, vanadium sulfide, chromium oxide, etc an electrolyte solution including an inorganic lithium salt such as lithium hexafluoroarsenate, lithium perchlorate, etc.

  9. Electrolyte optimization for cathodic growth of zinc oxide films

    SciTech Connect (OSTI)

    Izaki, Masanobu; Omi, Takashi

    1996-03-01

    Zinc oxide is of considerable interest to the optical and electronic industries, because of its electrical, optical, and acoustic characteristics. ZnO films can be prepared by several techniques, such as radio frequency (RF) magnetron sputtering, chemical vapor deposition, and molecular beam epitaxy. Preparation of oxide films by electrodeposition from aqueous solutions has several potential advantages over the other techniques. However, the formation of oxide films through electrochemical reactions have been demonstrated only on thallic oxide by Switzer and zirconium oxide by Gal-Or. In this work, the authors have prepared transparent ZnO films with optical bandgap energy of 3.3 eV by electrodeposition from an aqueous, 0.1 mol/liter zinc nitrate electrolyte. The deposition technology is still being developed. This paper reports the effects of the electrolyte concentration on the electrodeposition and properties of the ZnO films.

  10. Electrolytic method for the production of lithium using a lithium-amalgam electrode

    DOE Patents [OSTI]

    Cooper, John F.; Krikorian, Oscar H.; Homsy, Robert V.

    1979-01-01

    A method for recovering lithium from its molten amalgam by electrolysis of the amalgam in an electrolytic cell containing as a molten electrolyte a fused-salt consisting essentially of a mixture of two or more alkali metal halides, preferably alkali metal halides selected from lithium iodide, lithium chloride, potassium iodide and potassium chloride. A particularly suitable molten electrolyte is a fused-salt consisting essentially of a mixture of at least three components obtained by modifying an eutectic mixture of LiI-KI by the addition of a minor amount of one or more alkali metal halides. The lithium-amalgam fused-salt cell may be used in an electrolytic system for recovering lithium from an aqueous solution of a lithium compound, wherein electrolysis of the aqueous solution in an aqueous cell in the presence of a mercury cathode produces a lithium amalgam. The present method is particularly useful for the regeneration of lithium from the aqueous reaction products of a lithium-water-air battery.

  11. Equilibrium hydrate formation conditions for hydrogen sulfide, carbon dioxide, and ethane in aqueous solutions of ethylene glycol and sodium chloride

    SciTech Connect (OSTI)

    Majumdar, A.; Mahmoodaghdam, E.; Bishnoi, P.R.

    2000-02-01

    Natural gas components such as hydrogen sulfide, carbon dioxide, and ethane form gas hydrates of structure I under suitable temperature and pressure conditions. Information on such conditions is vital to the oil and gas industry in order to design and operate processing equipment and pipelines so that hydrate formation is avoided. Incipient equilibrium hydrate formation conditions for hydrogen sulfide, carbon dioxide, and ethane in aqueous solutions of ethylene glycol and sodium chloride were experimentally obtained in the temperature range 264--290 K and the pressure range 0.23--3.18 MPa. A variable-volume sapphire cell was used for the measurements.

  12. 2012 WATER & AQUEOUS SOLUTIONS GORDON RESEARCH CONFERENCE (GRC) AND GORDON RESEARCH SEMINAR (GRS), AUG 10-17, 2012

    SciTech Connect (OSTI)

    Dor Ben-Amotz, PI

    2012-08-17

    Understanding the fundamental principles governing the structure and dynamics of water - and particularly how water mediates chemical interactions and processes - continues to pose formidable challenges and yield abundant surprises. The focus of this Gordon Research Conference is on identifying key questions, describing emerging understandings, and unveiling surprising discoveries related to water and aqueous solutions. The talks and posters at this meeting will describe studies of water and its interactions with objects such as interfaces, channels, electrons, oils, ions, and proteins; probed using optical, electrical, and particle experiments, and described using classical, quantum, and multi-scale theories.

  13. Regeneration of an aqueous solution from an acid gas absorption process by matrix stripping

    DOE Patents [OSTI]

    Rochelle, Gary T.; Oyenekan, Babatunde A.

    2011-03-08

    Carbon dioxide and other acid gases are removed from gaseous streams using aqueous absorption and stripping processes. By replacing the conventional stripper used to regenerate the aqueous solvent and capture the acid gas with a matrix stripping configuration, less energy is consumed. The matrix stripping configuration uses two or more reboiled strippers at different pressures. The rich feed from the absorption equipment is split among the strippers, and partially regenerated solvent from the highest pressure stripper flows to the middle of sequentially lower pressure strippers in a "matrix" pattern. By selecting certain parameters of the matrix stripping configuration such that the total energy required by the strippers to achieve a desired percentage of acid gas removal from the gaseous stream is minimized, further energy savings can be realized.

  14. Boron compounds as anion binding agents for nonaqueous battery electrolytes

    DOE Patents [OSTI]

    Lee, Hung Sui; Yang, Xia-Oing; McBreen, James; Xiang, Caili

    2000-02-08

    Novel fluorinated boron-based compounds which act as anion receptors in non-aqueous battery electrolytes are provided. When added to non-aqueous battery electrolytes, the fluorinated boron-based compounds of the invention enhance ionic conductivity and cation transference number of non-aqueous electrolytes. The fluorinated boron-based anion receptors include borane and borate compounds bearing different fluorinated alkyl and aryl groups.

  15. Solubilities of toluene and n-octane in aqueous protosurfactant and surfactant solutions

    SciTech Connect (OSTI)

    Ho, P.C.

    1985-01-01

    The solubilities of toluene and n-octane in aqueous protosurfactant and surfactant solutins were determined at 25/sup 0/C. The protosurfactants studied are sodium salts of cyclohexanecarboxylic acid, 2,5-diisopropylbenzenesulfonic acid, and 3,5-diisopropyisalicylic acid. Each of them has six alkyl carbons (S /SUB AC/ =6) and does not form micelles in water. The two micelle-forming surfactants used are sodium n-hexanoate with six alkyl carbons (S /SUB AC/ =6) and sodium n-octanoate with eight alkyl carbons (S /SUB AC/ =8). In three-component systems of toluene or n-octane with water and organic salt (either protosurfactant or surfactant), the solubility of the hydrocarbon in the aqueous phase increases as the number of alkyl carbons of the organic salt and as the aqueous concentration of the organic salt increases. However, in this study we found that sodium 3,5-diisopropyisalicylate causes much more pronounced increases in hydrocarbon solubility than these two surfactants. Sodium 2,5-diisopropylbenzenesulfonate, although not as effective in solubilization as the salicylate, has much stronger hydrotropic properties for hydrocarbons than either of these two surfactants. Sodium cyclohexanoate, with a compact arrangement of the six alkyl carbons, shows a higher hydrotropic effect than sodium n-hexanoate.

  16. Molecular dynamics simulations of the electrical double layer on smectite surfaces contacting concentrated mixed electrolyte (NaCl-CaCl?) solutions

    SciTech Connect (OSTI)

    Bourg, Ian C.; Sposito, Garrison

    2011-01-01

    We report new molecular dynamics results elucidating the structure of the electrical double layer (EDL) on smectite surfaces contacting mixed NaClCaCl2 electrolyte solutions in the range of concentrations relevant to pore waters in geologic repositories for CO2 or high-level radioactive waste (0.341.83 molc dm-3). Our results confirm the existence of three distinct ion adsorption planes (0-, ?-, and d-planes), often assumed in EDL models, but with two important qualifications: (1) the location of the ?- and d-planes are independent of ionic strength or ion type and (2) indifferent electrolyte ions can occupy all three planes. Charge inversion occurred in the diffuse ion swarm because of the affinity of the clay surface for CaCl+ ion pairs. Therefore, at concentrations {>=0.34 molc dm-3}, properties arising from long-range electrostatics at interfaces (electrophoresis, electro-osmosis, co-ion exclusion, colloidal aggregation) will not be correctly predicted by most EDL models. Co-ion exclusion, typically neglected by surface speciation models, balanced a large part of the clay mineral structural charge in the more concentrated solutions. Water molecules and ions diffused relatively rapidly even in the first statistical water monolayer, contradicting reports of rigid ice-like structures for water on clay mineral surfaces.

  17. Polymorph selection and nanocrystallite rearrangement of calcium carbonate in carboxymethyl chitosan aqueous solution: Thermodynamic and kinetic analysis

    SciTech Connect (OSTI)

    Zhao, Donghui; Zhu, Yingchun; Li, Fang; Ruan, Qichao; Zhang, Shengmao; Zhang, Linlin; Xu, Fangfang

    2010-01-15

    In this article, the polymorph selection of calcium carbonate has been successfully achieved in water-soluble carboxymethyl chitosan aqueous solution at different temperatures (25-95 {sup o}C). Vaterite is formed in carboxymethyl chitosan solution 25 {sup o}C accompanied with trace of calcite, whereas pure aragonite is obtained at 95 {sup o}C. Scanning electron microscopy and transmission electron microscopy analyses show that the products are formed from the recrystallization of nanometer crystallites. Thermodynamic and kinetic analyses reveal that the polymorph of calcium carbonate is controlled and selected by kinetics in various temperatures. As a heterogeneous nucleator and stabilizing agent, carboxymethyl chitosan changes the nucleation and growth of calcium carbonate from thermodynamic into kinetic control. Under kinetic limitation, the reaction rate of aragonite increases along with the elevating of temperature and surpasses the rate of vaterite above 327 K.

  18. Nitrogen K-edge x-ray absorption near edge structure of pyrimidine-containing nucleotides in aqueous solution

    SciTech Connect (OSTI)

    Shimada, Hiroyuki Minami, Hirotake; Okuizumi, Naoto; Sakuma, Ichiro; Ukai, Masatoshi; Fujii, Kentaro; Yokoya, Akinari; Fukuda, Yoshihiro; Saitoh, Yuji

    2015-05-07

    X-ray absorption near edge structure (XANES) was measured at energies around the N K-edge of the pyrimidine-containing nucleotides, cytidine 5′-monophosphate (CMP), 2′-deoxythymidine 5′-monophosphate (dTMP), and uridine 5′-monophosphate (UMP), in aqueous solutions and in dried films under various pH conditions. The features of resonant excitations below the N K-edge in the XANES spectra for CMP, dTMP, and UMP changed depending on the pH of the solutions. The spectral change thus observed is systematically explained by the chemical shift of the core-levels of N atoms in the nucleobase moieties caused by structural changes due to protonation or deprotonation at different proton concentrations. This interpretation is supported by the results of theoretical calculations using density functional theory for the corresponding nucleobases in the neutral and protonated or deprotonated forms.

  19. Quantitative extraction and concentration of synthetic water-soluble acid dyes from aqueous media using a quinine-chloroform solution

    SciTech Connect (OSTI)

    Kobayashi, F.; Ozawa, N.; Hanai, J.; Isobe, M.; Watabe, T.

    1986-12-01

    Twenty-one water-soluble acid dyes, including eleven azo, five triphenylmethane four xanthene, one naphthol derivatives, used at practical concentrations for food coloration, were quantitatively extracted from water and various carbonated beverages into a 0.1 M quinine-chloroform solution in the presence of 0.5 M boric acid by brief shaking. Quantitative extraction of these dyes was also accomplished by the 0.1 M quinine-chloroform solution made conveniently from chloroform, quinine hydrochloride, and sodium hydroxide added successively to water or beverages containing boric acid. Quinine acted as a countercation on the dyes having sulfonic and/or carboxylic acid group(s) to form chloroform-soluble ion-pair complexes. The diacidic base alkaloid interacted with each acid group of mono-, di-, tri-, and tetrasulfonic acid dyes approximately in the ratio 0.8-0.9 to 1. The dyes in the chloroform solution were quantitatively concentrated into a small volume of sodium hydroxide solution also by brief shaking. The convenient quinine-chloroform method was applicable to the quantitative extraction of a mixture of 12 dyes from carbonated beverages, which are all currently used for food coloration. A high-pressure liquid chromatographic method is also presented for the systematic separation and determination of these 12 dyes following their concentration into the aqueous alkaline solution. The chromatogram was monitored by double-wavelength absorptiometry in the visible and ultraviolet ray regions.

  20. Sessile drop studies on polybromide/zinc-bromine battery electrolyte

    SciTech Connect (OSTI)

    Kinoshita, K.; Leach, S.C.

    1982-08-01

    Improvements in the performance of zinc-bromine batteries have been observed with electrolytes containing a quaternary ammonium salt that complexes the bromine to reduce the concentration of free bromine in solution. A variety of quaternary ammonium salts that complex bromine to form a so-called polybromide oil have been considered. Various papers have discussed measurements of the physicochemical properties of the two-component system of bromine-quaternary ammonium bromide in an aqueous medium. The purpose of this paper is to investigate the interfacial tension of polybromide oils on the electrolytes for zinc-bromine batteries by reporting a study of the interfacial tension and contact angle of polybromide oil drops in which the sessile drop method is used. The interfacial tensions for the polybromide phases are found to be considerably lower than the values commonly reported for two-phase systems containing organic and aqueous phases. However, several two-phase systems, such as benzyl alcohol/water, furfural/water, and ethyl acetate/water have low interfacial tension comparable to that of the polybromide/electrolyte system. The low interfacial tension of the polybromide oil phase has important practical implications for the zinc-bromine battery. A stable emulsion can be produced very readily; small drops of the polybromide-oil phase can thus be stabilized with the electrolyte phase and can be expected to enhance the mass transfer of bromine from the polybromide to the electrode.

  1. REDUCTION OF PLUTONIUM VALUES IN AN ACIDIC AQUEOUS SOLUTION WITH FORMALDEHYDE

    DOE Patents [OSTI]

    Olson, C.M.

    1959-06-01

    A method is given for reducing Pu to the tetravalent state and lowering the high acidity of dissolver solutions containing U and Pu. Formaldehyde is added to the HNO/sub 3/ solution of U and Pu to effect a formaldehyde to HNO/sub 3/ molar ratio of 0.375:1 to 1.5:1. The Pu can then be removed from the solution by carrier precipitation using BiPO/sub 4/ or by ion exchange. (T.R.H.)

  2. Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization

    SciTech Connect (OSTI)

    Custelcean, Radu; Sloop Jr, Frederick {Fred} V; Rajbanshi, Arbin; Wan, Shun; Moyer, Bruce A

    2015-01-01

    ABSTRACT: The thermodynamics and kinetics of crystallization of sodium sulfate with a tripodal tris-urea receptor (L1) from aqueous alkaline solutions have been measured in the 15 55 C temperature range, with the goal of identifying the optimal conditions for efficient and quick sulfate removal from nuclear wastes. The use of radiolabeled Na235SO4 provided a practical way to monitor the sulfate concentration in solution by liquid scintillation counting. Our results are consistent with a two-step crystallization mechanism, involving relatively quick dissolution of crystalline L1 followed by the rate-limiting crystallization of the Na2SO4(L1)2(H2O)4 capsules. We found that temperature exerted relatively little influence over the equilibrium sulfate concentration, which ranged between 0.004 and 0.011 M. This corresponds to 77 91% removal of sulfate from a solution containing 0.0475 M initial sulfate concentration, as found in a typical Hanford waste tank. The apparent pseudo-first-order rate constant for sulfate removal increased 20-fold from 15 to 55 C, corresponding to an activation energy of 14.1 kcal/mol. At the highest measured temperature of 55 C, 63% and 75% of sulfate was removed from solution within 8 h and 24 h, respectively.

  3. Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Custelcean, Radu; Sloop, Frederick V.; Rajbanshi, Arbin; Wan, Shun; Moyer, Bruce A.

    2014-12-04

    We measured the thermodynamics and kinetics of crystallization of sodium sulfate with a tripodal tris-urea receptor (L1) from aqueous alkaline solutions in the 15 55 C temperature range, with the goal of identifying the optimal conditions for efficient and quick sulfate removal from nuclear wastes. The use of radiolabeled Na235SO4 provided a practical way to monitor the sulfate concentration in solution by liquid scintillation counting. Our results are consistent with a two-step crystallization mechanism, involving relatively quick dissolution of crystalline L1 followed by the rate-limiting crystallization of the Na2SO4(L1)2(H2O)4 capsules. We found that temperature exerted relatively little influence over themore » equilibrium sulfate concentration, which ranged between 0.004 and 0.011 M. Moreover, this corresponds to 77 91% removal of sulfate from a solution containing 0.0475 M initial sulfate concentration, as found in a typical Hanford waste tank. The apparent pseudo-first-order rate constant for sulfate removal increased 20-fold from 15 to 55 C, corresponding to an activation energy of 14.1 kcal/mol. At the highest measured temperature of 55 C, 63% and 75% of sulfate was removed from solution within 8 h and 24 h, respectively.« less

  4. Solubility Measurements of Crystalline NiO in Aqueous Solution as a Function of Temperature and pH

    SciTech Connect (OSTI)

    Palmer, Donald; Benezeth, Pascale; Xiao, Caibin {nmn}; Wesolowski, David J; Anovitz, Lawrence {Larry} M

    2011-01-01

    Abstract Results of solubility experiments involving crystalline nickel oxide (bunsenite) in aqueous solutions are reported as functions of temperature (0 to 350 C) and pH at pressures slightly exceeding (with one exception) saturation vapor pressure. These experiments were carried out in either flow-through reactors or a hydrogen-electrode concentration cell for mildly acidic to near neutral pH solutions. The results were treated successfully with a thermodynamic model incorporating only the unhydrolyzed aqueous nickel species (viz., Ni2+ ) and the neutrally charged hydrolyzed species (viz., Ni(OH)02 ). The thermodynamic quantities obtained at 25 C and infinite dilution are, with 2 uncertainties: log10Ko s0 = (12.40 0.29), rGo m = (70.8 1.7) kJ mol 1; rHo m = (105.6 1.3) kJ mol 1; rSo m = (116.6 3.2) J K 1 mol 1; rCo p,m = (0 13) J K 1 mol 1; and log10Ko s2 = (8.76 0.15); rGo m = (50.0 1.7) kJ mol 1; rHo m = (17.7 1.7) kJ mol 1; rSo m = (108 7) J K 1 mol 1; rCo p,m = (108 3) J K 1 mol 1. These results are internally consistent, but the latter set differs from those gleaned from previous studies recorded in the literature. The corresponding thermodynamic quantities for the formation of Ni2+ and Ni(OH)02 are also estimated. Moreover, the Ni(OH) 3 anion was never observed, even in relatively strong basic solutions (mOH = 0.1 mol kg 1), contrary to the conclusions drawn from all but one previous study.

  5. The Influence of Pre-oxidation on the Corrosion of Copper Nuclear Waste Canisters in Aqueous Anoxic Sulphide Solutions

    SciTech Connect (OSTI)

    Smith, J.M.; Qin, Z.; Wren, J.C.; Shoesmith, D.W.

    2007-07-01

    Scandinavian/Canadian high-level nuclear waste repository conditions are expected to evolve from initially warm and oxic to eventually cool and anoxic. During the warm, oxic period corrosion products will accumulate on the container surface. These deposits could impede the reaction of Cu with aqueous sulphide, the only reaction that could lead to the significant accumulation of additional corrosion damage under the long-term anoxic conditions. The kinetics of the reaction of Cu with aqueous sulphide solutions have been studied using electrochemical and surface analytical techniques. Corrosion potential measurements were used to follow the evolution of the surface as oxides/hydroxides were converted to sulphides in the sulphide concentration range 10{sup -5} to 10{sup -3} mol/L. Changes in composition were followed by in-situ Raman spectroscopy. Of critical importance is whether or not a period of pre-oxidation of a Cu container surface can prevent subsequent reaction of the surface with remotely produced sulphide. (authors)

  6. LOW TEMPERATURE PROCESS FOR THE REMOVAL AND RECOVERY OF CHLORIDES AND NITRATES FROM AQUEOUS NITRATE SOLUTIONS

    DOE Patents [OSTI]

    Savolainen, J.E.

    1963-01-29

    A method is described for reducing the chloride content of a solution derived from the dissolution of a stainless steel clad nuclear fuel element with an aqua regia dissolution medium. The solutlon is adjusted to a nitric acid concentration in the range 5 to 10 M and is countercurrently contacted at room temperature with a gaseous oxide of nitrogen selected from NO, NO/sub 2/, N/sub 2/ O/sub 3/, and N/sub 2/O/sub 4/. Chlo ride is recovered from the contacted solution as nitrosyl chloride. After reduction of the chloride content, the solution is then contacted with gaseous NO to reduce the nitric acid molarity to a desired level. (AEC)

  7. Structure of 2 molar NaOH in aqueous solution from neutron diffraction and empirical potential structure refinement

    SciTech Connect (OSTI)

    McLain, Sylvia E.; Imberti, Silvia; Soper, Alan K.; Botti, Alberto; Bruni, Fabio; Ricci, Maria Antonietta

    2006-09-01

    Neutron diffraction with isotopic substitution has been used to investigate aqueous solutions of 2M NaOH in the liquid state. The data were modeled using empirical potential structure refinement which allows for the extraction of the ion-water and water-water correlations. The data show that the ion-water radial distribution functions are in accordance with those found by previous studies on NaOH solutions and follow a trend which is dependent on the concentration of the solute. In particular, the shape of the hydroxide hydration shell is found to be concentration independent, but the number of water molecules occupying this shell increases with dilution. Additionally, the water-water correlations show that there is still a measurable effect on water structure with the addition of ions at this concentration, as the second shell in the water oxygen radial distribution function is compressed relative to the first shell. The data are also used to discuss the recent claims that the published radial distribution functions of water are unreliable, showing that data taken at different neutron sources, with different diffraction geometry and systematic errors lead to the same structural information when analyzed via a realistic modeling regime.

  8. A XANES and EXAFS Study of Hydration and Ion Pairing in Ambient Aqueous MnBr[subscript 2] Solutions

    SciTech Connect (OSTI)

    Chen, Yongsheng; Fulton, John L.; Partenheimer, Walter

    2008-09-25

    Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopies were used to probe the first-shell coordination structure of Mn(II) in aqueous MnBr{sub 2} solutions at ambient conditions from very dilute to the near saturation limit. The Mn K-edge EXAFS spectra for 0.05 and 0.2 m solutions showed that there was no Br(-I) in the first shell, and that the Mn(II) was fully hydrated with six water molecules in an octahedral arrangement. In contrast, for 6 m solution, the coordination number of water was reduced to about 5, and an average of about one bromine atom was present in the first shell as a contact ion pair. The 1s {yields} 4p transition at 6545.5 eV confirmed the observation of Mn-Br contact ion pairs at high concentrations and the 1s {yields} 3d transition at 6539.5 eV showed that the first shell coordination symmetry remained octahedral even in the presence of Mn-Br ion pairs.

  9. Extraction equilibria of acetic and propionic acids from dilute aqueous solution by several solvents

    SciTech Connect (OSTI)

    Fahim, M.A. )

    1992-10-01

    Extraction equilibria of acetic acid and propionic acid with hexane solutions of trioctyl amine, trioctyl phosphine oxide, and tributyl phosphate were studied. The species formed in the systems were estimated, and the distribution coefficients and the equilibrium constants for these species were evaluated.s

  10. Tunable Encapsulation Structure of Block Copolymer Coated Single-Walled Carbon Nanotubes in Aqueous Solution

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Han, Youngkyu; Ahn, Suk-Kyun; Zhang, Zhe; Smith, Gregory Scott; Do, Changwoo

    2015-01-01

    The nano-sized and shape-tunable molecular building blocks can provide great opportunities for the fabrication of precisely controlled nanostructures. In this work, we have fabricated a molecular building block of single-walled carbon nanotubes (SWNTs) coated by PPO-PEO-PPO block copolymers whose encapsulation structure can be controlled via temperature or addition of small molecules. The structure and optical properties of SWNT-block copolymers have been investigated by small angle neutron scattering (SANS), ultraviolet-visible (UV-vis) spectroscopy, atomic force microscopy (AFM), and molecular dynamics (MD) simulation. The structure of the hydrated block copolymer layer surrounding SWNT can be controlled reversibly by varying temperature as well asmore » by irreversibly adding 5-methylsalicylic acid (5MS). Increasing hydrophobicity of the polymers with temperature and strong tendency of 5MS to interact with both block copolymers and orbitals of the SWNTs are likely to be responsible for the significant structural change of the block copolymer encapsulation layer, from loose corona shell to tightly encapsulating compact shell. These result shows an efficient and simple way to fabricate and manipulate carbon-based nano building blocks in aqueous systems with tunable structure.« less

  11. Coagulation of quartz particles in aqueous solutions of copper(II)

    SciTech Connect (OSTI)

    Larson, I.; Pugh, R.J.

    1998-12-15

    The colloidal stability of quartz suspension was determined over a wide range of pH in aqueous copper nitrate where the state of Cu(II) is changed from mainly aqua ions and monohydroxyl complexes in the acid and neutral pH to polynuclear hydroxo complexes and colloidal precipitated copper hydroxide at higher pH. Two regions of instability were observed and in both cases the particles were shown to have low electrophoretic mobility. In the neutral pH region, the uptake of Cu(II) was sufficient to reduce the mobility of the particles to zero, while in the high-pH region evidence suggested coagulation between precipitated Cu(OH){sub 2} and the quartz particles. It was shown that in all cases the coagulation was reversible and that the uptake of Cu(II) was dependent on the uncharged surface hydroxyl density. Studies of the coagulation kinetics showed that extended time scales were involved (several minutes in the neutral pH region to tens of minutes at high pH).

  12. Cesium cobaltdicarbollide-solubility, precipitation, and reactivity in basic aqueous solution

    SciTech Connect (OSTI)

    McCabe, D.J.; Fanning, J.C.; Hugg, L.A.; Smith, W.A.; Terrell, A.S.; Yasinsac, L.; Todd, L.J.; Jasper, S.A. Jr.

    1994-12-31

    The title compound, Cs{sup +}[Co((3)-1,2-C{sub 2}B{sub 9}H{sub 11}){sub 2}]{sup {minus}}(CsCDC), was precipitated with a NaCDC solution from solutions containing CsCl. The reaction was followed by measuring loss of light intensity as the precipitate formed. The [Cs{sup +}] and [CDC{sup {minus}}] at the point of precipitation were estimated and approximate values of the K{sub sp} for CsCDC determined at room temperature: 8 {times} 10{sup {minus}6} (water), 7 {times} 10{sup {minus}6} (1 M NaOH), and 2 {times} 10{sup {minus}6} (5M NaCl/0.1 M KOH/1.0 M NaOH). In some cases, NaCDC precipitated from solution when added to the latter salt solution. For the medium, 5 M NaNO{sub 3}/0.1 M KOH/1.0 M NaOH a four-fold excess of NaCDC was added to a 10mM Cs{sup +} solution at 40{degrees}C and the [CDC{sup {minus}}] measured spectrophotometrically. Only CsCDC precipitated, and a K{sub sp} of 3.9 {times} 10{sup {minus}6} was determined. The solubilities of CsCDC were measured in NaNO{sub 3} and NaCl solutions at 30{sub C} as a function of the Na salt concentration. Reaction of the CDC{sup {minus}} with OH{sup {minus}} slowly produces B(OH{sub 4}{sup {minus}}, H{sub 2}, and CoO(OH). Reaction of 22 {mu}M CsCDC with 1M NaOH has a first order rate constant at 56{degrees}C of 8.8 {times} 10{sup {minus}7} s{sup {minus}1}, while that for 14 mM NaCDC is 7.2 {times} 10{sup {minus}7} s {sup {minus}1}. Activation energy for the reaction is 110 kJ.

  13. Flat band potential measurements of naked and viologen-modified n-WS[sub 2] electrodes in aqueous iodide and triiodide solutions

    SciTech Connect (OSTI)

    Huang, J.; Wrighton, M.S. )

    1994-09-15

    The flat band potentials, E[sub FB], of naked n-WS[sub 2] electrodes and cationic viologen polymer-modified n-WS[sub 2] electrodes have been determined in KI and KI[sub 3] solutions by differential capacitance measurements. The E[sub FB] values for naked n-WS[sub 2] electrodes are shifted negatively in electrolyte media containing I[sup [minus

  14. Use of differential pulse polarography to study corrosion of galvanized steel in aqueous lithium bromide solution

    SciTech Connect (OSTI)

    Garcia-Anton, J.; Perez-Herranz, V.; Guinon, J.L. . Dept. de Ingenieria Quimica y Nuclear); Lacoste, G. )

    1994-02-01

    Static and dynamic corrosion of galvanized steel in 4.6 M lithium bromide (LiBr) solution at 20 C and at 70 C was studied using a new polarographic method for the determination of zinc (Zn) in LiBr solution. Static and dynamic corrosion of galvanize steel at 20 C and 70 C followed a linear tendency with exposure time. However, a change in the slope of dynamic corrosion was observed at 20 C. The corrosion product was studied using energy dispersive x-ray analysis (EDXA) and x-ray diffractometry and was considered to be a mixture of zinc hydroxide Zn(OH)[sub 2] and oxides. The corrosion product morphology was amorphous and gelatinous at 20 C and crystalline at 70 C.

  15. Measurement of free ammonia produced by X irradiation of glycylglycine in aqueous solution

    SciTech Connect (OSTI)

    Yoshida, H.; Bolch, W.E.; Jacobson, K.B.; Turner, J.E. )

    1990-03-01

    This research was initiated to test the validity of predictions based on Monte Carlo calculations of the effect of ionizing radiation on a simple dipeptide. The mechanism for the formation of ammonia, proposed by Garrison, Sokol, and Bennett-Corniea, was reevaluated by measuring the yields under deoxygenated and oxygenated conditions. Although free ammonia was formed under both conditions, the yields were different, depending on the concentrations of solute and molecular oxygen. The reaction probabilities of the specific interactions of free radicals formed in pure water with solute and oxygen are discussed to account for the observed difference. Our results obtained after low-dose-rate X irradiation are compared with those obtained by Garrison et al. after high-dose-rate 60Co gamma irradiation.

  16. Speciation of aqueous palladium(II) chloride solutions using optical spectroscopies

    SciTech Connect (OSTI)

    Tait, C.D.; Janecky, D.R.; Rogers, P.S.Z. (Los Alamos National Lab., NM (United States))

    1991-05-01

    Spectroscopic measurements of palladium(II) chloride solutions have been performed under ambient to elevated temperature conditions with systematic changes in pH and (Cl{sup {minus}}). Spectral signatures from electronic absorption spectra (Uv/Vis) and Raman vibrational spectra were determined, and these were subsequently used to systematically map out species along several paths of the predominance diagram. The species PdCl{sub x}(H{sub 2}O){sub 4{minus}x}{sup 2{minus}x} (x = 2, 3, or 4) and Pd(OH){sub 2} were observed, along with a precipitation product formed from > 10 {mu}M (Pd{sup 2+}) solutions under near-neutral conditions. The elemental composition of the precipitation product was examined with a scanning electron micrograph (SEM) and was found to contain chloride as well as palladium. While sub-stoichiometric amounts of available OH{sup {minus}} ligand produced UV/Vis solution spectra likely to be from mixed Pd-Cl-OH species, the pH field of these species would be vanishingly small at low, geologically relevant palladium ion concentrations where (OH{sup {minus}}) is no longer the limiting reagent in the transformation. In mildly acidic media, where chloropalladium(II) species predominate, elevated temperatures (up to 90C) cause lower charged palladium-chloride species to be favored, consistent with the lowered dielectric constant of water at higher temperatures.

  17. Acidity of the amidoxime functional group in aqueous solution. A combined experimental and computational study

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Mehio, Nada; Lashely, Mark A.; Nugent, Joseph W.; Tucker, Lyndsay; Correia, Bruna; Do-Thanh, Chi-Linh; Dai, Sheng; Hancock, Robert D.; Bryantsev, Vyacheslav S.

    2015-01-01

    Poly(acrylamidoxime) adsorbents are often invoked in discussions of mining uranium from seawater. It has been demonstrated repeatedly in the literature that the success of these materials is due to the amidoxime functional group. While the amidoxime-uranyl chelation mode has been established, a number of essential binding constants remain unclear. This is largely due to the wide range of conflicting pKa values that have been reported for the amidoxime functional group in the literature. To resolve this existing controversy we investigated the pKa values of the amidoxime functional group using a combination of experimental and computational methods. Experimentally, we used spectroscopicmore » titrations to measure the pKa values of representative amidoximes, acetamidoxime and benzamidoxime. Computationally, we report on the performance of several protocols for predicting the pKa values of aqueous oxoacids. Calculations carried out at the MP2 or M06-2X levels of theory combined with solvent effects calculated using the SMD model provide the best overall performance with a mean absolute error of 0.33 pKa units and 0.35 pKa units, respectively, and a root mean square deviation of 0.46 pKa units and 0.45 pKa units, respectively. Finally, we employ our two best methods to predict the pKa values of promising, uncharacterized amidoxime ligands. Hence, our study provides a convenient means for screening suitable amidoxime monomers for future generations of poly(acrylamidoxime) adsorbents used to mine uranium from seawater.« less

  18. Acidity of the amidoxime functional group in aqueous solution. A combined experimental and computational study

    SciTech Connect (OSTI)

    Mehio, Nada; Lashely, Mark A.; Nugent, Joseph W.; Tucker, Lyndsay; Correia, Bruna; Do-Thanh, Chi-Linh; Dai, Sheng; Hancock, Robert D.; Bryantsev, Vyacheslav S.

    2015-01-26

    Poly(acrylamidoxime) adsorbents are often invoked in discussions of mining uranium from seawater. It has been demonstrated repeatedly in the literature that the success of these materials is due to the amidoxime functional group. While the amidoxime-uranyl chelation mode has been established, a number of essential binding constants remain unclear. This is largely due to the wide range of conflicting pKa values that have been reported for the amidoxime functional group in the literature. To resolve this existing controversy we investigated the pKa values of the amidoxime functional group using a combination of experimental and computational methods. Experimentally, we used spectroscopic titrations to measure the pKa values of representative amidoximes, acetamidoxime and benzamidoxime. Computationally, we report on the performance of several protocols for predicting the pKa values of aqueous oxoacids. Calculations carried out at the MP2 or M06-2X levels of theory combined with solvent effects calculated using the SMD model provide the best overall performance with a mean absolute error of 0.33 pKa units and 0.35 pKa units, respectively, and a root mean square deviation of 0.46 pKa units and 0.45 pKa units, respectively. Finally, we employ our two best methods to predict the pKa values of promising, uncharacterized amidoxime ligands. Hence, our study provides a convenient means for screening suitable amidoxime monomers for future generations of poly(acrylamidoxime) adsorbents used to mine uranium from seawater.

  19. Novel Regenerated Solvent Extraction Processes for the Recovery of Carboxylic Acids or Ammonia from Aqueous Solutions Part I. Regeneration of Amine-Carboxylic Acid Extracts

    SciTech Connect (OSTI)

    Poole, L.J.; King, C.J.

    1990-03-01

    Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO{sub 2} and H{sub 2}S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, succinic acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility of lactic acid and the tendency of the acid to self-associate. The separate recovery of ammonia and acid gases from sour waters can be achieved by combining steam-stripping of the acid gases with simultaneous removal of ammonia by extraction with a liquid cation exchanger. The use of di-2,4,4-trimethylpentyl phosphinic acid as the liquid cation exchanger is explored in this work. Batch extraction experiments were carried out to measure the equilibrium distribution ratio of ammonia between an aqueous buffer solution and an organic solution of the phosphinic acid (0.2N) in Norpar 12. The concentration

  20. CNEEC - Electrolyte Gating by David Goldhaber-Gordon

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Electrolyte Gating

  1. Synthesis and Evaluation of Cu-SAPO-34 Catalysts for Ammonia Selective Catalytic Reduction. 1. Aqueous Solution Ion Exchange

    SciTech Connect (OSTI)

    Gao, Feng; Walter, Eric D.; Washton, Nancy M.; Szanyi, Janos; Peden, Charles HF

    2013-09-06

    SAPO-34 molecular sieves are synthesized using various structure directing agents (SDAs). Cu-SAPO-34 catalysts are prepared via aqueous solution ion exchange. Catalysts are characterized with surface area/pore volume measurements, temperature programmed reduction (TPR), electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies. Catalytic properties are examined using standard ammonia selective catalytic reduction (NH3-SCR) and ammonia oxidation reactions. During solution ion exchange, different SAPO-34 samples undergo different extent of structural damage via irreversible hydrolysis. Si content within the samples (i.e., Al-O-Si bond density) and framework stress are key factors that affect irreversible hydrolysis. Even using very dilute Cu acetate solutions, it is not possible to generate Cu-SAPO-34 samples with only isolated Cu2+ ions. Small amounts of CuOx species always coexist with isolated Cu2+ ions. Highly active and selective Cu-SAPO-34 catalysts for NH3-SCR are readily generated using this synthesis protocol, even for SAPO-34 samples that degrade substantially during solution ion exchange. High-temperature aging is found to improve the catalytic performance. This is likely due to reduction of intracrystalline mass-transfer limitations via formation of additional porosity in the highly defective SAPO-34 particles formed after ion exchange. The authors gratefully acknowledge the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Office of Vehicle Technologies for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOEs Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle Memorial Institute under contract number DE-AC05-76RL01830.

  2. Oxygen-17 NMR Shifts Caused by Cr{Sup ++} in Aqueous Solutions

    DOE R&D Accomplishments [OSTI]

    Jackson, J. A.; Lemons, J. F.; Taube, H.

    1962-01-01

    Cr{sup ++} in solution produces a paramagnetic shift in the NMR absorption of O{sup 17} in ClO{sub 4}{sup -}, as well as the expected paramagnetic shift for O{sup 17} in H{sub 2}O. As the concentration of ClO{sub 4}{sup -} increases, the shift in the H{sub 2}O{sup 17} absorption is diminished, and eventually changes sign. The effects are ascribed to preferential replacement by ClO{sub 4}{sup -} of water molecules from the axial positions in the first coordination sphere about Cr{sup ++}.

  3. Strong Circularly Polarized Luminescence from Highly Emissive Terbium Complexes in Aqueous Solution

    SciTech Connect (OSTI)

    Samuel, Amanda; Lunkley, Jamie; Muller, Gilles; Raymond, Kenneth

    2010-03-15

    Two luminescent terbium(III) complexes have been prepared from chiral ligands containing 2-hydroxyisophthalamide (IAM) antenna chromophores and their non-polarized and circularly-polarized luminescence properties have been studied. These tetradentate ligands, which form 2:1 ligand/Tb{sup III} complexes, utilize diaminocyclohexane (cyLI) and diphenylethylenediamine (dpenLI) backbones, which we reasoned would impart conformational rigidity and result in Tb{sup III} complexes that display both large luminescence quantum yield ({phi}) values and strong circularly polarized luminescence (CPL) activities. Both Tb{sup III} complexes are highly emissive, with {phi} values of 0.32 (dpenLI-Tb) and 0.60 (cyLI-Tb). Luminescence lifetime measurements in H{sub 2}O and D{sub 2}O indicate that while cyLI-Tb exists as a single species in solution, dpenLI-Tb exists as two species: a monohydrate complex with one H{sub 2}O molecule directly bound to the Tb{sup III} ion and a complex with no water molecules in the inner coordination sphere. Both cyLI-Tb and dpenLI-Tb display increased CPL activity compared to previously reported Tb{sup III} complexes made with chiral IAM ligands. The CPL measurements also provide additional confirmation of the presence of a single emissive species in solution in the case of cyLI-Tb, and multiple emissive species in the case of dpenLI-Tb.

  4. Coordination Chemistry in Magnesium Battery Electrolytes: How...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    March 3, 2014, Research Highlights Coordination Chemistry in Magnesium Battery Electrolytes: How Ligands Affect Their Performance (Top) Schematic illustration of the solution ...

  5. Interaction Between Like-Charged Colloidal Spheres in Electrolyte...

    Office of Scientific and Technical Information (OSTI)

    Country of Publication: United States Language: English Subject: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ELECTROLYTES; SOLUTIONS; CHEMISTRY; LAWRENCE BERKELEY ...

  6. Adsorption of Ions on Zirconium Oxide Surfaces from Aqueous Solutions at High Temperatures.

    SciTech Connect (OSTI)

    Palmer, Donald; Machesky, Michael L.; Benezeth, Pascale; Wesolowski, David J

    2009-07-01

    Surface titrations were carried out on suspensions of monoclinic ZrO{sub 2} from 25 to 290 C slightly above saturation vapor pressure at ionic strengths of 0.03, 0.1 and 1.0 mol {center_dot} kg{sup -1}(NaCl). A typical increase in surface charge was observed with increasing temperature. There was no correlation between the radius of the cations, Li{sup +}, Na{sup +}, K{sup +} and (CH{sub 3}){sub 4}N{sup +}, and the magnitude of their association with the surface. The combined results were treated with a 1-pK{sub a} MUSIC model, which yielded association constants for the cations (and chloride ion at low pH) at each temperature. The pH of zero-point-charge, pH{sub zpc}, decreased with increasing temperature as found for other metal oxides, reaching an apparent minimum value of 4.1 by 250 C. Batch experiments were performed to monitor the concentration of LiOH in solutions containing suspended ZrO{sub 2} particles from 200 to 360 C. At 350 and 360 C, Li{sup +} and OH{sup -} ions were almost totally adsorbed when the pressure was lowered to near saturation vapor pressure. This reversible trend has implications not only to pressure-water reactor, PWR, operations, but is also of general scientific and other applied interest. Additional experiments probed the feasibility that boric acid/borate ions adsorb reversibly onto ZrO{sub 2} surfaces at near-neutral pH conditions as indicated in earlier publications.

  7. Bio sorption of strontium from aqueous solution by New Strain Bacillus sp. GTG-83

    SciTech Connect (OSTI)

    Tajer Mohammad Ghazvini, P.; Ghorbanzadeh Mashkani, S.; Ghafourian, H.

    2007-07-01

    Attempt was made to isolate bacterial strains capable of removing Sr biologically. In this study we collected ten different water samples from naturally radioactive spring Neydasht in Iran and bacterial strains samples isolated. Initial screening of a total of 50 bacterial isolates resulted in selection of one strain. The strain showed maximum adsorption capacity with 55 mg Sr/g dry wt. It was tentatively identified as Bacillus sp. according to morphological and biochemical properties and called strain GTG-83. Studies indicated that Bacillus sp. GTG-83 was able to grow aerobically in the presence of 50 mM SrCl{sub 2} but showed severe growth inhibition at levels above that concentration. The bio-sorption capacity of Bacillus sp. GTG-83 strongly depends on solution pH, and the maximum Sr sorption capacity of Bacillus sp. GTG-83 were obtained at pH 10 independent of the absence or the presence of increasing concentrations of salt (MgCl{sub 2}). Sr-salt bio-sorption studies were also performed at this pH values. Equilibrium uptakes of Sr increased with increasing Sr concentrations up to 250 mg/l for Bacillus sp. GTG-83. Maximum bio-sorption of Sr was obtained at temperatures in the range of 30-35 deg. C. Bacillus sp. GTG-83 bio-sorbed 97 mg Sr/g dry wt at 100 mg/l initial Sr concentration without salt medium (MgCl{sub 2}). When salt concentration (MgCl{sub 2}) increased to 15% (w/v), these values dropped to 23.6 mg Sr/g dry wt at the same conditions. Uptake of Sr within 5 min of incubation was relatively rapid and the absorption continued slowly thereafter. (authors)

  8. Method Of Dispensing Microdoses Of A Aqueous Solutions Of S Ubstances Onto A Carrier And A Device For Carrying Out Said Method

    DOE Patents [OSTI]

    Ershov, Gennady Moiseevich; Kirillov, Eugenii Vladislavovich; Mirzabekov, Andrei Darievich

    1999-10-05

    A method and a device for dispensing microdoses of aqueous solutions are provided, whereby the substance is transferred by the free surface end of a rodlike transferring element; the temperature of the transferring element is maintained at essentially the dew point of the ambient air during the transfer. The device may comprise a plate-like base to which are affixed a plurality of rods; the unfixed butt ends of the rods are coplanar. The device further comprises a means for maintaining the temperature of the unfixed butt ends of the rods essentially equal to the dew point of the ambient air during transfer of the aqueous substance

  9. Radiolytic preparation of ultrafine colloidal gold particles in aqueous solution: Optical spectrum, controlled growth, and some chemical reactions

    SciTech Connect (OSTI)

    Henglein, A.

    1999-09-28

    Orange- or yellow-orange-colored aqueous dispersions of ultrafine gold particles ({approximately}2 nm) result from the {gamma}-irradiation of deaerated solutions containing hydrolyzed AuCl{sup {minus}}{sub 4} and poly(vinyl alcohol) or poly-(vinylpyrrolidone), respectively. The particles have a weak and very broad plasmon absorption band with maximum in the 490 to 500 nm range, i.e., at substantially shorter wavelengths than expected from classical Mie theory using bulk dielectric data; moreover, the specific UV adsorption increases as the particles become smaller. The particles are used as seeds in the radiolytic reduction of added Au(CN){sup {minus}}{sub 2} to yield larger particles of any desired size and improved monodispersity. The particles partially react with oxygen. Chemisorption of 3-mercapto propionic acid strongly affects the electronics of the particles, as indicated by the changes in optical absorption. The early stages of AuCl{sup {minus}}{sub 4} reduction are also investigated. The reduction occurs essentially in two steps: (1) formation, and (2) reduction of Au{sup +}. A203-nm absorption band is tentatively attributed to Au{sup +}. Without further irradiation, Au{sup +} disappears thermally within hours to yield larger particles (20--70 nm).

  10. Synthesis and utilization of a novel carbon nanotubes supported nanocables for the adsorption of dyes from aqueous solutions

    SciTech Connect (OSTI)

    Liu, Wei; Jiang, Xinyu; Chen, Xiaoqing

    2015-09-15

    Using multiwalled carbon nanotubes(MWCNTs) as mechanical support and glucose as carbon resource, a hydrothermal carbonization route was designed for the synthesis of MWCNTs@carbon nanocables with tunable diameter and length. MWCNTs are firstly used as templates for the formation of carbon-rich composite nanocables, and the diameter of the nanocables could be tailored through adjusting the hydrothermal time or the ratio of MWCNTs and glucose. Owing to abundant superficial oxygen-containing functional groups, porous surface and remarkable reactivity, the as-synthesized nanocables are capable of efficiently adsorbing cationic dye methylene blue (MB) and crystal violet (CV). Furthermore, the optimum adsorption conditions, kinetics, adsorption isotherms and adsorption thermodynamics of dyes were studied systematically. Additionally, the maximum adsorption capacities calculated from data analysis (298.5 mg/g for MB and 228.3 mg/g for CV) are significant higher than those of raw MWCNTs and some other adsorbents reported previously, which provides strong evidence for using MWCNTs@carbon nanocables as adsorbent to remove dyes from aqueous solutions. - Graphical abstract: MWCNTs@carbon nanocables has been successfully fabricated by a hydrothermal carbonization method. The as-synthesized novel samples were used as adsorbents and exhibited high adsorption capacity on MB and CV. - Highlights: • A simple, cost-effective and “green” method for the synthesis of the material. • The diameter and length of the material are relatively easy to control. • The surface has large oxygen-containing groups and preferable chemical reactivity. • Compared with raw MWCNTs and some other adsorbents, the adsorption capacity is much high.

  11. NO3- Coordination in Aqueous Solutions by 15N/14N and 18O/natO Isotopic Substitution: What Can We Learn from Molecular Simulation?

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Chialvo, Ariel A.; Vlcek, Lukas

    2014-12-16

    We explore the deconvolution of the water-nitrate correlations by the first-order difference approach involving neutron diffraction of heavy- and null-aqueous solutions of KNO3 under 14N 15N and natON 18ON substitutions to achieve a full characterization of the first water coordination around the nitrate ion. For that purpose we performed isobaric-isothermal simulations of 3.5m KNO3 aqueous solutions at ambient conditions to generate the relevant radial distribution functions (RDF) required in the analysis (a) to identify the individual partial contributions to the total neutron weighted distribution function, (b) to isolate and assess the contribution of NO3 -!K+ pair formation, (c) to testmore » the accuracy of the NDIS-based coordination calculations and XRDbased assumptions, and (d) to describe the water coordination around both the nitrogen and oxygen sites of the nitrate ion.« less

  12. The structure and stability of aqueous rare-earth elements in hydrothermal fluids: New results on neodymium(III) aqua and chloroaqua complexes in aqueous solutions to 500 °C and 520 MPa

    SciTech Connect (OSTI)

    Mayanovic, R.A.; Anderson, A.J.; Bassett, W.A.; Chou, I.-M.

    2009-02-04

    X-ray absorption spectroscopy (XAS) measurements were made at the Nd L{sub 3}-edge on neodymium(III) aqua and chloroaqua complexes in low pH aqueous solutions from 25 to 500 C and up to 520 MPa. Analysis of the extended X-ray absorption fine structure of the XAS spectra measured from a 0.07 m Nd/0.16 m HNO{sub 3} aqueous solution reveals a contraction of the Nd-O distance of the Nd{sup 3+} aqua ion at a uniform rate of {approx} 0.013 {angstrom}/100 C and a uniform reduction of the number of coordinated H{sub 2}O molecules from 10.0 {+-} 0.9 to 7.4 {+-} 0.9 over the range from 25 to 500 C and up to 370 MPa. The rate of reduction of the first-shell water molecules with temperature for Nd{sup 3+} (26%) is intermediate between the rate for the Gd{sup 3+} aqua ion (22% from 25 to 500 C) and the rates for the Eu{sup 3+} (29% from 25 to 400 C) and the Yb{sup 3+} aqua ions (42% from 25 to 500 C) indicating an intermediate stability of the Nd{sup 3+} aqua ion consistent with the tetrad effect. Nd L{sub 3}-edge XAS measurements of 0.05 m NdCl{sub 3} aqueous solution at 25 to 500 C and up to 520 MPa show that stepwise inner-sphere complexes most likely of the type Nd(H{sub 2}O){sub {delta}-n}Cl{sub n}{sup +3-n} occur in the solution at elevated temperatures, where {delta} {approx} 9 at 150 C decreasing to {approx} 6 at 500 C and the number of chloride ions (n) of the chloroaqua complexes increases uniformly with temperature from 1.2 {+-} 0.2 to 2.0 {+-} 0.2 in the solution upon increase of temperature from 150 to 500 C. Conversely, the number of H{sub 2}O ligands of Nd(H{sub 2}O){sub {delta}-n}Cl{sub n}{sup +3-n} complexes is uniformly reduced with temperature from 7.5 {+-} 0.8 to 3.7 {+-} 0.3 in the aqueous solution, in the same temperature range. These data show greater stability of neodymium(III) than gadolinium(III) and ytterbium(III) chloride complexes in low pH aqueous solutions at elevated temperatures. Our data suggest a greater stability of aqueous light REE than

  13. Solid electrolytes

    DOE Patents [OSTI]

    Abraham, Kuzhikalail M.; Alamgir, Mohamed

    1993-06-15

    This invention pertains to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized (encapsulated) in a solid organic polymer matrix. In particular, this invention relates to solid polymer electrolytes derived by immobilizing complexes (solvates) formed between a Li salt such as LiAsF.sub.6, LiCF.sub.3 SO.sub.3 or LiClO.sub.4 and a mixture of aprotic organic solvents having high dielectric constants such as ethylene carbonate (EC) (dielectric constant=89.6) and propylene carbonate (PC) (dielectric constant=64.4) in a polymer matrix such as polyacrylonitrile, poly(tetraethylene glycol diacrylate), or poly(vinyl pyrrolidinone).

  14. Novel electrolytes and electrolyte additives for PHEV applications...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Novel electrolytes and electrolyte additives for PHEV applications 2009 DOE Hydrogen ... More Documents & Publications Novel Electrolytes and Additives Novel Electrolytes and ...

  15. Recovery of mercury from mercury compounds via electrolytic methods

    DOE Patents [OSTI]

    Grossman, Mark W.; George, William A.

    1988-01-01

    A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg.sub.2 Cl.sub.2 employing as the electrolyte solution a mixture of HCl and H.sub.2 O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H.sub.2 O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds.

  16. Recovery of mercury from mercury compounds via electrolytic methods

    DOE Patents [OSTI]

    Grossman, Mark W.; George, William A.

    1991-01-01

    A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg.sub.2 Cl.sub.2 employing as the electrolyte solution a mixture of HCl and H.sub.2 O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H.sub.2 O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds.

  17. Recovery of mercury from mercury compounds via electrolytic methods

    DOE Patents [OSTI]

    Grossman, Mark W.; George, William A.

    1989-01-01

    A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg.sub.2 Cl.sub.2 employing as the electrolyte solution a mixture of HCl and H.sub.2 O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H.sub.2 O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds.

  18. Recovery of mercury from mercury compounds via electrolytic methods

    DOE Patents [OSTI]

    Grossman, M.W.; George, W.A.

    1989-11-07

    A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg[sub 2]Cl[sub 2] employing as the electrolyte solution a mixture of HCl and H[sub 2]O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H[sub 2]O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds. 3 figs.

  19. Recovery of mercury from mercury compounds via electrolytic methods

    DOE Patents [OSTI]

    Grossman, M.W.; George, W.A.

    1991-06-18

    A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg[sub 2]Cl[sub 2] employing as the electrolyte solution a mixture of HCl and H[sub 2]O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H[sub 2]O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds. 3 figures.

  20. Electrolytic orthoborate salts for lithium batteries

    DOE Patents [OSTI]

    Angell, Charles Austen; Xu, Wu

    2008-01-01

    Orthoborate salts suitable for use as electrolytes in lithium batteries and methods for making the electrolyte salts are provided. The electrolytic salts have one of the formulae (I). In this formula anionic orthoborate groups are capped with two bidentate chelating groups, Y1 and Y2. Certain preferred chelating groups are dibasic acid residues, most preferably oxalyl, malonyl and succinyl, disulfonic acid residues, sulfoacetic acid residues and halo-substituted alkylenes. The salts are soluble in non-aqueous solvents and polymeric gels and are useful components of lithium batteries in electrochemical devices.

  1. Electrolytic orthoborate salts for lithium batteries

    DOE Patents [OSTI]

    Angell, Charles Austen [Mesa, AZ; Xu, Wu [Tempe, AZ

    2009-05-05

    Orthoborate salts suitable for use as electrolytes in lithium batteries and methods for making the electrolyte salts are provided. The electrolytic salts have one of the formulae (I). In this formula anionic orthoborate groups are capped with two bidentate chelating groups, Y1 and Y2. Certain preferred chelating groups are dibasic acid residues, most preferably oxalyl, malonyl and succinyl, disulfonic acid residues, sulfoacetic acid residues and halo-substituted alkylenes. The salts are soluble in non-aqueous solvents and polymeric gels and are useful components of lithium batteries in electrochemical devices.

  2. Electrolyte salts for nonaqueous electrolytes

    DOE Patents [OSTI]

    Amine, Khalil; Zhang, Zhengcheng; Chen, Zonghai

    2012-10-09

    Metal complex salts may be used in lithium ion batteries. Such metal complex salts not only perform as an electrolyte salt in a lithium ion batteries with high solubility and conductivity, but also can act as redox shuttles that provide overcharge protection of individual cells in a battery pack and/or as electrolyte additives to provide other mechanisms to provide overcharge protection to lithium ion batteries. The metal complex salts have at least one aromatic ring. The aromatic moiety may be reversibly oxidized/reduced at a potential slightly higher than the working potential of the positive electrode in the lithium ion battery. The metal complex salts may also be known as overcharge protection salts.

  3. Laser Raman spectroscopy study of the zinc and bromide ion complex equilibrium in zinc/bromine battery electrolytes. [2M ZnBr/sub 2/ and 1M KBr solution

    SciTech Connect (OSTI)

    Grimes, P.G.; Larrabee, J.A.

    1985-01-01

    Laser Raman spectroscopy was used to study the zinc and bromide ion complex equilibrium in zinc bromine battery model electrolytes. Solutions of zinc bromide with added KBr, HBr and N-methyl, N-ethyl morpholinium (MEM) bromide were examined and compared. Solutions studied ranged from 1 to 3 molar in zinc and from 2.5 to 8 molar in bromide. A typical Raman spectrum of a zinc bromide solution is shown in Figure 1. Each of the zinc species is identified, Zn/sup + +/ (aq), ZnBr/sup +/, ZnBr/sub 2/ (aq), ZnBr/sub 3//sup -/ and ZnBr/sub 4//sup 2 -/. By the use of peak heights or deconvolution/integration along with published Raman cross sections, the amount of each zinc species could be quantitatively determined. The addition of bromide ions to the zinc bromide solutions will shift the equilibrium toward higher bromide complexes. The added cations will influence the shifts. It has been noted that the conductivity of the electrolyte decreases when the quaternary ammonium ions are present compared to cations such as potassium or hydrogen. Significantly more free zinc is present in zinc bromide solutions with added KBr than with either MEMBr or HBr. Shifts are also noted with the other zinc ion containing species. It appears that the quaternary ammonium ions and possibly the pH could have a stabilizing effect on zinc bromide complex ion formation. 2 figs.

  4. SYNTHESIS OF A NEW FAMILY OF FLUORINATED BORONATE COMPOUNDS AS ANION RECEPTORS AND STUDIES OF THEIR USE AS ADDITIVES IN LITHIUM BATTERY ELECTROLYTES.

    SciTech Connect (OSTI)

    MCBREEN,J.; LEE,H.S.; YANG,X.Q.

    2001-06-08

    Numerous studies have been done on developing new electrolytes for lithium batteries with high ionic conductivity, and good chemical and electrochemical stability. In addition to the research on new salts and solvents, the use of cation receptors to reduce ion pairing in non-aqueous electrolytes has been considered as an approach to improve the properties of electrolytes. Although both cation and anion receptors enhance the dissociation of ion pairs and increase the conductivity of electrolytes, the use of anion receptors is more attractive for a lithium battery electrolyte because anion receptors increase the lithium transference number in the electrolyte. However, most available neutral anion receptors complex with anions through hydrogen binding and cannot be used in lithium batteries. Recently, we have reported on synthesis of a series of new neutral boron compounds as anion receptors based on the idea that electron-deficient boron would complex the anion of the ion pair. The anion complexation effect of these boron compounds was further enhanced by attaching electron-withdrawing groups. Here we report synthesis of another new family of boronate compounds. The effect of these new compounds on conductivity of lithium salts in non-aqueous solution was studied. The molecular weights of these new boronate compounds are lower than our previously reported boron compounds. Therefore, their effects on conductivity enhancement are superior. They also display high electrochemical stability up to 5 V.

  5. X-ray Studies of the Interface Between Two Polar Liquids: Neat and with Electrolytes

    SciTech Connect (OSTI)

    Luo, G.; Malkova, S.; Pingali, S.V.; Schultz, D.; Lin, B.; Meron, M.; Graber, T.; Gebhardt, J.; Vanysek, P.; Schlossman, M.L.

    2010-11-30

    We demonstrate the use of X-ray reflectivity to probe the electron density profile normal to the interface between two polar liquids. Measurements of the interfacial width at the neat nitrobenzene/water and the neat water/2-heptanone interfaces are presented. These widths are consistent with predictions from capillary wave theory that describe thermal interfacial fluctuations determined by the tension and bending rigidity of the interface. Variation of the temperature of the water/nitrobenzene interface from 25 C to 55 C indicates that the role of the bending rigidity decreases with increasing temperature. X-ray reflectivity measurements of the electrified interface between an aqueous solution of BaCl{sub 2} and a nitrobenzene solution of TBATPB demonstrate the sensitivity of these measurements to the electrolyte distribution at the interface. A preliminary analysis of these data illustrates the inadequacy of the simplest, classical Gouy-Chapman theory of the electrolyte distribution.

  6. Pseudo-capacitor device for aqueous electrolytes

    DOE Patents [OSTI]

    Prakash, J.; Thackeray, M.M.; Dees, D.W.; Vissers, D.R.; Myles, K.M.

    1998-11-24

    A pseudo-capacitor having a high energy storage capacity develops a double layer capacitance as well as a Faradaic or battery-like redox reaction, also referred to as pseudo-capacitance. The Faradaic reaction gives rise to a capacitance much greater than that of the typical ruthenate oxide ultracapacitor which develops only charge separation-based double layer capacitance. The capacitor employs a lead and/or bismuth/ruthenate and/or iridium system having the formula A{sub 2}[B{sub 2{minus}x}Pb{sub x}]O{sub 7{minus}y}, where A=Pb, Bi, and B=Ru, Ir, and O

  7. Pseudo-capacitor device for aqueous electrolytes

    DOE Patents [OSTI]

    Prakash, Jai; Thackeray, Michael M.; Dees, Dennis W.; Vissers, Donald R.; Myles, Kevin M.

    1998-01-01

    A pseudo-capacitor having a high energy storage capacity develops a double layer capacitance as well as a Faradaic or battery-like redox reaction, also referred to as pseudo-capacitance. The Faradaic reaction gives rise to a capacitance much greater than that of the typical ruthenate oxide ultracapacitor which develops only charge separation-based double layer capacitance. The capacitor employs a lead and/or bismuth/ruthenate and/or iridium system having the formula A.sub.2 ›B.sub.2-x Pb.sub.x !O.sub.7-y, where A=Pb, Bi, and B=Ru, Ir, and O

  8. Pseudo-capacitor device for aqueous electrolytes

    DOE Patents [OSTI]

    Prakash, Jai (3849 NW. 65th Ave., Gainesville, FL 32653); Thackeray, Michael M. (1763 Cliffside Ct., Naperville, IL 60565); Dees, Dennis W. (6224 Middaugh Ave., Downers Grove, IL 60516); Vissers, Donald R. (611 Clover Ct., Naperville, IL 60540); Myles, Kevin M. (1231 60th Pl., Downers Grove, IL 60516-1856)

    1998-01-01

    A pseudo-capacitor having a high energy storage capacity develops a double layer capacitance as well as a Faradaic or battery-like redox reaction, also referred to as pseudo-capacitance. The Faradaic reaction gives rise to a capacitance much greater than that of the typical ruthenate oxide ultracapacitor which develops only charge separation-based double layer capacitance. The capacitor employs a lead and/or bismuth/ruthenate and/or iridium system having the formula A.sub.2 B.sub.2-x Pb.sub.x !O.sub.7-y, where A=Pb, Bi, and B=Ru, Ir, and O

  9. Me-3,2-HOPO Complexes of Near Infra-Red (NIR) Emitting Lanthanides: Efficient Sensitization of Yb(III) and Nd(III) in Aqueous Solution

    SciTech Connect (OSTI)

    Moore, Evan G.; Xu, Jide; Dodani, Sheel; Jocher, Christoph; D'Aleo, Anthony; Seitz, Michael; Raymond, Kenneth

    2009-11-10

    The synthesis, X-ray structure, solution stability, and photophysical properties of several trivalent lanthanide complexes of Yb(III) and Nd(III) using both tetradentate and octadentate ligand design strategies and incorporating the 1-methyl-3-hydroxy-pyridin-2-one (Me-3,2-HOPO) chelate group are reported. Both the Yb(III) and Nd(III) complexes have emission bands in the Near Infra-Red (NIR) region, and this luminescence is retained in aqueous solution ({Phi}{sub tot}{sup Yb} {approx} 0.09-0.22%). Furthermore, the complexes demonstrate very high stability (pYb {approx} 18.8-21.9) in aqueous solution, making them good candidates for further development as probes for NIR imaging. Analysis of the low temperature (77 K) photophysical measurements for a model Gd(III) complex were used to gain an insight into the electronic structure, and were found to agree well with corresponding TD-DFT calculations at the B3LYP/6-311G{sup ++}(d,p) level of theory for a simplified model monovalent sodium complex.

  10. In situ soft X-ray absorption spectroscopy investigation of electrochemical corrosion of copper in aqueous NaHCO3 solution

    SciTech Connect (OSTI)

    Jiang, Peng; Chen, Jeng-Lung; Borondics, Ferenc; Glans, Per-Anders; West, Mark W.; Chang, Ching-Lin; Salmeron, Miquel; Guo, Jinghua

    2010-03-31

    A novel electrochemical setup has been developed for soft x-ray absorption studies of the electronic structure of electrode materials during electrochemical cycling. In this communication we illustrate the operation of the cell with a study of the corrosion behavior of copper in aqueous NaHCO3 solution via the electrochemically induced changes of its electronic structure. This development opens the way for in situ investigations of electrochemical processes, photovoltaics, batteries, fuel cells, water splitting, corrosion, electrodeposition, and a variety of important biological processes.