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Sample records for geothermometry cation geothermometers

  1. Cation Geothermometers | Open Energy Information

    Open Energy Info (EERE)

    prospect the fastest is obtaining attractive chemical confirmation (geothermometry, gas analyses) that a thermal resource exists in that location. As with all geothermal...

  2. Improvements in geothermometry. Final technical report

    SciTech Connect (OSTI)

    Potter, J.; Dibble, W.; Parks, G.; Nur, A.

    1982-07-01

    The following are covered: the basis of the Na-K-Ca geothermometer, geothermometry via model calculations, non ideality and complexing, and experimental calibration.

  3. Geothermometry At Yellowstone Region (Fournier, 1979) | Open...

    Open Energy Info (EERE)

    Geothermal Region Exploration Technique Geothermometry Activity Date Usefulness useful DOE-funding Unknown Notes Enthalpy-Chloride digram. Not exactly cation geothermometry...

  4. Multicomponent Equilibrium Models for Testing Geothermometry Approaches

    SciTech Connect (OSTI)

    Cooper, D. Craig; Palmer, Carl D.; Smith, Robert W.; McLing, Travis L.

    2013-02-01

    Geothermometry is an important tool for estimating deep reservoir temperature from the geochemical composition of shallower and cooler waters. The underlying assumption of geothermometry is that the waters collected from shallow wells and seeps maintain a chemical signature that reflects equilibrium in the deeper reservoir. Many of the geothermometers used in practice are based on correlation between water temperatures and composition or using thermodynamic calculations based a subset (typically silica, cations or cation ratios) of the dissolved constituents. An alternative approach is to use complete water compositions and equilibrium geochemical modeling to calculate the degree of disequilibrium (saturation index) for large number of potential reservoir minerals as a function of temperature. We have constructed several “forward” geochemical models using The Geochemist’s Workbench to simulate the change in chemical composition of reservoir fluids as they migrate toward the surface. These models explicitly account for the formation (mass and composition) of a steam phase and equilibrium partitioning of volatile components (e.g., CO2, H2S, and H2) into the steam as a result of pressure decreases associated with upward fluid migration from depth. We use the synthetic data generated from these simulations to determine the advantages and limitations of various geothermometry and optimization approaches for estimating the likely conditions (e.g., temperature, pCO2) to which the water was exposed in the deep subsurface. We demonstrate the magnitude of errors that can result from boiling, loss of volatiles, and analytical error from sampling and instrumental analysis. The estimated reservoir temperatures for these scenarios are also compared to conventional geothermometers. These results can help improve estimation of geothermal resource temperature during exploration and early development.

  5. Geothermometry At Coso Geothermal Area (1980) | Open Energy Informatio...

    Open Energy Info (EERE)

    DOE-funding Unknown Exploration Basis Fluid temperature of feed water Notes Cation and sulfate isotope geothermometers indicate that the reservoir feeding water to the Coso Hot...

  6. Geothermometry | Open Energy Information

    Open Energy Info (EERE)

    In The Past 20 Years- Geochemistry In Geothermal Exploration Resource Evaluation And Reservoir Management Geothermometry (Powell and Cumming, 2010) Any Spreadsheets for...

  7. Liquid Geothermometry | Open Energy Information

    Open Energy Info (EERE)

    Exploration Group: Geochemical Techniques Exploration Sub Group: Geochemical Data Analysis Parent Exploration Technique: Geothermometry Information Provided by Technique...

  8. Gas Geothermometry | Open Energy Information

    Open Energy Info (EERE)

    Exploration Group: Geochemical Techniques Exploration Sub Group: Geochemical Data Analysis Parent Exploration Technique: Geothermometry Information Provided by Technique...

  9. Isotope Geothermometry | Open Energy Information

    Open Energy Info (EERE)

    Exploration Group: Geochemical Techniques Exploration Sub Group: Geochemical Data Analysis Parent Exploration Technique: Geothermometry Information Provided by Technique...

  10. Category:Geothermometry | Open Energy Information

    Open Energy Info (EERE)

    Technique Subcategories This category has the following 2 subcategories, out of 2 total. G Gas Geothermometry 1 pages I Isotope Geothermometry 1 pages Pages in...

  11. Category:Gas Geothermometry | Open Energy Information

    Open Energy Info (EERE)

    Gas Geothermometry Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Geothermalpower.jpg Looking for the Gas Geothermometry page? For detailed information on Gas...

  12. Evaluation Of Chemical Geothermometers For Calculating Reservoir...

    Open Energy Info (EERE)

    Geothermometers For Calculating Reservoir Temperatures At Nevada Geothermal Power Plants Jump to: navigation, search OpenEI Reference LibraryAdd to library Conference Paper:...

  13. Improvements in geothermometry. Final technical report. Rev

    SciTech Connect (OSTI)

    Potter, J.; Dibble, W.; Parks, G.; Nur, A.

    1982-08-01

    Alkali and alkaline earth geothermometers are useful for estimating geothermal reservoir temperatures, though a general theoretical basis has yet to be established and experimental calibration needs improvement. Equilibrium cation exchange between feldspars provided the original basis for the Na-K and Na-K-Ca geothermometers (Fournier and Truesdell, 1973), but theoretical, field and experimental evidence prove that neither equilibrium nor feldspars are necessary. Here, evidence is summarized in support of these observations, concluding that these geothermometers can be expected to have a surprisingly wide range of applicability, but that the reasons behind such broad applicability are not yet understood. Early experimental work proved that water-rock interactions are slow at low temperatures, so experimental calibration at temperatures below 150/sup 0/ is impractical. Theoretical methods and field data were used instead for all work at low temperatures. Experimental methods were emphasized for temperatures above 150/sup 0/C, and the simplest possible solid and solution compositions were used to permit investigation of one process or question at a time. Unexpected results in experimental work prevented complete integration of the various portions of the investigation.

  14. Geothermometry At Lassen Volcanic National Park Area (Janik ...

    Open Energy Info (EERE)

    sample taken had a pH of 8.35 and contained 2100 ppm Cl and 0.55 ppm NH3. Ratios of Na+K+ and Na+Cl remained nearly constant throughout the flow test. Cation geothermometers...

  15. Integrated Chemical Geothermometry System for Geothermal Exploration |

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

    Department of Energy Chemical Geothermometry System for Geothermal Exploration Integrated Chemical Geothermometry System for Geothermal Exploration DOE Geothermal Peer Review 2010 - Presentation. Develop practical and reliable system to predict geothermal reservoir temperatures from integrated chemical analyses of spring and well fluids. tracers_spycher_integrated_chemical.pdf (272.32 KB) More Documents & Publications Integrated Chemical Geothermometry System for Geothermal Exploration

  16. Derivation and calibration of semi-empirical gas geothermometers for Mahanagdong Geothermal Project, Philippines

    SciTech Connect (OSTI)

    Sanchez, D.R.

    1996-12-31

    The dissolved CO{sub 2}, H{sub 2}S, and H{sub 2} gases in Mahanagdong aquifer fluids are controlled by specific gas-mineral equilibria. At temperature range of 250 to 310 {degrees}C, CO{sub 2} is buffered by clinozoisite + K-feldspar + calcite + muscovite (illite) + quartz mineral assemblage. For H{sub 2}S and H{sub 2} dissolved gases, they are more likely buffered by pyrrhotite + pyrite + magnetite mineral assemblage at similar temperature range. Calibration of five Mahanagdong (MG) gas geothermometers is presented, three of which used CO{sub 2}, H{sub 2}S, and H{sub 2} concentration in steam. The remaining two use CO{sub 2}/H{sub 2} and H{sub 2}S/H{sub 2} ratios. The calibration is based on the relation between gas content of drillhole discharges and measured aquifer temperatures. After establishing the gas content in the aquifer, gas concentrations were computed in steam after adiabatic boiling to atmospheric condition (100 {degrees}C), to obtain gas geothermometry functions. These functions could also be used in evaluating fraction of steam condensation and temperature of phase separation. A demonstration given the Mahanagdong fumarole data, indicates that there is generally a fair relation between computed temperatures using Mahanagdong gas geothermometers and the actual field trend`s temperatures.

  17. Geothermometry At Central Nevada Seismic Zone Region (Shevenell...

    Open Energy Info (EERE)

    Geothermometry At Central Nevada Seismic Zone Region (Shevenell & De Rocher, 2005) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry...

  18. Geothermometry At Nw Basin & Range Region (Shevenell & De Rocher...

    Open Energy Info (EERE)

    Geothermometry At Nw Basin & Range Region (Shevenell & De Rocher, 2005) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Nw...

  19. Geothermometry At Blackfoot Reservoir Area (Hutsinpiller & Parry...

    Open Energy Info (EERE)

    Activity Details Location Blackfoot Reservoir Area Exploration Technique Geothermometry Activity Date Usefulness useful DOE-funding Unknown References Amy Hutsinpiller, W. T....

  20. Cation Geothermometers At Lightning Dock Geothermal Area (Witcher...

    Open Energy Info (EERE)

    Usefulness useful DOE-funding Unknown Exploration Basis Part of the Geothermal Resource Evaluation and Definition (GRED) Program administered by DOE-AAO under Cooperative...

  1. Colorado thermal spring water geothermometry (public dataset...

    Open Energy Info (EERE)

    chemical geothermometers for Colorado thermal springs. Data citations include Barrett, J. K. and Pearl, R. H. (1976), George, R. D., Curtis, H. A., Lester, O. C., Crook, J. K.,...

  2. Improved Geothermometry Through Multivariate Reaction-path Modeling and Evaluation of Geomicrobiological Influences on Geochemical Temperature Indicators: Final Report

    SciTech Connect (OSTI)

    Mattson, Earl; Smith, Robert; Fujita, Yoshiko; McLing, Travis; Neupane, Ghanashyam; Palmer, Carl; Reed, David; Thompson, Vicki

    2015-03-01

    The project was aimed at demonstrating that the geothermometric predictions can be improved through the application of multi-element reaction path modeling that accounts for lithologic and tectonic settings, while also accounting for biological influences on geochemical temperature indicators. The limited utilization of chemical signatures by individual traditional geothermometer in the development of reservoir temperature estimates may have been constraining their reliability for evaluation of potential geothermal resources. This project, however, was intended to build a geothermometry tool which can integrate multi-component reaction path modeling with process-optimization capability that can be applied to dilute, low-temperature water samples to consistently predict reservoir temperature within ±30 °C. The project was also intended to evaluate the extent to which microbiological processes can modulate the geochemical signals in some thermal waters and influence the geothermometric predictions.

  3. Geothermometry At Mt St Helens Area (Shevenell & Goff, 1995)...

    Open Energy Info (EERE)

    St Helens Area (Shevenell & Goff, 1995) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Mt St Helens Area (Shevenell & Goff,...

  4. Geothermometry At Walker-Lane Transitional Zone Region (Shevenell...

    Open Energy Info (EERE)

    (Shevenell & De Rocher, 2005) Exploration Activity Details Location Walker-Lane Transition Zone Geothermal Region Exploration Technique Geothermometry Activity Date Usefulness...

  5. Geothermometry At Walker-Lane Transitional Zone Region (Laney...

    Open Energy Info (EERE)

    Zone Region (Laney, 2005) Exploration Activity Details Location Walker-Lane Transition Zone Geothermal Region Exploration Technique Geothermometry Activity Date Usefulness...

  6. Geothermometry At Blue Mountain Geothermal Area (Casteel, Et...

    Open Energy Info (EERE)

    Details Location Blue Mountain Geothermal Area Exploration Technique Geothermometry Activity Date 2010 - 2010 Usefulness useful DOE-funding Unknown Exploration Basis A water...

  7. Geothermometry At Upper Hot Creek Ranch Area (Benoit & Blackwell...

    Open Energy Info (EERE)

    Activity Details Location Upper Hot Creek Ranch Area Exploration Technique Geothermometry Activity Date Usefulness useful DOE-funding Unknown Notes Ten water samples were collected...

  8. Geothermometry At Clear Lake Area (Thompson, Et Al., 1992) |...

    Open Energy Info (EERE)

    Activity Details Location Clear Lake Area Exploration Technique Geothermometry Activity Date Usefulness useful DOE-funding Unknown Notes Based on the above discussion,...

  9. Geothermometry At Silver Peak Area (DOE GTP) | Open Energy Information

    Open Energy Info (EERE)

    Silver Peak Area (DOE GTP) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Silver Peak Area (DOE GTP) Exploration Activity...

  10. Geothermometry At Alum Area (DOE GTP) | Open Energy Information

    Open Energy Info (EERE)

    Alum Area (DOE GTP) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Alum Area (DOE GTP) Exploration Activity Details Location...

  11. Geothermometry At The Needles Area (DOE GTP) | Open Energy Information

    Open Energy Info (EERE)

    The Needles Area (DOE GTP) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At The Needles Area (DOE GTP) Exploration Activity...

  12. Geothermometry At New River Area (DOE GTP) | Open Energy Information

    Open Energy Info (EERE)

    New River Area (DOE GTP) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At New River Area (DOE GTP) Exploration Activity Details...

  13. Geothermometry At Fort Bliss Area (DOE GTP) | Open Energy Information

    Open Energy Info (EERE)

    Fort Bliss Area (DOE GTP) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Fort Bliss Area (DOE GTP) Exploration Activity...

  14. Geothermometry At Lassen Volcanic National Park Area (Thompson...

    Open Energy Info (EERE)

    Thompson, 1985) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Lassen Volcanic National Park Area (Thompson, 1985) Exploration...

  15. Geothermometry At Chena Geothermal Area (Kolker, 2008) | Open...

    Open Energy Info (EERE)

    1973 - 1974 Usefulness not indicated DOE-funding Unknown Exploration Basis Masters thesis Norma Biggar, Geophysical Institute University of Alaska Notes Geothermometry...

  16. Geothermometry At Fish Lake Valley Area (DOE GTP) | Open Energy...

    Open Energy Info (EERE)

    Fish Lake Valley Area (DOE GTP) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Fish Lake Valley Area (DOE GTP) Exploration...

  17. Geothermometry At Akutan Fumaroles Area (Kolker, Et Al., 2010...

    Open Energy Info (EERE)

    Geothermometry Activity Date Usefulness useful DOE-funding Unknown Notes The chemistry of the hot springs strongly suggests the existence of a neutral chloride reservoir...

  18. Geothermometry At Desert Queen Area (Garchar & Arehart, 2008...

    Open Energy Info (EERE)

    Desert Queen Area (Garchar & Arehart, 2008) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Desert Queen Area (Garchar &...

  19. Geothermometry At Nevada Test And Training Range Area (Sabin...

    Open Energy Info (EERE)

    Nevada Test And Training Range Area (Sabin, Et Al., 2004) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Nevada Test And...

  20. Geothermometry At Teels Marsh Area (Coolbaugh, Et Al., 2006)...

    Open Energy Info (EERE)

    useful DOE-funding Unknown Notes Follow up (to ASTER satellite imaging) analysis of spring and well waters yielded geothermometer reservoir estimates up to 192C References...

  1. Geothermometry At Rhodes Marsh Area (Coolbaugh, Et Al., 2006...

    Open Energy Info (EERE)

    useful DOE-funding Unknown Notes Follow up (to ASTER satellite imaging) analysis of spring and well waters yielded geothermometer reservoir estimates up to 162C References...

  2. New Mexico conservative ion water chemistry data and chalcedony geothermometry

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Shari Kelley

    2015-10-21

    Compilation of boron, lithium, bromine, and silica data from wells and springs throughout New Mexico from a wide variety of sources. The chalcedony geothermometry calculation is included in this file.

  3. Microbial impacts on geothermometry temperature predictions

    SciTech Connect (OSTI)

    Yoshiko Fujita; David W. Reed; Kaitlyn R. Nowak; Vicki S. Thompson; Travis L. McLing; Robert W. Smith

    2013-02-01

    Conventional geothermometry approaches assume that the composition of a collected water sample originating in a deep geothermal reservoir still reflects chemical equilibration of the water with the deep reservoir rocks. However, for geothermal prospecting samples whose temperatures have dropped to <120°C, temperature predictions may be skewed by the activity of microorganisms; microbial metabolism can drastically and rapidly change the water’s chemistry. We hypothesize that knowledge of microbial impacts on exploration sample geochemistry can be used to constrain input into geothermometry models and thereby improve the reliability of reservoir temperature predictions. To evaluate this hypothesis we have chosen to focus on sulfur cycling, because of the significant changes in redox state and pH associated with sulfur chemistry. Redox and pH are critical factors in defining the mineral-fluid equilibria that form the basis of solute geothermometry approaches. Initially we are developing assays to detect the process of sulfate reduction, using knowledge of genes specific to sulfate reducing microorganisms. The assays rely on a common molecular biological technique known as quantitative polymerase chain reaction (qPCR), which allows estimation of the number of target organisms in a particular sample by enumerating genes specific to the organisms rather than actually retrieving and characterizing the organisms themselves. For quantitation of sulfate reducing genes using qPCR, we constructed a plasmid (a piece of DNA) containing portions of two genes (known as dsrA and dsrB) that are directly involved with sulfate reduction and unique to sulfate reducing microorganisms. Using the plasmid as well as DNA from other microorganisms known to be sulfate reducers or non-sulfate reducers, we developed qPCR protocols and showed the assay’s specificity to sulfate reducers and that a qPCR standard curve using the plasmid was linear over >5 orders of magnitude. As a first test

  4. Mineral Selection for Multicomponent Equilibrium Geothermometry

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

    Plamer, C. D.; Ohly, S. R.; Smith, R. W.; Neupane, G.; McLing, T.; Mattson, E.

    2015-04-01

    Multicomponent geothermometry requires knowledge of the mineral phases in the reservoir with which the geothermal fluids may be equilibrated. These minerals phases are most often alteration products rather than primary minerals. We have reviewed the literature on geothermal systems representing most major geologic environments typically associated with geothermal activity and identified potential alteration products in various environments. We have included this information in RTEst, a code we have developed to estimate reservoir conditions (temperature, CO2 fugacity) from the geochemistry of near-surface geothermal waters. The information has been included in RTEst through the addition of filters that decrease the potential numbermore » of minerals from all possibilities based on the basis species to those that are more relevant to the particular conditions in which the user is interested. The three groups of filters include host rock type (tholeiitic, calc-alkaline, silicic, siliciclastic, carbonate), water type (acidic, neutral), and the temperature range over which the alteration minerals were formed (low, medium, high). The user-chosen mineral assemblage is checked to make sure that it does not violate the Gibbs phase rule. The user can select one of three mineral saturation weighting schemes that decrease the chance the optimization from being skewed by reaction stoichiometry or analytical uncertainty.« less

  5. Mineral Selection for Multicomponent Equilibrium Geothermometry

    SciTech Connect (OSTI)

    Plamer, C. D.; Ohly, S. R.; Smith, R. W.; Neupane, G.; McLing, T.; Mattson, E.

    2015-04-01

    Multicomponent geothermometry requires knowledge of the mineral phases in the reservoir with which the geothermal fluids may be equilibrated. These minerals phases are most often alteration products rather than primary minerals. We have reviewed the literature on geothermal systems representing most major geologic environments typically associated with geothermal activity and identified potential alteration products in various environments. We have included this information in RTEst, a code we have developed to estimate reservoir conditions (temperature, CO2 fugacity) from the geochemistry of near-surface geothermal waters. The information has been included in RTEst through the addition of filters that decrease the potential number of minerals from all possibilities based on the basis species to those that are more relevant to the particular conditions in which the user is interested. The three groups of filters include host rock type (tholeiitic, calc-alkaline, silicic, siliciclastic, carbonate), water type (acidic, neutral), and the temperature range over which the alteration minerals were formed (low, medium, high). The user-chosen mineral assemblage is checked to make sure that it does not violate the Gibbs phase rule. The user can select one of three mineral saturation weighting schemes that decrease the chance the optimization from being skewed by reaction stoichiometry or analytical uncertainty.

  6. New Improved Equations For Na-K, Na-Li And Sio2 Geothermometers...

    Open Energy Info (EERE)

    Improved Equations For Na-K, Na-Li And Sio2 Geothermometers By Outlier Detection And Rejection Jump to: navigation, search OpenEI Reference LibraryAdd to library Journal Article:...

  7. Improved Geothermometry Through Multivariate Reaction Path Modeling and Evaluation of Geomicrobiological Influences on Geochemical Temperature Indicators

    Broader source: Energy.gov [DOE]

    Improved Geothermometry Through Multivariate Reaction Path Modeling and Evaluation of Geomicrobiological Influences on Geochemical Temperature Indicators presentation at the April 2013 peer review meeting held in Denver, Colorado.

  8. Improved Geothermometry Through Multivariate Reaction Path Modeling and Evaluation of Geomicrobiological Influences on Geochemical Temperature Indicators

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

    Improved Geothermometry Through Multivariate Reaction Path Modeling and Evaluation of Geomicrobiological Influences on Geochemical Temperature Indicators Project Officer: Eric Hass Total Project Funding: $999,000 April 24, 2013 Craig Cooper Larry Hull Idaho National Laboratory This presentation does not contain any proprietary confidential, or otherwise restricted information. 2 | US DOE Geothermal Program eere.energy.gov Relevance/Impact of Research Geothermometry enables estimation of

  9. Geochemistry Sampling for Traditional and Multicomponent Equilibrium Geothermometry in Southeast Idaho

    SciTech Connect (OSTI)

    Cannon, Cody; Wood, Thomas; Neupane, Ghanashyam; McLing, Travis; Mattson, Earl; Dobson, Patrick; Conrad, Mark

    2014-10-01

    The Eastern Snake River Plain (ESRP) is an area of high regional heat flux due the movement of the North American Plate over the Yellowstone Hotspot beginning ca.16 Ma. Temperature gradients between 45-60 °C/km (up to double the global average) have been calculated from deep wells that penetrate the upper aquifer system (Blackwell 1989). Despite the high geothermal potential, thermal signatures from hot springs and wells are effectively masked by the rapid flow of cold groundwater through the highly permeable basalts of the Eastern Snake River Plain aquifer (ESRPA) (up to 500+ m thick). This preliminary study is part of an effort to more accurately predict temperatures of the ESRP deep thermal reservoir while accounting for the effects of the prolific cold water aquifer system above. This study combines the use of traditional geothermometry, mixing models, and a multicomponent equilibrium geothermometry (MEG) tool to investigate the geothermal potential of the ESRP. In March, 2014, a collaborative team including members of the University of Idaho, the Idaho National Laboratory, and the Lawrence Berkeley National Laboratory collected 14 thermal water samples from and adjacent to the Eastern Snake River Plain. The preliminary results of chemical analyses and geothermometry applied to these samples are presented herein.

  10. Multicomponent Geothermometers | Open Energy Information

    Open Energy Info (EERE)

    of using full chemical analyses of water samples to compute the saturation indices (log(QK)) of reservoir minerals over a range of temperatures. The saturation indices are graphed...

  11. Silica Geothermometers | Open Energy Information

    Open Energy Info (EERE)

    in the Past 20 Years: Geochemistry in Geothermal Exploration, Resource Evaluation and Reservoir Management 2.0 2.1 Lectures on Geochemical Interpretation of Hydrothermal...

  12. The Role of Cation-Water Disorder during Cation Exchange in Small...

    Office of Scientific and Technical Information (OSTI)

    The Role of Cation-Water Disorder during Cation Exchange in Small-Pore Zeolite Sodium Natrolite Citation Details In-Document Search Title: The Role of Cation-Water Disorder during ...

  13. Cationic electrodepositable coating composition comprising lignin

    DOE Patents [OSTI]

    Fenn, David; Bowman, Mark P; Zawacky, Steven R; Van Buskirk, Ellor J; Kamarchik, Peter

    2013-07-30

    A cationic electrodepositable coating composition is disclosed. The present invention in directed to a cationic electrodepositable coating composition comprising a lignin-containing cationic salt resin, that comprises (A) the reaction product of: lignin, an amine, and a carbonyl compound; (B) the reaction product of lignin, epichlorohydrin, and an amine; or (C) combinations thereof.

  14. Geology, hydrothermal petrology, stable isotope geochemistry, and fluid inclusion geothermometry of LASL geothermal test well C/T-1 (Mesa 31-1), East Mesa, Imperial Valley, California, USA

    SciTech Connect (OSTI)

    Miller, K.R.; Elders, W.A.

    1980-08-01

    Borehole Mesa 31-1 (LASL C/T-1) is an 1899-m (6231-ft) deep well located in the northwestern part of the East Mesa Geothermal Field. Mesa 31-1 is the first Calibration/Test Well (C/T-1) in the Los Alamos Scientific Laboratory (LASL), Geothermal Log Interpretation Program. The purpose of this study is to provide a compilation of drillhole data, drill cuttings, well lithology, and formation petrology that will serve to support the use of well LASL C/T-1 as a calibration/test well for geothermal logging. In addition, reviews of fluid chemistry, stable isotope studies, isotopic and fluid inclusion geothermometry, and the temperature log data are presented. This study provides the basic data on the geology and hydrothermal alteration of the rocks in LASL C/T-1 as background for the interpretation of wireline logs.

  15. ADSORPTION METHOD FOR SEPARATING METAL CATIONS

    DOE Patents [OSTI]

    Khym, J.X.

    1959-03-10

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

  16. Role of Cation-Water Disorder during Cation Exchange in Small-Pore Zeolite

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

    Sodium Natrolite | Stanford Synchrotron Radiation Lightsource Role of Cation-Water Disorder during Cation Exchange in Small-Pore Zeolite Sodium Natrolite Thursday, October 31, 2013 Structural changes leading to disordering of the cation-water arrangement within the pores of zeolite natrolite while exchanging sodium (Na+) with potassium (K+) have been investigated using x-ray diffraction (XRD) and oxygen K-edge x-ray absorption spectroscopy (XAS). cation in zeolite sodium natrolite fig1

  17. Method for encapsulating and isolating hazardous cations, medium for encapsulating and isolating hazardous cations

    DOE Patents [OSTI]

    Wasserman, Stephen R.; Anderson, Kenneth B.; Song, Kang; Yuchs, Steven E.; Marshall, Christopher L.

    1998-01-01

    A method for encapsulating hazardous cations is provided comprising supplying a pretreated substrate containing the cations; contacting the substrate with an organo-silane compound to form a coating on the substrate; and allowing the coating to cure. A medium for containing hazardous cations is also provided, comprising a substrate having ion-exchange capacity and a silane-containing coating on the substrate.

  18. Advancements in Anion Exchange Membrane Cations

    SciTech Connect (OSTI)

    Sturgeon, Matthew R.; Long, Hai; Park, Andrew M.; Pivovar, Bryan S.

    2015-10-15

    Anion-exchange membrane fuel cells (AME-FCs) are of increasingly popular interest as they enable the use of non-Pt fuel cell catalysts, the primary cost limitation of proton exchange membrane fuel cells. Benzyltrimethyl ammonium (BTMA) is the standard cation that has historically been utilized as the hydroxide conductor in AEMs. Herein we approach AEMs from two directions. First and foremost we study the stability of several different cations in a hydroxide solution at elevated temperatures. We specifically targeted BTMA and methoxy and nitro substituted BTMA. We've also studied the effects of adding an akyl spacer units between the ammonium cation and the phenyl group. In the second approach we use computational studies to predict stable ammonium cations, which are then synthesized and tested for stability. Our unique method to study cation stability in caustic conditions at elevated temperatures utilizes Teflon Parr reactors suitable for use under various temperatures and cation concentrations. NMR analysis was used to determine remaining cation concentrations at specific time points with GCMS analysis verifying product distribution. We then compare the experimental results with calculated modeling stabilities. Our studies show that the electron donating methoxy groups slightly increase stability (compared to that of BTMA), while the electron withdrawing nitro groups greatly decrease stability in base. These results give insight into possible linking strategies to be employed when tethering a BTMA like ammonium cation to a polymeric backbone; thus synthesizing an anion exchange membrane.

  19. Method for encapsulating and isolating hazardous cations, medium for encapsulating and isolating hazardous cations

    DOE Patents [OSTI]

    Wasserman, S.R.; Anderson, K.B.; Song, K.; Yuchs, S.E.; Marshall, C.L.

    1998-04-28

    A method for encapsulating hazardous cations is provided comprising supplying a pretreated substrate containing the cations; contacting the substrate with an organo-silane compound to form a coating on the substrate; and allowing the coating to cure. A medium for containing hazardous cations is also provided, comprising a substrate having ion-exchange capacity and a silane-containing coating on the substrate. 3 figs.

  20. ABSORPTION METHOD FOR SEPARATING METAL CATIONS

    DOE Patents [OSTI]

    Tompkins, E.R.; Parker, G.W.

    1959-03-10

    An improved method is presented for the chromatographic separation of fission products wherein a substantial reduction in liquid volume is obtained. The process consists in contacting a solution containing fission products with a body of ion-exchange adsorbent to effect adsorption of fission product cations. The loaded exchange resin is then contacted with a small volume of a carboxylic acid eluant, thereby recovering the fission products. The fission product carrying eluate is acidified without increasing its volume to the volume of the original solution, and the acidified eluate is then used as a feed solution for a smaller body of ion-exchange resin effecting readsorption of the fission product cations.

  1. Process and apparatus for the production of BI-213 cations

    DOE Patents [OSTI]

    Horwitz, E. Philip; Hines, John J.; Chiarizia, Renato; Dietz, Mark

    1998-01-01

    A process for producing substantially impurity-free Bi-213 cations is disclosed. An aqueous acid feed solution containing Ac-225 cations is contacted with an ion exchange medium to bind the Ac-225 cations and form an Ac-225-laden ion exchange medium. The bound Ac-225 incubates on the ion exchange medium to form Bi-213 cations by radioactive decay. The Bi-213 cations are then recovered from the Ac-225-laden ion exchange medium to form a substantially impurity-free aqueous Bi-213 cation acid solution. An apparatus for carrying out this process is also disclosed.

  2. Process and apparatus for the production of Bi-213 cations

    DOE Patents [OSTI]

    Horwitz, E.P.; Hines, J.J.; Chiarizia, R.; Dietz, M.

    1998-12-29

    A process for producing substantially impurity-free Bi-213 cations is disclosed. An aqueous acid feed solution containing Ac-225 cations is contacted with an ion exchange medium to bind the Ac-225 cations and form an Ac-225-laden ion exchange medium. The bound Ac-225 incubates on the ion exchange medium to form Bi-213 cations by radioactive decay. The Bi-213 cations are then recovered from the Ac-225-laden ion exchange medium to form a substantially impurity-free aqueous Bi-213 cation acid solution. An apparatus for carrying out this process is also disclosed. 7 figs.

  3. Role of Cation-Water Disorder during Cation Exchange in Small...

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

    while exchanging sodium (Na+) with potassium (K+) have been investigated using x-ray diffraction (XRD) and oxygen K-edge x-ray absorption spectroscopy (XAS). cation in zeolite...

  4. Alkaline earth cation extraction from acid solution

    DOE Patents [OSTI]

    Dietz, Mark; Horwitz, E. Philip

    2003-01-01

    An extractant medium for extracting alkaline earth cations from an aqueous acidic sample solution is described as are a method and apparatus for using the same. The separation medium is free of diluent, free-flowing and particulate, and comprises a Crown ether that is a 4,4'(5')[C.sub.4 -C.sub.8 -alkylcyclohexano]18-Crown-6 dispersed on an inert substrate material.

  5. Nanoheterostructure Cation Exchange: Anionic Framework Conservation

    SciTech Connect (OSTI)

    Jain, Prashant K.; Amirav, Lilac; Aloni, Shaul; Alivisatos, A. Paul

    2010-05-11

    In ionic nanocrystals the cationic sub-lattice can be replaced with a different metal ion via a fast, simple, and reversible place-exchange, allowing post-synthetic modification of the composition of the nanocrystal, while preserving its size and shape. Here, we demonstrate for the first time that during such an exchange, the anionic framework of the crystal is preserved. When applied to nanoheterostructures, this phenomenon ensures that compositional interfaces within the heterostructure are conserved throughout the transformation. For instance, a morphology composed of a CdSe nanocrystal embedded in a CdS rod (CdSe/CdS) was exchanged to a PbSe/PbS nanorod via a Cu2Se/Cu2S structure. During every exchange cycle, the seed size and position within the nanorod were preserved, as evident by excitonic features, Z-contrast imaging, and elemental line-scans. Anionic framework conservation extends the domain of cation exchange to the design of more complex and unique nanostructures.

  6. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOE Patents [OSTI]

    O`Neill, M.A.; Pellerin, P.J.M.; Warrenfeltz, D.; Vidal, S.; Darvill, A.G.; Albersheim, P.

    1999-03-02

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations. 15 figs.

  7. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOE Patents [OSTI]

    O'Neill, Malcolm A.; Pellerin, Patrice J. M.; Warrenfeltz, Dennis; Vidal, Stephane; Darvill, Alan G.; Albersheim, Peter

    1999-01-01

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations.

  8. Colloid-Facilitated Transport of Cations in an Unsaturated Fractured...

    Office of Scientific and Technical Information (OSTI)

    Fractured Soil Under Transient Conditions Citation Details In-Document Search Title: Colloid-Facilitated Transport of Cations in an Unsaturated Fractured Soil Under Transient ...

  9. High capacity nickel battery material doped with alkali metal cations

    DOE Patents [OSTI]

    Jackovitz, John F.; Pantier, Earl A.

    1982-05-18

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

  10. CATION EXCHANGE METHOD FOR THE RECOVERY OF PROTACTINIUM

    DOE Patents [OSTI]

    Studier, M.H.; Sullivan, J.C.

    1959-07-14

    A cation exchange prccess is described for separating protactinium values from thorium values whereby they are initially adsorbed together from an aqueous 0.1 to 2 N hydrochloric acid on a cation exchange resin in a column. Then selectively eluting the thorium by an ammonium sulfate solution and subsequently eluting the protactinium by an oxalate solution.

  11. Improved Geothermometry Through Multivariate Reaction Path Modeling...

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

    at the April 2013 peer review meeting held in Denver, Colorado. geothermometrycooperpeer2013.pdf (922.86 KB) More Documents & Publications track 4: enhanced geothermal ...

  12. Geothermometry (Klein, 2007) | Open Energy Information

    Open Energy Info (EERE)

    In The Past 20 Years- Geochemistry In Geothermal Exploration Resource Evaluation And Reservoir Management Additional References Retrieved from "http:en.openei.orgw...

  13. Integrated Chemical Geothermometry System for Geothermal Exploration

    Broader source: Energy.gov [DOE]

    DOE Geothermal Peer Review 2010 - Presentation. Develop practical and reliable system to predict geothermal reservoir temperatures from integrated chemical analyses of spring and well fluids.

  14. Method for the chromatographic separation of cations from aqueous samples

    DOE Patents [OSTI]

    Horwitz, E. Philip (Naperville, IL); Chiarizia, Renato (Elmhurst, IL); Dietz, Mark L. (Evanston, IL)

    1997-01-01

    An extraction chromatographic material for extracting metal cations from a iquid stream. The extraction chromatographic material is prepared by adsorbing a diesterified methanediphosphonic acid on an inert particulate support.

  15. Method for the chromatographic separation of cations from aqueous samples

    DOE Patents [OSTI]

    Horwitz, E.P.; Chiarizia, R.; Dietz, M.L.

    1997-07-29

    An extraction chromatographic material is described for extracting metal cations from a liquid stream. The extraction chromatographic material is prepared by adsorbing a diesterified methanediphosphonic acid on an inert particulate support. 7 figs.

  16. Method for the chromatographic separation of cations from aqueous samples

    DOE Patents [OSTI]

    Horwitz, E.P.; Chiarizia, R.; Dietz, M.L.

    1998-12-22

    An extraction chromatographic material is described for extracting metal cations from a liquid stream. The extraction chromatographic material is prepared by adsorbing a diesterified methane-diphosphonic acid on an inert particulate support. 7 figs.

  17. Method for the chromatographic separation of cations from aqueous samples

    DOE Patents [OSTI]

    Horwitz, E. Philip (Naperville, IL); Chiarizia, Renato (Elmhurst, IL); Dietz, Mark L. (Evanston, IL)

    1998-12-22

    An extraction chromatographic material for extracting metal cations from a liquid stream. The extraction chromatographic material is prepared by adsorbing a diesterified methanediphosphonic acid on an inert particulate support.

  18. Mechanistic Insight into the Formation of Cationic Naked Nanocrystals

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

    Generated Under Equilibrium Control - Joint Center for Energy Storage Research October 24, 2014, Research Highlights Mechanistic Insight into the Formation of Cationic Naked Nanocrystals Generated Under Equilibrium Control Pre-JCESR stripping chemistries (for cationic NC): NOBF4 (strong oxidant, not suitable for many compositions, ~$600/mol) Et3OBF4 (mild, but still causes adatom desorption for some sensitive compositions, ~$800/mol) New ligand-stripping chemistry developed within JCESR:

  19. Characterization of Selective Binding of Alkali Cations with Carboxylate

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

    Characterization of Selective Binding of Alkali Cations with Carboxylate Characterization of Selective Binding of Alkali Cations with Carboxylate Print Wednesday, 24 September 2008 00:00 During its lifetime, a cell spends a considerable fraction of its energy pumping sodium and calcium out and potassium in. This balancing process is similar to that found in the coils of the DNA double helix, where specific ions nestle and help stabilize this macromolecule. These are only two examples of

  20. Cation Uptake and Allocation by Red Pine Seedlings under Cation-Nutrient Stress in a Column Growth Experiment

    SciTech Connect (OSTI)

    Shi, Zhenqing; Balogh-Brunstad, Zsuzsanna; Grant, Michael R.; Harsh, James B.; Gill, Richard; Thomashow, Linda; Dohnalkova, Alice; Stacks, Daryl; Letourneau, Melissa; Keller, Chester K.

    2014-01-10

    Background and Aims Plant nutrient uptake is affected by environmental stress, but how plants respond to cation-nutrient stress is poorly understood. We assessed the impact of varying degrees of cation-nutrient limitation on cation uptake in an experimental plant-mineral system. Methods Column experiments, with red pine (Pinus resinosa Ait.) seedlings growing in sand/mineral mixtures, were conducted for up to nine months under a range of Ca- and K-limited conditions. The Ca and K were supplied from both minerals and nutrient solutions with varying Ca and K concentrations. Results Cation nutrient stress had little impact on carbon allocation after nine months of plant growth and K was the limiting nutrient for biomass production. The Ca/Sr and K/Rb ratio results allowed independent estimation of dissolution incongruency and discrimination against Sr and Rb during cation uptake processes. The fraction of K in biomass from biotite increased with decreasing K supply from nutrient solutions. The mineral anorthite was consistently the major source of Ca, regardless of nutrient treatment. Conclusions Red pine seedlings exploited more mineral K in response to more severe K deficiency. This did not occur for Ca. Plant discrimination factors must be carefully considered to accurately identify nutrient sources using cation tracers.

  1. Chemical Geothermometers And Mixing Models For Geothermal Systems...

    Open Energy Info (EERE)

    to outline favorable places to explore for geothermal energy. Some of the qualitative methods, such as the delineation of mercury and helium anomalies in soil gases, do not...

  2. Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations

    DOE Patents [OSTI]

    Marks, Tobin J.; Chen, You-Xian

    1999-01-01

    A cationic metallocene complex with trisperfluorobiphenyl borate for use as a polymerization catalyst.

  3. In situ remediation process using divalent metal cations

    DOE Patents [OSTI]

    Brady, Patrick V.; Khandaker, Nadim R.; Krumhansl, James L.; Teter, David M.

    2004-12-14

    An in situ process for treating ambient solid materials (e.g., soils, aquifer solids, sludges) by adding one or more divalent metal cations to the ambient solid material. The added divalent metal cations, such as Cu.sup.2+ or Zn.sup.2+, combine with metal oxide/hydroxides (e.g., ferric oxide/hydroxide or aluminum oxide/hydroxide) already present in the ambient solid material to form an effective sorbent material having a large number of positively-charged surface complexes that binds and immobilizes anionic contaminant species (e.g., arsenic or chromate). Divalent metal cations can be added, for example, by injecting an aqueous solution of CuSO.sub.4 into an aquifer contaminated with arsenic or chromate. Also, sludges can be stabilized against leaching of anionic contaminants through the addition of divalent metal cations. Also, an inexpensive sorbent material can be easily formed by mixing divalent metal cations with soil that has been removed from the ground.

  4. All-inorganic Germanium nanocrystal films by cationic ligand exchange

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

    Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; Anderson, Nicholas C.; Beard, Matthew C.; Neale, Nathan R.

    2016-01-21

    In this study, we introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport inmore » germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.« less

  5. Bistability of Cation Interstitials in II-VI Semiconductors

    SciTech Connect (OSTI)

    Wei, S. H.; Dalpian, G. M.

    2005-11-01

    The stability of cation interstitials in II-VI semiconductors is studied using ab initio methods. We find that interstitials in the neutral charge state are more stable in the tetrahedral interstitial site near the cation, whereas in the (2+) charge state, they are more stable near the anion. The diffusion energy barrier changes when the defect charge state changes. Therefore, if electrons/holes are taken from the defect level by light, changing its charge state, the interstitial atom will be able to diffuse almost spontaneously due to a reduced diffusion barrier.

  6. Geochemical Techniques | Open Energy Information

    Open Energy Info (EERE)

    Geothermometers Multicomponent Geothermometers Silica Geothermometers Thermal Ion Dispersion Thermochronometry References General References Technical References No exploration...

  7. Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations

    DOE Patents [OSTI]

    Marks, T.J.; Chen, Y.X.

    1999-01-05

    A cationic metallocene complex with trisperfluorobiphenyl borate is described for use as a polymerization catalyst. 7 figs.

  8. Characterization of Selective Binding of Alkali Cations with Carboxylate

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

    Characterization of Selective Binding of Alkali Cations with Carboxylate Print During its lifetime, a cell spends a considerable fraction of its energy pumping sodium and calcium out and potassium in. This balancing process is similar to that found in the coils of the DNA double helix, where specific ions nestle and help stabilize this macromolecule. These are only two examples of selective ion interactions in biology; there are many others also vital to life. The existence of these interactions

  9. Characterization of Selective Binding of Alkali Cations with Carboxylate

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

    Characterization of Selective Binding of Alkali Cations with Carboxylate Print During its lifetime, a cell spends a considerable fraction of its energy pumping sodium and calcium out and potassium in. This balancing process is similar to that found in the coils of the DNA double helix, where specific ions nestle and help stabilize this macromolecule. These are only two examples of selective ion interactions in biology; there are many others also vital to life. The existence of these interactions

  10. Solvation Structure and Transport Properties of Alkali Cations in Dimethyl

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

    Sulfoxide Under Exogenous Static Electric Fields - Joint Center for Energy Storage Research June 14, 2015, Research Highlights Solvation Structure and Transport Properties of Alkali Cations in Dimethyl Sulfoxide Under Exogenous Static Electric Fields Top: Snapshots of molecular dynamics simulations of alkali ions in DMSO at 298 K and zero-applied electric field: (left) Li+ and (right) Cs+. Sulfur atoms are shown in yellow, oxygen atoms in red, and methyl groups in gray. Graph: Average

  11. Characterization of Selective Binding of Alkali Cations with Carboxylate

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

    Characterization of Selective Binding of Alkali Cations with Carboxylate Print During its lifetime, a cell spends a considerable fraction of its energy pumping sodium and calcium out and potassium in. This balancing process is similar to that found in the coils of the DNA double helix, where specific ions nestle and help stabilize this macromolecule. These are only two examples of selective ion interactions in biology; there are many others also vital to life. The existence of these interactions

  12. Characterization of Selective Binding of Alkali Cations with Carboxylate

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

    Characterization of Selective Binding of Alkali Cations with Carboxylate Print During its lifetime, a cell spends a considerable fraction of its energy pumping sodium and calcium out and potassium in. This balancing process is similar to that found in the coils of the DNA double helix, where specific ions nestle and help stabilize this macromolecule. These are only two examples of selective ion interactions in biology; there are many others also vital to life. The existence of these interactions

  13. Characterization of Selective Binding of Alkali Cations with Carboxylate

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

    Characterization of Selective Binding of Alkali Cations with Carboxylate Print During its lifetime, a cell spends a considerable fraction of its energy pumping sodium and calcium out and potassium in. This balancing process is similar to that found in the coils of the DNA double helix, where specific ions nestle and help stabilize this macromolecule. These are only two examples of selective ion interactions in biology; there are many others also vital to life. The existence of these interactions

  14. Selective Facet Reactivity During Cation Exchange in Cadmium Sulfide Nanorods

    SciTech Connect (OSTI)

    Sadtler, Bryce; Demchenko, Denis; Zheng, Haimei; Hughes, Steven; Merkle, Maxwell; Dahmen, Ulrich; Wang, Lin-Wang; Alivisatos, A. Paul

    2008-12-18

    The partial transformation of ionic nanocrystals through cation exchange has been used to synthesize nanocrystal heterostructures. We demonstrate that the selectivity for cation exchange to take place at different facets of the nanocrystal plays an important role in determining the resulting morphology of the binary heterostructure. In the case of copper I (Cu+) cation exchange in cadmium sulfide (CdS) nanorods, the reaction starts preferentially at the ends of the nanorods such that copper sulfide (Cu2S) grows inwards from either end. The resulting morphology is very different from the striped pattern obtained in our previous studies of silver I (Ag+) exchange in CdS nanorods where non-selective nucleation of silver sulfide (Ag2S) occurs. From interface formation energies calculated for several models of epitaxialconnections between CdS and Cu2S or Ag2S, we infer the relative stability of each interface during the nucleation and growth of Cu2S or Ag2S within the CdS nanorods. The epitaxial connections of Cu2S to the end facets of CdS nanorods minimize the formation energy, making these interfaces stable throughout the exchange reaction. However, as the two end facets of wurtzite CdS nanorods are crystallographically nonequivalent, asymmetric heterostructures can be produced.

  15. Advective (heat sweep) geothermal systems | Open Energy Information

    Open Energy Info (EERE)

    temperatures can be predicted from the unchecked application of cation-based Na-K-Ca geo-thermometers. This study shows that in half of the prospects fully equilibrated...

  16. CATIONIC EXCHANGE PROCESS FOR THE SEPARATION OF RARE EARTHS

    DOE Patents [OSTI]

    Choppin, G.R.; Thompson, S.G.; Harvey, B.G.

    1960-02-16

    A process for separating mixtures of elements in the lanthanum and actinium series of the periodic table is described. The mixture of elements is dissolved in 0.05 M HCI, wherein the elements exist as tripositive ions. The resulting solution is then transferred to a column of cationic exchange resin and the column eluted with 0.1 to 0.6 M aqueous ammonium alpha hydroxy isobutyrate solution of pH 3.8 to 5.0. The use of ammonium alpha hydroxy isobutyrate as an eluting agent results in sharper and more rapid separations than previously obtainable with eluants such as citric, tartaric, glycolic, and lactic acids.

  17. Spontaneous Superlattice Formation in Nanorods through PartialCation Exchange

    SciTech Connect (OSTI)

    Robinson, Richard D.; Sadtler, Bryce; Demchenko, Denis O.; Erdonmez, Can K.; Wang, Lin-Wang; Alivisatos, A. Paul

    2007-03-14

    Lattice mismatch strains are widely known to controlnanoscale pattern formation in heteroepitaxy, but such effects have notbeen exploited in colloidal nanocrystal growth. We demonstrate acolloidal route to synthesizing CdS-Ag2S nanorod superlattices throughpartial cation exchange. Strain induces the spontaneous formation ofperiodic structures. Ab initio calculations of the interfacial energy andmodeling of strain energies show that these forces drive theself-organization. The nanorod superlattices exhibit high stabilityagainst ripening and phase mixing. These materials are tunablenear-infrared emitters with potential applications as nanometer-scaleoptoelectronic devices.

  18. Nitrogen-doped zirconia: A comparison with cation stabilized zirconia

    SciTech Connect (OSTI)

    Lee, Jong-Sook . E-mail: jong-sook.lee@fkf.mpg.de; Lerch, Martin; Maier, Joachim

    2006-01-15

    The conductivity behavior of nitrogen-doped zirconia is compared with that of zirconia doped with lower-valent cations and discussed in the framework of defect-defect interactions. While nominally introducing the same number of vacancies as yttrium, nitrogen dopants introduced in the anion sublattice of zirconia lead to substantially different defect kinetics and energetics. Compared to the equivalent yttrium doping nitrogen doping in the Y-Zr-O-N system substantially increases the activation energy and correspondingly decreases the conductivity at temperatures below 500{sup -}bar C in the vacancy range below 4mol%. The comparison of N-doped zirconia and zirconia systems doped with size-matched cation stabilizers, such as Sc, Yb and Y, shows that elastically driven vacancy-vacancy ordering interactions can phenomenologically account for the temperature- and composition-dependence. It is striking that materials with superior high-temperature conductivities due to weak dopant-vacancy interactions undergo severe deterioration at low temperature due to the strong vacancy-ordering. The analysis also explains qualitatively similar effects of Y co-doping in Yb-, Sc-, and N-doped zirconia. Small amount of Y in N-doped zirconia as well as in Sc-doped zirconia appears to hinder the formation of the long-range ordered phase and thus enhance the conductivity substantially.

  19. Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical

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

    Peter R. Craig; Miller, John R.; Havlas, Zdenek; Trujillo, Marianela; Rempala, Pawel; Kirby, James P.; Noll, Bruce C.; Michl, Josef

    2016-05-02

    In this study, properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative 1a have been measured and calculated. The B3LYP/TZP optimized geometry of the free cation 1 agrees with a single-crystal X-ray diffraction structure except that in the crystal one of the phenyl substituents is strongly twisted to permit a close-packing interaction of two of its hydrogens with a nearby BF–4 anion. The low-energy parts of the solution electronic absorption and magnetic circular dichroism (MCD) spectra of 1 and 1a have been interpreted by comparison with TD-DFT (B3LYP/TZP) results. Reduction or pulse radiolysis lead to a neutral 19-electron radical,more » whose visible absorption and MCD spectra have been recorded and interpreted as well. The reduction is facilitated by ~0.1 V upon going from 1 to 1a« less

  20. Insights into dynamic processes of cations in pyrochlores and other complex oxides

    SciTech Connect (OSTI)

    Uberuaga, Blas Pedro; Perriot, Romain

    2015-08-26

    Complex oxides are critical components of many key technologies, from solid oxide fuel cells and superionics to inert matrix fuels and nuclear waste forms. In many cases, understanding mass transport is important for predicting performance and, thus, extensive effort has been devoted to understanding mass transport in these materials. However, most work has focused on the behavior of oxygen while cation transport has received relatively little attention, even though cation diffusion is responsible for many phenomena, including sintering, radiation damage evolution, and deformation processes. Here, we use accelerated molecular dynamics simulations to examine the kinetics of cation defects in one class of complex oxides, A₂B₂O₇ pyrochlore. In some pyrochlore chemistries, B cation defects are kinetically unstable, transforming to A cation defects and antisites at rates faster than they can diffuse. When this occurs, transport of B cations occurs through defect processes on the A sublattice. Further, these A cation defects, either interstitials or vacancies, can interact with antisite disorder, reordering the material locally, though this process is much more efficient for interstitials than vacancies. Whether this behavior occurs in a given pyrochlore depends on the A and B chemistry. Pyrochlores with a smaller ratio of cation radii exhibit this complex behavior, while those with larger ratios exhibit direct migration of B interstitials. Similar behavior has been reported in other complex oxides such as spinels and perovskites, suggesting that this coupling of transport between the A and B cation sublattices, while not universal, occurs in many complex oxide.

  1. Cation-exchange fiber reduces iron oxide leakage

    SciTech Connect (OSTI)

    MacClure, S.L.

    1993-10-01

    This article describes how addition of new fiber in powdered-resin precoat improves demineralizer crud-retention capability and reduces disposal cost for radioactive spent resin. Various attempts have been made to reduce the concentrations of iron oxide at the outlet of filter/demineralizer (FTD) vessels. Each vessel is fitted with an array of tubular septa that are precoated with powdered ion-exchange resin. The coatings perform filtering and ion-exchange actions on incoming feedwater, removing both suspended and dissolved solids. Experience at Duane Arnold Energy Center (CAED) indicates that use of a powdered-resin precoat containing cation-exchange fibers rather than cellulose fibers can reduce iron oxide levels in FTD effluent significantly.

  2. Separation of certain carboxylic acids utilizing cation exchange membranes

    DOE Patents [OSTI]

    Chum, Helena L. (Arvada, CO); Sopher, David W. (Maarssenbroek, NL)

    1984-01-01

    A method of substantially separating monofunctional lower carboxylic acids from a liquid mixture containing the acids wherein the pH of the mixture is adjusted to a value in the range of from about 1 to about 5 to form protonated acids. The mixture is heated to an elevated temperature not greater than about 100.degree. C. and brought in contact with one side of a perfluorinated cation exchange membrane having sulfonate or carboxylate groups or mixtures thereof with the mixture containing the protonated acids. A pressure gradient can be established across the membrane with the mixture being under higher pressure, so that protonated monofunctional lower carboxylic acids pass through the membrane at a substantially faster rate than the remainder of the mixture thereby substantially separating the acids from the mixture.

  3. Kinetics for Tautomerizations and Dissociations of Triglycine Radical Cations

    SciTech Connect (OSTI)

    Siu, Chi-Kit; Zhao, Junfang; Laskin, Julia; Chu, Ivan K.; Hopkinson, Alan C.; Siu , K W Michael

    2009-06-01

    Fragmentations of tautomers of the α-centered radical triglycine radical cation, [GGG*]+, [GG*G]+, and [G*GG]+, are charge-driven, giving b-type ions; these are processes that are facilitated by a mobile proton, as in the fragmentation of protonated triglycine (Rodriquez, C.F. et al. J. Am. Chem. Soc. 2001, 123, 3006 - 3012). By contrast, radical centers are less mobile. Two mechanisms have been examined theoretically utilizing density functional theory and Rice-Ramsperger-Kassel-Marcus modeling: (1) a direct hydrogen-atom migration between two α-carbons, and (2) a two-step proton migration involving a canonical [GGG]*+ as an intermediate. Predictions employing the latter mechanism are in good agreement with results of recent CID experiments (Chu, I.K. et al. J. Am. Chem. Soc. 2008, 130, 7862 - 7872).

  4. Method of separating and recovering uranium and related cations from spent Purex-type systems

    DOE Patents [OSTI]

    Mailen, J.C.; Tallent, O.K.

    1987-02-25

    A process for separating uranium and related cations from a spent Purex-type solvent extraction system which contains degradation complexes of tributylphosphate wherein the system is subjected to an ion-exchange process prior to a sodium carbonate scrubbing step. A further embodiment comprises recovery of the separated uranium and related cations. 5 figs.

  5. Influence of rubidium cations on hydrogen and deuterium electrosorption in palladium

    SciTech Connect (OSTI)

    Czerwinski, A.; Frydrych, J.; Kiersztyn, I.

    1996-11-01

    A comparative cyclic voltammetric study of the hydrogen and deuterium sorptions into a thin layer palladium electrode has been performed in acidic and basic solutions containing rubidium cations. As in the case of other alkali cations, rubidium appears to clearly influence the {alpha}- to {beta}- phase transition only in basic solution.

  6. Ionic Liquids with Ammonium Cations as Lubricants or Additives

    SciTech Connect (OSTI)

    Qu, Jun; Blau, Peter Julian; Dai, Sheng; Luo, Huimin; Truhan, Jr., John J

    2006-01-01

    Friction and wear are estimated to cost 6% of the US gross national product, or around $700 billion annually. A new class of more effective lubricants could lead to huge energy savings. Limited recent literature has suggested potential for using room-temperature ionic liquids as lubricants, however only a few out of millions (or more) of species have been evaluated. Recent ORNL work discovered a new category of ionic liquids with ammonium cations that have demonstrated promising lubricating properties as net lubricants or lubricant additives, particularly in lubricating difficult-to-lubricate metals like aluminum. More than 30% friction reduction has been observed on ammonium-based ionic liquids compared to conventional hydrocarbon oils. The inherent polarity of ionic liquids is believed to provide strong adhesion to contact surfaces and form a boundary lubricating film leading to friction and wear reductions. Other advantages of ionic liquids include (1) negligible volatility, (2) high thermal stability, (3) non-flammability, and (4) better intrinsic properties that eliminate the necessity of many expensive lubricant additives. With very flexible molecular structures, this new class of lubricants, particularly ammonium-based ionic liquids, can be tailored to fit a big variety of applications including but not limited to bearings, combustion engines, MEMS, and metal forming.

  7. Cation exchange pretreatment studies for high recovery - Yuma desalting plant

    SciTech Connect (OSTI)

    Kaakinen, J.W.; Laverty, P.E.

    1983-10-01

    The main purpose of the High Recovery Test Program was to obtain feasibility design data for cation exchange softening to allow a greater fractional recovery of desalted product water at the YDP(Yuma Desalting Plant). Compared to the original YDP design with 70-percent desalting recovery, additional removal of calcium in the desalting feed would allow recoveries over 90 percent. Pilot plant equipment to test this process was operated at the YDTF(Yuma Desalting Test Facility) and consisted of an IX unit and an electrodialyzer to supply reject-brine regenerant for the IX experiments. Gypsum scale buildup in the resin bed could be avoided by regeneration with a high upward flow rate causing a fluidized bed. Reuse of regenerant was also beneficial. Results show that the ion exchange high recovery pretreatment process is highly feasible, and that it is technically possible to achieve high recovery in the YDP. Numerous recommendations for a plant design are given and future studies are noted.

  8. Novel alkyd-type coating resins produced using cationic polymerization

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

    Chisholm, Bret J.; Kalita, Harjyoti; Alam, Samim; Jayasooriyamu, Anurad; Fernando, Shashi; Samanata, Satyabrata; Bahr, James; Selvakumar, Sermadurai; Sibi, Mukund; Vold, Jessica; et al

    2015-05-06

    Novel, partially bio-based poly(vinyl ether) copolymers derived from soybean oil and cyclohexyl vinyl ether (CHVE) were produced by cationic polymerization and investigated for application as alkyd-type surface coatings. Compared to conventional alkyd resins, which are produced by high temperature melt condensation polymerization, the poly(v9nyl ether)s provide several advantages. These advantages include milder, more energy efficient polymer synthesis, elimination of issues associated with gelation during polymer synthesis, production of polymers with well-defined composition and relatively narrow molecular weight distribution, and elimination of film formation and physical property issues associated with entrained monomers, dimers, trimers, etc. The results of the studied showedmore » that the thermal, mechanical, and physical properties of the coatings produced from these novel polymers varied considerably as a function of polymer composition and cure temperature. Overall, the results suggest a good potential for these novel copolymers to be used for coatings cured by autoxidation.« less

  9. Organic cation secretion by Cancer borealis urinary bladder

    SciTech Connect (OSTI)

    Miller, D.S.; Holliday, C.W.

    1987-01-01

    In the crab, Cancer borealis, initial clearance studies showed a potent renal excretory system for the model organic cation, tetraethylammonium (TEA). (/sup 14/C)-TEA clearance averaged 145 +/- 32 ml/day, which was 18 times the paired polyethylene glycol clearance. TEA uptake by slices of urinary bladder was concentrative, saturable, inhibitable by N/sup 1/-methylnicotinamide chloride, and dependent on glycolytic, but not oxidative, metabolism. When mounted in flux chambers, bladders exhibited a large net secretory flux. For 0.1 mM TEA, the ratio of secretory to reabsorptive fluxes was 65. Urinary bladders from another crab, Cancer irroratus, and a lobster, Homarus americanus, also exhibited net TEA secretion. In C. borealis bladder, secretory transport was concentrative, saturable, and nearly abolished by addition of 1 mM quinine to the serosol bath. Reabsorptive transport was not concentrative and was not reduced by luminal quinine. The data are consistent with a secretory pathway that is transcellular and mediated by carriers at both the serosal and luminal membranes.

  10. Insights into dynamic processes of cations in pyrochlores and other complex oxides

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

    Uberuaga, Blas Pedro; Perriot, Romain

    2015-08-26

    Complex oxides are critical components of many key technologies, from solid oxide fuel cells and superionics to inert matrix fuels and nuclear waste forms. In many cases, understanding mass transport is important for predicting performance and, thus, extensive effort has been devoted to understanding mass transport in these materials. However, most work has focused on the behavior of oxygen while cation transport has received relatively little attention, even though cation diffusion is responsible for many phenomena, including sintering, radiation damage evolution, and deformation processes. Here, we use accelerated molecular dynamics simulations to examine the kinetics of cation defects in onemore » class of complex oxides, A₂B₂O₇ pyrochlore. In some pyrochlore chemistries, B cation defects are kinetically unstable, transforming to A cation defects and antisites at rates faster than they can diffuse. When this occurs, transport of B cations occurs through defect processes on the A sublattice. Further, these A cation defects, either interstitials or vacancies, can interact with antisite disorder, reordering the material locally, though this process is much more efficient for interstitials than vacancies. Whether this behavior occurs in a given pyrochlore depends on the A and B chemistry. Pyrochlores with a smaller ratio of cation radii exhibit this complex behavior, while those with larger ratios exhibit direct migration of B interstitials. Similar behavior has been reported in other complex oxides such as spinels and perovskites, suggesting that this coupling of transport between the A and B cation sublattices, while not universal, occurs in many complex oxide.« less

  11. Geothermometry At Mt Princeton Hot Springs Geothermal Area (Pearl...

    Open Energy Info (EERE)

    Celcius References R.H. Pearl, J.K. Barrett (1976) Geothermal resources of the Upper San Luis and Arkansas valleys, Colorado Additional References Retrieved from "http:...

  12. Geothermometry At Salt Wells Area (Coolbaugh, Et Al., 2006) ...

    Open Energy Info (EERE)

    and ICP emission for anions. The hottest sampled spring appears to match the location and temperature of the Borax Spring, first described in 1885, but reportedly inactive in 1981...

  13. Geothermometry At Salt Wells Area (Henkle, Et Al., 2005) | Open...

    Open Energy Info (EERE)

    were carried out in conjunction with geologic mapping to test the application of these ground-based techniques to geothermal exploration at three prospects in Nevada by Henkle...

  14. Geothermometry At Hot Springs Ranch Area (Szybinski, 2006) |...

    Open Energy Info (EERE)

    of two distinct waters in this group of samples (Tom Powell of Thermochem Inc., personal communication, 2005). Powell found that MDH, TRS-1 and TRS-6 are the most prospective...

  15. Geothermometry At Kawaihae Area (Thomas, 1986) | Open Energy...

    Open Energy Info (EERE)

    however, the data that are available strongly substantiate the presence of a thermal resource. A measured water temperature of 31 degrees C in one well is clearly above normal...

  16. Geothermometry At U.S. Midwest Region (Vugrinovich, 1987) | Open...

    Open Energy Info (EERE)

    Activity Date Usefulness useful DOE-funding Unknown Notes Michigan "The silica heat flow estimator does provide estimates of surface heat flow which appear to be in good...

  17. Geothermal Reservoir Temperatures in Southeastern Idaho using Multicomponent Geothermometry

    SciTech Connect (OSTI)

    Neupane, Ghanashyam; Mattson, Earl D.; McLing, Travis L.; Palmer, Carl D.; Smith, Robert W.; Wood, Thomas R.; Podgorney, Robert K.

    2015-03-01

    Southeastern Idaho exhibits numerous warm springs, warm water from shallow wells, and hot water within oil and gas test wells that indicate a potential for geothermal development in the area. Although the area exhibits several thermal expressions, the measured geothermal gradients vary substantially (19 – 61 ºC/km) within this area, potentially suggesting a redistribution of heat in the overlying ground water from deeper geothermal reservoirs. We have estimated reservoir temperatures from measured water compositions using an inverse modeling technique (Reservoir Temperature Estimator, RTEst) that calculates the temperature at which multiple minerals are simultaneously at equilibrium while explicitly accounting for the possible loss of volatile constituents (e.g., CO2), boiling and/or water mixing. Compositions of a selected group of thermal waters representing southeastern Idaho hot/warm springs and wells were used for the development of temperature estimates. The temperature estimates in the the region varied from moderately warm (59 ºC) to over 175 ºC. Specifically, hot springs near Preston, Idaho resulted in the highest temperature estimates in the region.

  18. Geothermometry At Northern Basin & Range Region (Cole, 1983)...

    Open Energy Info (EERE)

    Fish (Wilson), Twin Peak, Cudahy, Laverkin, Grantsville, Crystal Prison, Arrowhead, Red Hill, Monroe, Joseph, Castilla, Saratoga, Thermo, Crater, Wasatch, Beck, Deseret, Big...

  19. Geothermometry At Reese River Area (Henkle & Ronne, 2008) | Open...

    Open Energy Info (EERE)

    DOE-funding Unknown Notes Four formation water samples were collected from well 56-4, during an airlift test which took place between November 11 and November 14, 2007....

  20. Geothermometry At Roosevelt Hot Springs Geothermal Area (Ward...

    Open Energy Info (EERE)

    Area. References S. H. Ward, W. T. Parry, W. P. Nash, W. R. Sill, K. L. Cook, R. B. Smith, D. S. Chapman, F. H. Brown, J. A. Whelan, J. R. Bowman (1978) A Summary of the...

  1. Geothermometry At Raft River Geothermal Area (1980) | Open Energy...

    Open Energy Info (EERE)

    River geothermal system, Cassia County, Idaho Urban, T.C.; Diment, W.H.; Nathenson, M.; Smith, E.P.; Ziagos, J.P.; Shaeffer, M.H. (1 January 1986) Temperature,...

  2. Geothermometry At Long Valley Caldera Geothermal Area (Sorey...

    Open Energy Info (EERE)

    studies, and seem to prove useful in most cases (Flexser, 1991; Goff et al., 1991; Smith and Suemnicht, 1991). Results from these studies are also summarized in Sorey et al....

  3. Geochemistry And Geothermometry Of Spring Water From The Blackfoot...

    Open Energy Info (EERE)

    for eight springs along the Corral Creek drainage. The springs along Corral Creek have Na-K-Ca temperatures that average 354C, a direct result of high potassium concentrations in...

  4. Geothermometry At Lualualei Valley Area (Thomas, 1986) | Open...

    Open Energy Info (EERE)

    have been commonly used in Hawaii for identifying geothermal potential (i.e. silica concentration and chloride to magnesium ion ratios) were anomalous in the groundwater of this...

  5. Geothermometry At Long Valley Caldera Geothermal Area (McKenzie...

    Open Energy Info (EERE)

    published in 1976 (Mariner and Willey, 1976). Details of sampling practices and field treatment are detailed in the text. Water samples were passed through a 0.7x4 cm column...

  6. Geothermometry At Socorro Mountain Area (Owens, Et Al., 2005...

    Open Energy Info (EERE)

    thermal waters with a minimum of 82oC at depth References Lara Owens, Richard Baars, David Norman, Harold Tobin (2005) New Methods In Exploration At The Socorro Peak Kgra- A...

  7. Geothermometry At Lahaina-Kaanapali Area (Thomas, 1986) | Open...

    Open Energy Info (EERE)

    Date Usefulness not indicated DOE-funding Unknown Notes Groundwater temperature and chemistry surveys were similarly unable to identify any detectable thermal influence on...

  8. Geothermometry At Long Valley Caldera Geothermal Area (Mariner...

    Open Energy Info (EERE)

    California R.O. Fournier, Michael L. Sorey, Robert H. Mariner, Alfred H. Truesdell (1979) Chemical and Isotopic Prediction of Aquifer Temperatures in the Geothermal System at Long...

  9. Geothermometry At Coso Geothermal Area (1978) | Open Energy Informatio...

    Open Energy Info (EERE)

    analysis to determine fluid origin. The surface expression of fumarole and acid sulfate pools and shallow steam wells gives a false indication of an extensive vapor...

  10. Geothermometry At Long Valley Caldera Geothermal Area (Farrar...

    Open Energy Info (EERE)

    stages of hydrothermal activity, flow, and recharge in the Long Valley caldera groundwater system. Fluids were sampled from LVEW during flow testing in May 2000, July 2000,...

  11. Geothermometry At Salt Wells Area (Edmiston & Benoit, 1984) ...

    Open Energy Info (EERE)

    and drilled during the early 1980's that had not been documented previously in the literature, (2) summarize and compare chemical and temperature data from known moderate- to...

  12. Geothermometry At Gabbs Alkali Flat Area (Kratt, Et Al., 2008...

    Open Energy Info (EERE)

    Mark Coolbaugh, Chris Sladek, Rick Zehner, Robin Penfield, Ben Delwiche (2008) A New Gold Pan For The West- Discovering Blind Geothermal Systems With Shallow Temperature Surveys...

  13. Geothermometry At Columbus Salt Marsh Area (Shevenell, Et Al...

    Open Energy Info (EERE)

    References Lisa Shevenell, Mark Coolbaugh, Chris Sladek, Rick Zehner, Chris Kratt, James Faulds, Robin Penfield (2008) Our Evolving Knowledge Of Nevada'S Geothermal Resource...

  14. Geothermometry At Teels Marsh Area (Shevenell, Et Al., 2008)...

    Open Energy Info (EERE)

    References Lisa Shevenell, Mark Coolbaugh, Chris Sladek, Rick Zehner, Chris Kratt, James Faulds, Robin Penfield (2008) Our Evolving Knowledge Of Nevada'S Geothermal Resource...

  15. Geothermometry At Rhodes Marsh Area (Shevenell, Et Al., 2008...

    Open Energy Info (EERE)

    References Lisa Shevenell, Mark Coolbaugh, Chris Sladek, Rick Zehner, Chris Kratt, James Faulds, Robin Penfield (2008) Our Evolving Knowledge Of Nevada'S Geothermal Resource...

  16. Isotope Geothermometry At Lightning Dock Geothermal Area (Witcher...

    Open Energy Info (EERE)

    Usefulness useful DOE-funding Unknown Exploration Basis Part of the Geothermal Resource Evaluation and Definition (GRED) Program administered by DOE-AAO under Cooperative...

  17. Geothermometry At Northern Basin & Range Region (Laney, 2005...

    Open Energy Info (EERE)

    Nevada, Shevenell and Garside. The objective of this project is to obtain geochemical data from springs (and some wells) for which data are not publicly available, or for which...

  18. Geothermometry At Buffalo Valley Hot Springs Area (Laney, 2005...

    Open Energy Info (EERE)

    Nevada, Shevenell and Garside. The objective of this project is to obtain geochemical data from springs (and some wells) for which data are not publicly available, or for which...

  19. Geothermometry At Nw Basin & Range Region (Laney, 2005) | Open...

    Open Energy Info (EERE)

    Nevada, Shevenell and Garside. The objective of this project is to obtain geochemical data from springs (and some wells) for which data are not publicly available, or for which...

  20. Geothermometry At Central Nevada Seismic Zone Region (Laney,...

    Open Energy Info (EERE)

    Nevada, Shevenell and Garside. The objective of this project is to obtain geochemical data from springs (and some wells) for which data are not publicly available, or for which...

  1. Cationic Liposome-Microtuble Complexes: Lipid-Protein Bio-Nanotubles with

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

    Open or Closed Ends Cationic Liposome-Microtubule Complexes: Lipid-Protein Bio-Nanotubes with Open or Closed Ends Uri Raviv,*,+ Daniel J. Needleman,*,+ Youli Li,*,+ Herbert P. Miller,+ Leslie Wilson,+ and Cyrus R. Safinya *,+ *Materials Department, Physics Department +Molecular, Cellular, and Developmental Biology Department, Biomolecular Science and Engineering Program, University of California, Santa Barbara, CA 93106 In this work we explored the structured that form when cationic

  2. Infrared spectroscopy of the methanol cation and its methylene-oxonium isomer

    SciTech Connect (OSTI)

    Mosley, J. D.; Young, J. W.; Duncan, M. A. E-mail: maduncan@uga.edu; Huang, M.; McCoy, A. B. E-mail: maduncan@uga.edu

    2015-03-21

    The carbenium ion with nominal formula [C,H{sub 4},O]{sup +} is produced from methanol or ethylene glycol in a pulsed-discharge supersonic expansion source. The ion is mass selected, and its infrared spectrum is measured from 2000 to 4000 cm{sup ?1} using laser photodissociation spectroscopy and the method of rare gas atom tagging. Computational chemistry predicts two isomers, the methanol and methylene-oxonium cations. Predicted vibrational spectra based on scaled harmonic and reduced dimensional treatments are compared to the experimental spectra. The methanol cation is the only isomer produced when methanol is used as a precursor. When ethylene glycol is used as the precursor, methylene-oxonium is produced in addition to the methanol cation. Theoretical results at the CCSD(T)/cc-pVTZ level show that methylene-oxonium is lower in energy than methanol cation by 6.4 kcal/mol, and is in fact the global minimum isomer on the [C,H{sub 4},O]{sup +} potential surface. Methanol cation is trapped behind an isomerization barrier in our source, providing a convenient method to produce and characterize this transient species. Analysis of the spectrum of the methanol cation provides evidence for strong CH stretch vibration/torsion coupling in this molecular ion.

  3. Enhanced Mixed Electronic-Ionic Conductors through Cation Ordering

    SciTech Connect (OSTI)

    Jacobson, Allan J.; Morgan, Dane; Grey, Clare

    2014-08-31

    The performance of many energy conversion and storage devices depend on the properties of mixed ionic-electronic conducting (miec) materials. Mixed or ambipolar conductors simultaneously transport ions and electrons and provide the critical interface between chemical and electrical energy in devices such as fuel cells, ion transport membranes, and batteries. Enhancements in storage capacity, reversibility, power density and device lifetime all require new materials and a better understanding of the fundamentals of ambipolar conductivity and surface reactivity.The high temperature properties of the ordered perovksites AA’B2O5+x, where A = rare earth ion, Y and B = Ba, Sr were studied. The work was motivated by the high oxygen transport and surface exchange rates observed for members of this class of mixed ionic and electronic conductors. A combined experimental and computational approach, including structural, electrochemical, and transport characterization and modeling was used. The approach attacks the problem simultaneously at global (e.g., neutron diffraction and impedance spectroscopy), local (e.g., pair distribution function, nuclear magnetic resonance) and molecular (ab initio thermokinetic modeling) length scales. The objectives of the work were to understand how the cation and associated anion order lead to exceptional ionic and electronic transport properties and surface reactivity in AA’B2O5+x perovskites. A variety of compounds were studied by X-ray and neutron diffraction, measurements of thermodynamics and transport and theoretically. These included PrBaCo2O5+x and NdBaCo2O5+x, PrBaCo2-xFexO6- δ (x = 0, 0.5, 1.0, 1.5 and 2) and LnBaCoFeO6- δ (Ln = La, Pr, Nd, Sm, Eu and Gd), Sr3YCo4O10.5, YBaMn2O5+x. A0.5A’0.5BO3 (where A=Y, Sc, La, Ce, Pr, Nd, Pm, Sm; A’= Sr

  4. Mesophase stabilization in ionic liquid crystals through pairing equally shaped mesogenic cations and anions

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

    Stappert, Kathrin; Lipinski, Gregor; Kopiec, Gabriel; Spielberg, Eike T.; Mudring, Anja -Verena

    2015-07-23

    The synthesis and properties of a set of novel ionic liquid crystals with congruently shaped cations and anions are reported to check whether pairing mesogenic cations with mesogenic anions leads to a stabilization of a liquid crystalline phase. To that avail 1-alkyl-3-methyl-triazolium cations with an alkyl chain length of 10, 12, and 14 carbon atoms have been combined with p-alkyloxy-benzenesulfonate anions with different alkyl chain lengths (n = 10, 12, and 14). The corresponding triazolium iodides have been synthesized as reference compounds where the cation and anion have strong size and shape mismatch. The mesomorphic behavior of all compounds ismore » studied by differential scanning calorimetry and polarizing optical microscopy. All compounds except 1-methyl-3-decyltriazolium iodide, which qualifies as an ionic liquid, are thermotropic ionic liquid crystals. All other compounds adopt smectic A phases. As a result, a comparison of the thermal phase behavior of the 1-methyl-3-decyltriazolium bromides to the corresponding p-alkoxy-benzensulfonates reveals that definitely the mesophase is stabilized by pairing the rod-shaped 1-alkyl-3-methyltriazolium cation with a rod-like anion of similar size.« less

  5. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

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

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-04-05

    Here, benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt−1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through a combinationmore » of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

  6. Colloid Facilitated Transport of Radioactive Cations in the Vadose Zone: Field Experiments Oak Ridge

    SciTech Connect (OSTI)

    James E. Saiers

    2012-09-20

    The overarching goal of this study was to improve understanding of colloid-facilitated transport of radioactive cations through unsaturated soils and sediments. We conducted a suite of laboratory experiments and field experiments on the vadose-zone transport of colloids, organic matter, and associated contaminants of interest to the U.S. Department of Energy (DOE). The laboratory and field experiments, together with transport modeling, were designed to accomplish the following detailed objectives: 1. Evaluation of the relative importance of inorganic colloids and organic matter to the facilitation of radioactive cation transport in the vadose zone; 2. Assessment of the role of adsorption and desorption kinetics in the facilitated transport of radioactive cations in the vadose zone; 3. Examination of the effects of rainfall and infiltration dynamics and in the facilitated transport of radioactive cations through the vadose zone; 4. Exploration of the role of soil heterogeneity and preferential flow paths (e.g., macropores) on the facilitated transport of radioactive cations in the vadose zone; 5. Development of a mathematical model of facilitated transport of contaminants in the vadose zone that accurately incorporates pore-scale and column-scale processes with the practicality of predicting transport with readily available parameters.

  7. Mesophase stabilization in ionic liquid crystals through pairing equally shaped mesogenic cations and anions

    SciTech Connect (OSTI)

    Stappert, Kathrin; Lipinski, Gregor; Kopiec, Gabriel; Spielberg, Eike T.; Mudring, Anja -Verena

    2015-07-23

    The synthesis and properties of a set of novel ionic liquid crystals with congruently shaped cations and anions are reported to check whether pairing mesogenic cations with mesogenic anions leads to a stabilization of a liquid crystalline phase. To that avail 1-alkyl-3-methyl-triazolium cations with an alkyl chain length of 10, 12, and 14 carbon atoms have been combined with p-alkyloxy-benzenesulfonate anions with different alkyl chain lengths (n = 10, 12, and 14). The corresponding triazolium iodides have been synthesized as reference compounds where the cation and anion have strong size and shape mismatch. The mesomorphic behavior of all compounds is studied by differential scanning calorimetry and polarizing optical microscopy. All compounds except 1-methyl-3-decyltriazolium iodide, which qualifies as an ionic liquid, are thermotropic ionic liquid crystals. All other compounds adopt smectic A phases. As a result, a comparison of the thermal phase behavior of the 1-methyl-3-decyltriazolium bromides to the corresponding p-alkoxy-benzensulfonates reveals that definitely the mesophase is stabilized by pairing the rod-shaped 1-alkyl-3-methyltriazolium cation with a rod-like anion of similar size.

  8. Effect of cation ordering on oxygen vacancy diffusion pathways in double perovskites

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

    Uberuaga, Blas Pedro; Pilania, Ghanshyam

    2015-07-08

    Perovskite structured oxides (ABO3) are attractive for a number of technological applications, including as superionics because of the high oxygen conductivities they exhibit. Double perovskites (AA’BB’O6) provide even more flexibility for tailoring properties. Using accelerated molecular dynamics, we examine the role of cation ordering on oxygen vacancy mobility in one model double perovskite SrLaTiAlO6. We find that the mobility of the vacancy is very sensitive to the cation ordering, with a migration energy that varies from 0.6 to 2.7 eV. In the extreme cases, the mobility is both higher and lower than either of the two end member single perovskites.more » Further, the nature of oxygen vacancy diffusion, whether one-dimensional, two-dimensional, or three-dimensional, also varies with cation ordering. We correlate the dependence of oxygen mobility on cation structure to the distribution of Ti4+ cations, which provide unfavorable environments for the positively charged oxygen vacancy. The results demonstrate the potential of using tailored double perovskite structures to precisely control the behavior of oxygen vacancies in these materials.« less

  9. Properties of some ionic liquids based on1-methyl-3-octylimidazolium and 4-methyl-N-butylpyridinium cations.

    SciTech Connect (OSTI)

    Papaiconomou, Nicolas; Yakelis, Neal; Salminen, Justin; Bergman,Robert; Prausnitz, John M.

    2005-09-29

    Syntheses are reported for ionic liquids containing 1-methyl-3octylimidazolium and 4-methyl-N-butylpyridinium cations, and trifluoromethansulfonate, dicyanamide, bis(trifluoromethylsulfonyl)imide, and nonafluorobutanesulfonate anions. Densities, melting points and glass transition points, solubility in water as well as polarities have been measured. Ionic liquids based on pyridinium cations exhibit higher melting points, lower solubility in water, and higher polarity than those based on imidazolium cations.

  10. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

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

    Kim, M. J.; Zoerb, M. C.; Campbell, N. R.; Zimmermann, K. J.; Blomquist, B. W.; Huebert, B. J.; Bertram, T. H.

    2015-10-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e. DMS, ?-caryophyllene) as well as previously studied VOCs (i.e., isoprene, ?-pinene). Using a field deployable chemical ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt?1) to DMS, isoprene, and ?-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a weaker electric field, demonstrated that ion-molecule reactions likely proceed through amorecombination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (R2=0.80) over a wide range of sampling conditions.less

  11. Differential inhibition of organic cations by the renal tubule of the chicken: relationship to Tm

    SciTech Connect (OSTI)

    Springate, J.; Hasan, M.; Rennick, B.; Acara, M.

    1986-03-01

    The ability of organic cations to differentially inhibit the renal excretion of two prototypical organic cations, tetraethylammonium (TEA) and N/sup 1/-methylnicotinamide (NMN), was investigated using the Sperber technique in chickens. /sup 3/H-TEA and /sup 14/C-NMN were infused simultaneously into the renal portal circulation and their transport efficiencies (TE) determined to be 106 +/- 11% and 81 +/- 13% respectively. Quinine, unlabelled NMN or TEA, added in increasing amounts, produced differential inhibition of TEA, NMN, or cimetidine (infused in separate experiments). Data using other competing organic cations (guinidine, ranitidine, triethylcholine) indicated that TEA was never more susceptible to inhibition than NMN. These results suggest that the magnitude of T/sub m/ is directly related to susceptibility to inhibition and indirectly to inhibitory potency.

  12. DFT studies of all fluorothiophenes and their cations as candidate monomers for conductive polymers

    SciTech Connect (OSTI)

    Shirani, Hossein; Jameh-Bozorghi, Saeed; Yousefi, Ali

    2015-01-22

    In this paper, electronic, structural, and properties of mono-, di-, tri-, and tetrafluorothiophenes and their radical cations are studied using the density functional theory and B3LYP method with 6-311++G** basis set. Also, the effects of the number and position of the substituent of fluorine atoms on the properties of the thiophene ring have been studied using optimized structures obtained for these molecules and their radical cations; vibrational frequencies, spin-density distribution, size and direction of the dipole moment vector, ionization potential, electric Polarizabilities, HOMO–LUMO gaps and NICS values of these compounds have been calculated and analyzed.

  13. Non-immunogenic, hydrophilic/cationic block copolymers and uses thereof

    DOE Patents [OSTI]

    Scales, Charles W.; Huang, Faqing; McCormick, Charles L.

    2010-05-18

    The present invention provides novel non-immunogenic, hydrophilic/cationic block copolymers comprising a neutral-hydrophilic polymer and a cationic polymer, wherein both polymers have well-defined chain-end functionality. A representative example of such a block copolymer comprises poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA) and poly(N-[3-(dimethylamino)propyl]methacrylamide) (PDMAPMA). Also provided is a synthesis method thereof in aqueous media via reversible addition fragmentation chain transfer (RAFT) polymerization. Further provided are uses of these block copolymers as drug delivery vehicles and protection agents.

  14. Spectroscopic signatures of proton transfer dynamics in the water dimer cation

    SciTech Connect (OSTI)

    Kamarchik, Eugene; Kostko, Oleg; Bowman, Joel M.; Ahmed, Musahid; Krylov, Anna I.

    2009-12-21

    Using full dimensional EOM-IP-CCSD/aug-cc-pVTZ potential energy surfaces, the photoelectron spectrum, vibrational structure, and ionization dynamics of the water dimer radical cation, (H2O)+2, were computed. We also report an experimental photoelectron spectrum which is derived from photoionization efficiency measurements and compares favorably with the theoretical spectrum. The vibrational structure is also compared with the recent experimental work of Gardenier et al. [J. Phys. Chem. A 113, 4772 (2009)] and the recent theoretical calculations by Cheng et al. [J. Phys. Chem. A 113 13779 (2009)]. A reduced dimensionality nuclear Hamiltonian was used to compute the ionization dynamics for both the ground state and first excited state of the cation. The dynamics show markedly different behavior and spectroscopic signatures depending on which state of the cation is accessed by the ionization. Ionization to the ground-state cation surface induces a hydrogen transfer which is complete within 50 femtoseconds, whereas ionization to the first excited state results in a much slower process.

  15. High energy electron beam curing of epoxy resin systems incorporating cationic photoinitiators

    DOE Patents [OSTI]

    Janke, C.J.; Lopata, V.J.; Havens, S.J.; Dorsey, G.F.; Moulton, R.J.

    1999-03-02

    A mixture of epoxy resins such as a semi-solid triglycidyl ether of tris (hydroxyphenyl) methane and a low viscosity bisphenol A glycidyl ether and a cationic photoinitiator such as a diaryliodonium salt is cured by irradiating with a dosage of electron beams from about 50 to about 150 kGy, forming a cross-linked epoxy resin polymer.

  16. Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations

    DOE Patents [OSTI]

    Marks, Tobin J.; Chen, You-Xian

    2002-01-01

    Organo-Lewis acids of the formula BR'R".sub.2 wherein B is boron, R' is fluorinated biphenyl, and R" is a fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic fused ring group, and cationic metallocene complexes formed therewith. Such complexes are useful as polymerization catalysts.

  17. Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations

    DOE Patents [OSTI]

    Marks, Tobin J.; Chen, You-Xian

    2001-01-01

    Organo-Lewis acids of the formula BR'R".sub.2 wherein B is boron, R' is fluorinated biphenyl, and R" is a fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic fused ring group, and cationic metallocene complexes formed therewith. Such complexes are useful as polymerization catalysts.

  18. High energy electron beam curing of epoxy resin systems incorporating cationic photoinitiators

    DOE Patents [OSTI]

    Janke, Christopher J.; Lopata, Vincent J.; Havens, Stephen J.; Dorsey, George F.; Moulton, Richard J.

    1999-01-01

    A mixture of epoxy resins such as a semi-solid triglycidyl ether of tris (hydroxyphenyl) methane and a low viscosity bisphenol A glycidyl ether and a cationic photoinitiator such as a diaryliodonium salt is cured by irradiating with a dosage of electron beams from about 50 to about 150 kGy, forming a cross-linked epoxy resin polymer.

  19. Misfit strain driven cation inter-diffusion across an epitaxial multiferroic thin film interface

    SciTech Connect (OSTI)

    Sankara Rama Krishnan, P. S.; Munroe, Paul; Nagarajan, V.; Morozovska, Anna N.; Eliseev, Eugene A.; Ramasse, Quentin M.; Kepaptsoglou, Demie; Liang, Wen-I.; Chu, Ying-Hao

    2014-02-07

    Cation intermixing at functional oxide interfaces remains a highly controversial area directly relevant to interface-driven nanoelectronic device properties. Here, we systematically explore the cation intermixing in epitaxial (001) oriented multiferroic bismuth ferrite (BFO) grown on a (001) lanthanum aluminate (LAO) substrate. Aberration corrected dedicated scanning transmission electron microscopy and electron energy loss spectroscopy reveal that the interface is not chemically sharp, but with an intermixing of ?2?nm. The driving force for this process is identified as misfit-driven elastic strain. Landau-Ginzburg-Devonshire-based phenomenological theory was combined with the Sheldon and Shenoy formula in order to understand the influence of boundary conditions and depolarizing fields arising from misfit strain between the LAO substrate and BFO film. The theory predicts the presence of a strong potential gradient at the interface, which decays on moving into the bulk of the film. This potential gradient is significant enough to drive the cation migration across the interface, thereby mitigating the misfit strain. Our results offer new insights on how chemical roughening at oxide interfaces can be effective in stabilizing the structural integrity of the interface without the need for misfit dislocations. These findings offer a general formalism for understanding cation intermixing at highly strained oxide interfaces that are used in nanoelectronic devices.

  20. Phosphonium-Organophosphate Ionic Liquids as Lubricant Additives: Effects of Cation Structure on Physicochemical and Tribological Characteristics

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

    Barnhill, William C.; Qu, Jun; Luo, Huimin; Meyer III, Harry M.; Ma, Cheng; Chi, Miaofang; Papke, Brian L.

    2014-11-17

    In our previous work we suggest great potential for a phosphonium-organophosphate ionic liquid (IL) as an antiwear lubricant additive. In this study, a set of five ILs were carefully designed and synthesized, with identical organophosphate anions but dissimilar phosphonium cations, to allow systematic investigation of the effects of cation alkyl chain length and symmetry on physicochemical and tribological properties. Symmetric cations with shorter alkyl chains seem to increase the density and thermal stability due to closer packing. On the other hand, either higher cation symmetry or longer alkyl moieties induce a higher viscosity, though the viscosity index is dependent moremore » on molecular mass than on symmetry. While a larger cation size generally increases an IL’s solubility in nonpolar hydrocarbon oils, six-carbon seems to be the critical minimum alkyl chain length for high oil miscibility. Both the two ILs, that are mutually oil miscible, have demonstrated promising lubricating performance at 1.04% treat rate, though the symmetric-cation IL moderately outperformed the asymmetric-cation IL. Moreover, characterizations on the tribofilm formed by the best-performing symmetric-cation IL revealed the film thickness, nanostructure, and chemical composition. Our results provide fundamental insights for future molecular design in developing oil-soluble ILs as lubricant additives.« less

  1. Effect of Divalent Cation Removal on the Structure of Gram-Negative Bacterial Outer Membrane Models

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

    Clifton, Luke A.; Skoda, Maximilian W. A.; Le Brun, Anton P.; Ciesielski, Filip; Kuzmenko, Ivan; Holt, Stephen A.; Lakey, Jeremy H.

    2014-12-09

    The Gram-negative bacterial outer membrane (GNB-OM) is asymmetric in its lipid composition with a phospholipid-rich inner leaflet and an outer leaflet predominantly composed of lipopolysaccharides (LPS). LPS are polyanionic molecules, with numerous phosphate groups present in the lipid A and core oligosaccharide regions. The repulsive forces due to accumulation of the negative charges are screened and bridged by the divalent cations (Mg2+ and Ca2+) that are known to be crucial for the integrity of the bacterial OM. Indeed, chelation of divalent cations is a well-established method to permeabilize Gram-negative bacteria such as Escherichia coli. Here, we use X-ray and neutronmore » reflectivity (XRR and NR, respectively) techniques to examine the role of calcium ions in the stability of a model GNB-OM. Using XRR we show that Ca2+ binds to the core region of the rough mutant LPS (RaLPS) films, producing more ordered structures in comparison to divalent cation free monolayers. Using recently developed solid-supported models of the GNB-OM, we study the effect of calcium removal on the asymmetry of DPPC:RaLPS bilayers. We show that without the charge screening effect of divalent cations, the LPS is forced to overcome the thermodynamically unfavorable energy barrier and flip across the hydrophobic bilayer to minimize the repulsive electrostatic forces, resulting in about 20% mixing of LPS and DPPC between the inner and outer bilayer leaflets. These results reveal for the first time the molecular details behind the well-known mechanism of outer membrane stabilization by divalent cations. This confirms the relevance of the asymmetric models for future studies of outer membrane stability and antibiotic penetration.« less

  2. Effect of Divalent Cation Removal on the Structure of Gram-Negative Bacterial Outer Membrane Models

    SciTech Connect (OSTI)

    Clifton, Luke A.; Skoda, Maximilian W. A.; Le Brun, Anton P.; Ciesielski, Filip; Kuzmenko, Ivan; Holt, Stephen A.; Lakey, Jeremy H.

    2014-12-09

    The Gram-negative bacterial outer membrane (GNB-OM) is asymmetric in its lipid composition with a phospholipid-rich inner leaflet and an outer leaflet predominantly composed of lipopolysaccharides (LPS). LPS are polyanionic molecules, with numerous phosphate groups present in the lipid A and core oligosaccharide regions. The repulsive forces due to accumulation of the negative charges are screened and bridged by the divalent cations (Mg2+ and Ca2+) that are known to be crucial for the integrity of the bacterial OM. Indeed, chelation of divalent cations is a well-established method to permeabilize Gram-negative bacteria such as Escherichia coli. Here, we use X-ray and neutron reflectivity (XRR and NR, respectively) techniques to examine the role of calcium ions in the stability of a model GNB-OM. Using XRR we show that Ca2+ binds to the core region of the rough mutant LPS (RaLPS) films, producing more ordered structures in comparison to divalent cation free monolayers. Using recently developed solid-supported models of the GNB-OM, we study the effect of calcium removal on the asymmetry of DPPC:RaLPS bilayers. We show that without the charge screening effect of divalent cations, the LPS is forced to overcome the thermodynamically unfavorable energy barrier and flip across the hydrophobic bilayer to minimize the repulsive electrostatic forces, resulting in about 20% mixing of LPS and DPPC between the inner and outer bilayer leaflets. These results reveal for the first time the molecular details behind the well-known mechanism of outer membrane stabilization by divalent cations. This confirms the relevance of the asymmetric models for future studies of outer membrane stability and antibiotic penetration.

  3. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

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

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-01-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt−1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through a combination of ligand-switching and directmore » charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

  4. A New Improved Na-K Geothermometer By Artificial Neural Networks...

    Open Energy Info (EERE)

    567-577), Truesdell (1975; Proc. 2nd UN Symposium), Tonani (1980; Proc. Adv. Eur. Geoth. Research, 2nd Symposium), Fournier (1979a; J. Volcanol. Geotherm. Res. 5, 1-16), Nieva and...

  5. An Empirical Na-K-Ca Geothermometer For Natural Waters | Open...

    Open Energy Info (EERE)

    temperature environments ranging from 4 to 340C. The data for most geothermal waters cluster near a straight line when plotted as the function vs reciprocal of absolute...

  6. Are the Radical Centers in Peptide Radical Cations Mobile? The Generation, Tautomerism, and Dissociation of Isomeric α-Carbon-Centered Triglycine Radical Cations in the Gas Phase

    SciTech Connect (OSTI)

    Chu, Ivan K.; Zhao, Junfang; Xu, Minjie; Siu, Shiu On; Hopkinson, Alan C.; Siu , K W Michael

    2008-05-31

    The mobility of the radical center in three isomeric triglycine radical cationss[G•GG]+, [GG•G]+, and [GGG•]+shas been investigated theoretically via density functional theory (DFT) and experimentally via tandem mass spectrometry. These radical cations were generated by collision-induced dissociations (CIDs) of Cu(II)-containing ternary complexes that contain the tripeptides YGG, GYG, and GGY, respectively (G and Y are the glycine and tyrosine residues, respectively). Dissociative electron transfer within the complexes led to observation of [Y•GG]+, [GY•G]+, and [GGY•]+; CID resulted in cleavage of the tyrosine side chain as p-quinomethide, yielding [G•GG]+, [GG•G]+, and [GGG•]+, respectively. Interconversions between these isomeric triglycine radical cations have relatively high barriers (g44.7 kcal/mol), in support of the thesis that isomerically pure [G•GG]+, [GG•G]+, and [GGG•]+ can be experimentally produced. This is to be contrasted with barriers < 17 kcal/mol that were encountered in the tautomerism of protonated triglycine [Rodriquez C. F. et al. J. Am. Chem. Soc. 2001, 123, 3006-3012]. The CID spectra of [G•GG]+, [GG•G]+, and [GGG•]+ were substantially different, providing experimental proof that initially these ions have distinct structures. DFT calculations showed that direct dissociations are competitive with interconversions followed by dissociation.

  7. Preferential solvation of lithium cations and impacts on oxygen reduction in lithium–air batteries

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

    Zheng, Dong; Qu, Deyu; Yang, Xiao -Qing; Lee, Hung -Sui; Qu, Deyang

    2015-09-16

    The solvation of Li⁺ with eleven non-aqueous solvents commonly used as the electrolytes for Li batteries were studied. The solvation preferences of different solvents were compared by means of electrospray mass spectrometry and collision-induced dissociation. The relative strength of the solvent for the solvation of Li⁺ was determined. The Lewis acidity of the solvated Li⁺ cations was determined by the preferential solvation of the solvent in the solvation shell. The kinetics of the catalytic disproportionation of the O₂⁻ depends on the relative Lewis acidity of the solvated Li⁺ ion. The impact of the solvated Li⁺ cation on the O₂ redoxmore » reaction was also investigated.« less

  8. Controlling the actuation properties of MXene paper electrodes upon cation intercalation

    SciTech Connect (OSTI)

    Come, Jeremy E.; Black, Jennifer M.; Naguib, Michael; Lukatskaya, Maria R.; Beidaghi, Majid; Wesolowski, David J.; Gogotsi, Yury; Rondinone, Adam J.; Balke, Nina; Kalinin, Sergei V.

    2015-08-05

    Atomic force microscopy was used to monitor the macroscopic deformation in a delaminated Ti?C? paper electrode in-situ, during charge/discharge in a variety of aqueous electrolytes to examine the effect of the cation intercalation on the electrochemical behavior and mechanical response. The results show a strong dependence of the electrode deformation on cation size and charge. The electrode undergoes a large contraction during Li?, Na? or Mg? intercalation, differentiating the Ti?C? paper from conventional electrodes where redox intercalation of ions (e.g. Li?) into the bulk phase (e.g. graphite, silicon) results in volumetric expansion. This feature may explain the excellent rate performance and cyclability reported for MXenes. We also demonstrated that the variation of the electromechanical contraction can be easily adjusted by electrolyte exchange, and shows interesting characteristics for the design of actuators based on 2D metal carbides.

  9. Aza Cope Rearrangement of Propargyl Enammonium Cations Catalyzed By a Self-Assembled `Nanozyme

    SciTech Connect (OSTI)

    Hastings, Courntey J.; Fiedler, Dorothea; Bergman, Robert G.; Raymond, Kenneth N.

    2008-02-27

    The tetrahedral [Ga{sub 4}L{sub 6}]{sup 12-} assembly (L = N,N-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene) encapsulates a variety of cations, including propargyl enammonium cations capable of undergoing the aza Cope rearrangement. For propargyl enammonium substrates that are encapsulated in the [Ga{sub 4}L{sub 6}]{sup 12-} assembly, rate accelerations of up to 184 are observed when compared to the background reaction. After rearrangement, the product iminium ion is released into solution and hydrolyzed allowing for catalytic turnover. The activation parameters for the catalyzed and uncatalyzed reaction were determined, revealing that a lowered entropy of activation is responsible for the observed rate enhancements. The catalyzed reaction exhibits saturation kinetics; the rate data obey the Michaelis-Menten model of enzyme kinetics, and competitive inhibition using a non-reactive guest has been demonstrated.

  10. Controlling the actuation properties of MXene paper electrodes upon cation intercalation

    SciTech Connect (OSTI)

    Come, Jeremy E.; Black, Jennifer M.; Naguib, Michael; Lukatskaya, Maria R.; Beidaghi, Majid; Wesolowski, David J.; Gogotsi, Yury; Rondinone, Adam J.; Balke, Nina; Kalinin, Sergei V.

    2015-08-05

    Atomic force microscopy was used to monitor the macroscopic deformation in a delaminated Ti₃C₂ paper electrode in-situ, during charge/discharge in a variety of aqueous electrolytes to examine the effect of the cation intercalation on the electrochemical behavior and mechanical response. The results show a strong dependence of the electrode deformation on cation size and charge. The electrode undergoes a large contraction during Li⁺, Na⁺ or Mg²⁺ intercalation, differentiating the Ti₃C₂ paper from conventional electrodes where redox intercalation of ions (e.g. Li⁺) into the bulk phase (e.g. graphite, silicon) results in volumetric expansion. This feature may explain the excellent rate performance and cyclability reported for MXenes. We also demonstrated that the variation of the electromechanical contraction can be easily adjusted by electrolyte exchange, and shows interesting characteristics for the design of actuators based on 2D metal carbides.

  11. Preferential solvation of lithium cations and impacts on oxygen reduction in lithium–air batteries

    SciTech Connect (OSTI)

    Zheng, Dong; Qu, Deyu; Yang, Xiao -Qing; Lee, Hung -Sui; Qu, Deyang

    2015-09-16

    The solvation of Li⁺ with eleven non-aqueous solvents commonly used as the electrolytes for Li batteries were studied. The solvation preferences of different solvents were compared by means of electrospray mass spectrometry and collision-induced dissociation. The relative strength of the solvent for the solvation of Li⁺ was determined. The Lewis acidity of the solvated Li⁺ cations was determined by the preferential solvation of the solvent in the solvation shell. The kinetics of the catalytic disproportionation of the O₂⁻ depends on the relative Lewis acidity of the solvated Li⁺ ion. The impact of the solvated Li⁺ cation on the O₂ redox reaction was also investigated.

  12. Cloning and first functional characterization of a plant cyclic nucleotide-gated cation channel

    SciTech Connect (OSTI)

    Leng, Q.; Mercier, R.W.; Yao, W.; Berkowitz, G.A.

    1999-11-01

    Cyclic nucleotide-gated (cng) non-selective cation channels have been cloned from a number of animal systems. These channels are characterized by direct gating upon cAMO or cGMO binding to the intracellular portion of the channel protein, which leads to an increase in channel conductance. Animal cng channels are involved in signal transduction systems; they translate stimulus-induced changes in cytosolic cyclic nucleotide into altered cell membrane potential and/or cation flux as part of a signal cascade pathway. Putative plant homologs of animal cng channels have been identified. However, functional characterization (i.e., demonstration of cyclic-nucleotide-dependent ion currents) of a plant cng channel has not yet been accomplished. The authors report the cloning and first functional characterization of a plant member of this family of ion channels. The Arabidopsis cDNA AtCNGC2 encodes a polypeptide with deduced homology to the {alpha}-subunit of animal channels, and facilitates cyclic nucleotide-dependent cation currents upon expression in a number of heterologous systems. AtCNGC2 expression in a yeast mutant lacking a low-affinity K{sup +} uptake system complements growth inhibition only when lipophilic nucleotides are present in the culture medium. Voltage clamp analysis indicates that Xenopus lawvis oocytes injected with AtCNGC2 cRNA demonstrate cyclic-nucleotide-dependent, inward-rectifying K{sup +} currents. Human embryonic kidney cells (HEK293) transfected with AtCNGC2 cDNA demonstrate increased permeability to Ca{sup 2+} only in the presence of lipophilic cyclic nucleotides. The evidence presented here supports the functional classification of AtCNGC2 as a cyclic-nucleotide-gated cation channel, and presents the first direct evidence identifying a plant member of this ion channel family.

  13. Water soluble/dispersible and easy removable cationic adhesives and coating for paper recycling

    DOE Patents [OSTI]

    Deng, Yulin; Yan, Zegui

    2005-11-29

    The present invention is an adhesive or coating composition that is dispersible or dissolvable in water, making it useful in as a coating or adhesive in paper intended for recycling. The composition of the present invention is cationically charged thereby binding with the fibers of the paper slurry and thus, resulting in reduced deposition of adhesives on equipment during the recycling process. The presence of the composition of the present invention results in stronger interfiber bonding in products produced from the recycled fibers.

  14. Enhancing Cation-Exchange Capacity of Biochar for Soil Amendment and Global

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

    Carbon Sequestration - Energy Innovation Portal Biomass and Biofuels Biomass and Biofuels Find More Like This Return to Search Enhancing Cation-Exchange Capacity of Biochar for Soil Amendment and Global Carbon Sequestration Oak Ridge National Laboratory Contact ORNL About This Technology Technology Marketing SummaryPhotosynthesis captures more carbon dioxide from the atmosphere than any other process on Earth. However, because biomass is not stable and is always decomposing, it is of limited

  15. The Lightest Organic Radical Cation for Charge Storage in Redox Flow

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

    Batteries - Joint Center for Energy Storage Research August 25, 2016, Research Highlights The Lightest Organic Radical Cation for Charge Storage in Redox Flow Batteries A family of dimethoxybenzene derivatives have been designed and screened using a systematic pruning approach and a stepwise work flow. Compound 6 and 7 not only show promising results in the screening work flow, including cyclic voltammetry, bulk electrolysis cell tests, flow cell tests and EPR kinetic test, but also offer

  16. Strategies to Suppress Cation Vacancies in Metal Oxide Alloys: Consequences for Solar Energy Conversion

    SciTech Connect (OSTI)

    Toroker, Maytal; Carter, Emily A.

    2015-09-01

    First-row transition metal oxides (TMOs) are promising alternative materials for inexpensive and efficient solar energy conversion. However, their conversion efficiency can be deleteriously affected by material imperfections, such as atomic vacancies. In this work, we provide examples showing that in some iron-containing TMOs, iron cation vacancy formation can be suppressed via alloying. We calculate within density functional theory+U theory the iron vacancy formation energy in binary rock-salt oxide alloys that contain iron, manganese, nickel, zinc, and/or magnesium. We demonstrate that formation of iron vacancies is less favorable if we choose to alloy iron(II) oxide with metals that cannot readily accept vacancy-generated holes, e.g., magnesium, manganese, nickel, or zinc. Since there are less available sites for holes and the holes are forced to reside on iron cations, the driving force for iron vacancy formation decreases. These results are consistent with an experiment observing a sharp drop in cation vacancy concentration upon alloying iron(II) oxide with manganese.

  17. HYDROGENATION OF PAH CATIONS: A FIRST STEP TOWARD H{sub 2} FORMATION

    SciTech Connect (OSTI)

    Boschman, L.; Cazaux, S.; Spaans, M.; Reitsma, G.; Schlathoelter, T.; Hoekstra, R.; Gonzalez-Magana, O.

    2012-12-20

    Molecular hydrogen is the most abundant molecule in the universe. A large fraction of H{sub 2} forms by association of hydrogen atoms adsorbed on polycyclic aromatic hydrocarbons (PAHs), where formation rates depend crucially on the H sticking probability. We have experimentally studied PAH hydrogenation by exposing coronene cations, confined in a radio-frequency ion trap, to gas phase atomic hydrogen. A systematic increase of the number of H atoms adsorbed on the coronene with the time of exposure is observed. Odd coronene hydrogenation states dominate the mass spectrum up to 11 H atoms attached. This indicates the presence of a barrier preventing H attachment to these molecular systems. For the second and fourth hydrogenations, barrier heights of 72 {+-} 6 meV and 40 {+-} 10 meV, respectively, are found, which are in good agreement with theoretical predictions for the hydrogenation of neutral PAHs. Our experiments, however, prove that the barrier does not vanish for higher hydrogenation states. These results imply that PAH cations, as their neutral counterparts, exist in highly hydrogenated forms in the interstellar medium. Due to this catalytic activity, PAH cations and neutrals seem to contribute similarly to the formation of H{sub 2}.

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

    DOE Patents [OSTI]

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

    2013-08-13

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

  19. Gas-phase energies of actinide oxides -- an assessment of neutral and cationic monoxides and dioxides from thorium to curium

    SciTech Connect (OSTI)

    Marcalo, Joaquim; Gibson, John K.

    2009-08-10

    An assessment of the gas-phase energetics of neutral and singly and doubly charged cationic actinide monoxides and dioxides of thorium, protactinium, uranium, neptunium, plutonium, americium, and curium is presented. A consistent set of metal-oxygen bond dissociation enthalpies, ionization energies, and enthalpies of formation, including new or revised values, is proposed, mainly based on recent experimental data and on correlations with the electronic energetics of the atoms or cations and with condensed-phase thermochemistry.

  20. Effect of a-site cation deficiency and YSZ additions on sintering and properties of doped lanthanum manganite

    SciTech Connect (OSTI)

    Stevenson, J.W.; Armstrong, T.R.; Weber, W.J.

    1995-06-01

    The sintering behavior of Ca- and Sr-doped lanthanum manganite (the preferred SOFC cathode material) is highly dependent on the relative proportion of A and B site cations in the material. In general, A-site cation deficiency increases sintered density. The effect of additions of YSZ to lanthanum manganite (to expand the reactive region at the cathode/electrolyte interface and improve thermal expansion and sintering shrinkage matches) on sintering and other properties will also be reported.

  1. Synergistic extraction of some univalent cations into nitrobenzene by using cesium dicarbollylcobaltate and calix[4]arene-...

    SciTech Connect (OSTI)

    Makrlik, Emanuel; Selucky, P.; Vanura, Petr; Moyer, Bruce A

    2013-01-01

    From extraction experiments and c-activity measurements, the exchange extraction constants corresponding to the general equilibrium M+ (aq) + CsL+ (nb) , ML+ (nb) + Cs+ (aq) taking place in the two-phase water nitrobenzene system (M+ = K+, Rb+, NH+4,Ag+, Tl+; L = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Furthermore, the stability constants of the ML+ complexes in nitrobenzene saturated with water were calculated; they were found to increase in the following cation order: NH+4 < K+ < Ag+ < Rb+ < Tl+.

  2. Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries

    DOE Patents [OSTI]

    Manthiram, Arumugam; Choi, Wongchang

    2014-05-13

    The present invention includes compositions and methods of making cation-substituted and fluorine-substituted spinel cathode compositions by firing a LiMn.sub.2-y-zLi.sub.yM.sub.zO.sub.4 oxide with NH.sub.4HF.sub.2 at low temperatures of between about 300 and 700.degree. C. for 2 to 8 hours and a .eta. of more than 0 and less than about 0.50, mixed two-phase compositions consisting of a spinel cathode and a layered oxide cathode, and coupling them with unmodified or surface modified graphite anodes in lithium ion cells.

  3. Functional Mn–Mg{sub k} cation complexes in GaN featured by Raman spectroscopy

    SciTech Connect (OSTI)

    Devillers, T. Bonanni, A.; Leite, D. M. G.; Dias da Silva, J. H.

    2013-11-18

    The evolution of the optical branch in the Raman spectra of (Ga,Mn)N:Mg epitaxial layers as a function of the Mn and Mg concentrations, reveals the interplay between the two dopants. We demonstrate that the various Mn-Mg-induced vibrational modes can be understood in the picture of functional Mn–Mg{sub k} complexes formed when substitutional Mn cations are bound to k substitutional Mg through nitrogen atoms, the number of ligands k being driven by the ratio between the Mg and the Mn concentrations.

  4. Ionic charge transport between blockages: Sodium cation conduction in freshly excised bulk brain tissue

    SciTech Connect (OSTI)

    Emin, David; Akhtari, Massoud; Ellingson, B. M.; Mathern, G. W.

    2015-08-15

    We analyze the transient-dc and frequency-dependent electrical conductivities between blocking electrodes. We extend this analysis to measurements of ions’ transport in freshly excised bulk samples of human brain tissue whose complex cellular structure produces blockages. The associated ionic charge-carrier density and diffusivity are consistent with local values for sodium cations determined non-invasively in brain tissue by MRI (NMR) and diffusion-MRI (spin-echo NMR). The characteristic separation between blockages, about 450 microns, is very much shorter than that found for sodium-doped gel proxies for brain tissue, >1 cm.

  5. In-Situ TEM and DFT Study of Large Cation Transport and Failure Mechanism

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

    In Single SnO2 Nanowire - Joint Center for Energy Storage Research July 18, 2013, Research Highlights In-Situ TEM and DFT Study of Large Cation Transport and Failure Mechanism In Single SnO2 Nanowire (Top)Captured in-situ TEM movie frame showing the pristine SnO2 nanowire, displacement reaction upon Na insertion leads to two phases materials and the corresponding electron diffraction pattern. Upon desodiation, pore forms, leading to high impedence of the electrode. (Bottom) High resolution

  6. Solvation structure and transport properties of alkali cations in dimethyl sulfoxide under exogenous static electric fields

    SciTech Connect (OSTI)

    Kerisit, Sebastien; Vijayakumar, M. E-mail: karl.mueller@pnnl.gov; Han, Kee Sung; Mueller, Karl T. E-mail: karl.mueller@pnnl.gov

    2015-06-14

    A combination of molecular dynamics simulations and pulsed field gradient nuclear magnetic resonance spectroscopy is used to investigate the role of exogenous electric fields on the solvation structure and dynamics of alkali ions in dimethyl sulfoxide (DMSO) and as a function of temperature. Good agreement was obtained, for select alkali ions in the absence of an electric field, between calculated and experimentally determined diffusion coefficients normalized to that of pure DMSO. Our results indicate that temperatures of up to 400 K and external electric fields of up to 1 V nm{sup −1} have minimal effects on the solvation structure of the smaller alkali cations (Li{sup +} and Na{sup +}) due to their relatively strong ion-solvent interactions, whereas the solvation structures of the larger alkali cations (K{sup +}, Rb{sup +}, and Cs{sup +}) are significantly affected. In addition, although the DMSO exchange dynamics in the first solvation shell differ markedly for the two groups, the drift velocities and mobilities are not significantly affected by the nature of the alkali ion. Overall, although exogenous electric fields induce a drift displacement, their presence does not significantly affect the random diffusive displacement of the alkali ions in DMSO. System temperature is found to have generally a stronger influence on dynamical properties, such as the DMSO exchange dynamics and the ion mobilities, than the presence of electric fields.

  7. Elucidating the Higher Stability of Vanadium (V) Cations in Mixed Acid Based Redox Flow Battery Electrolytes

    SciTech Connect (OSTI)

    Vijayakumar, M.; Wang, Wei; Nie, Zimin; Sprenkle, Vincent L.; Hu, Jian Z.

    2013-11-01

    The Vanadium (V) cation structures in mixed acid based electrolyte solution were analysed by density functional theory (DFT) based computational modelling and 51V and 35Cl Nuclear Magnetic Resonance (NMR) spectroscopy. The Vanadium (V) cation exists as di-nuclear [V2O3Cl2.6H2O]2+ compound at higher vanadium concentrations (≥1.75M). In particular, at high temperatures (>295K) this di-nuclear compound undergoes ligand exchange process with nearby solvent chlorine molecule and forms chlorine bonded [V2O3Cl2.6H2O]2+ compound. This chlorine bonded [V2O3Cl2.6H2O]2+ compound might be resistant to the de-protonation reaction which is the initial step in the precipitation reaction in Vanadium based electrolyte solutions. The combined theoretical and experimental approach reveals that formation of chlorine bonded [V2O3Cl2.6H2O]2+ compound might be central to the observed higher thermal stability of mixed acid based Vanadium (V) electrolyte solutions.

  8. Modeling cation diffusion in compacted water-saturatedNa-bentonite at low ionic strength

    SciTech Connect (OSTI)

    Bourg, Ian C.; Sposito, Garrison; Bourg, Alain C.M.

    2007-08-28

    Sodium bentonites are used as barrier materials for the isolation of landfills and are under consideration for a similar use in the subsurface storage of high-level radioactive waste. The performance of these barriers is determined in large part by molecular diffusion in the bentonite pore space. We tested two current models of cation diffusion in bentonite against experimental data on the relative apparent diffusion coefficients of two representative cations, sodium and strontium. On the 'macropore/nanopore' model, solute molecules are divided into two categories, with unequal pore-scale diffusion coefficients, based on location: in macropores or in interlayer nanopores. On the 'surface diffusion' model, solute molecules are divided into categories based on chemical speciation: dissolved or adsorbed. The macropore/nanopore model agrees with all experimental data at partial montmorillonite dry densities ranging from 0.2 (a dilute bentonite gel) to 1.7 kg dm{sup -3} (a highly compacted bentonite with most of its pore space located in interlayer nanopores), whereas the surface diffusion model fails at partial montmorillonite dry densities greater than about 1.2 kg dm{sup -3}.

  9. Electron channeling X-ray microanalysis for cation configuration in irradiate magnesium aluminate spinel

    SciTech Connect (OSTI)

    Matsumura, S.; Soeda, T.; Zaluzec, N. J.; Kinoshita, C.

    1999-12-22

    High angular resolution electron channeling X-ray spectroscopy (HARECXS) was examined as a practical tool to locate lattice-ions in spinel crystals. The orientation dependent intensity distribution of emitted X-rays obtained by HARECXS is so sensitive to lattice-ion configuration in the illuminated areas that the occupation probabilities on specific positions in the crystal lattice can be determined accurately through comparison with the theoretical rocking curves. HARECXS measurements have revealed partially disordered cation arrangement in MgO{center_dot}nAl{sub 2}O{sub 3} with n = 1.0 and 2.4. Most Al{sup 3+} lattice-ions occupy the octahedral (VIII) sites, while Mg{sup 2} lattice-ions reside on both the tetrahedral (IV) and the octahedral (VIII) sites. The structural vacancies are enriched in the IV-sites. Further evacuation of cations from the IV-sites to the VIII-sites is recognized in a disordering process induced by irradiation with 1 MeV Ne{sup +} ions up to 8.9 dpa at 870 K.

  10. Controlling the actuation properties of MXene paper electrodes upon cation intercalation

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

    Come, Jeremy E.; Black, Jennifer M.; Naguib, Michael; Lukatskaya, Maria R.; Beidaghi, Majid; Wesolowski, David J.; Gogotsi, Yury; Rondinone, Adam J.; Balke, Nina; Kalinin, Sergei V.

    2015-08-05

    Atomic force microscopy was used to monitor the macroscopic deformation in a delaminated Ti₃C₂ paper electrode in-situ, during charge/discharge in a variety of aqueous electrolytes to examine the effect of the cation intercalation on the electrochemical behavior and mechanical response. The results show a strong dependence of the electrode deformation on cation size and charge. The electrode undergoes a large contraction during Li⁺, Na⁺ or Mg²⁺ intercalation, differentiating the Ti₃C₂ paper from conventional electrodes where redox intercalation of ions (e.g. Li⁺) into the bulk phase (e.g. graphite, silicon) results in volumetric expansion. This feature may explain the excellent rate performancemore » and cyclability reported for MXenes. We also demonstrated that the variation of the electromechanical contraction can be easily adjusted by electrolyte exchange, and shows interesting characteristics for the design of actuators based on 2D metal carbides.« less

  11. Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes

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

    Berg, John M.; Gaunt, Andrew J.; May, Iain; Pugmire, Alison L.; Reilly, Sean D.; Scott, Brian L.; Wilkerson, Marianne P.

    2015-04-22

    A-type tri-lacunary heteropolyoxotungstate anions (e.g., [PW9O34]9-, [AsW9O34]9-, [SiW9O34]10- and [GeW9O34]10-) are multi-dentate oxygen donor ligands that readily form sandwich complexes with actinyl cations ({UO2}2+, {NpO2}+, {NpO2}2+ & {PuO2}2+) in near neutral/slightly alkaline aqueous solutions. Two or three actinyl cations are sandwiched between two trilacunary anions, with additional cations (Na+, K+ or NH4 +) also often held within the cluster. Studies thus far have indicated that it is these additional +I cations, rather than the specific actinyl cation, that direct the structural variation in the complexes formed. We now report the structural characterization of the neptunyl (VI) cluster complex (NH4)13 [Na(NpO2)2(A-α-more » PW9O34)2]·12H2O. The anion in this complex, [Na(NpO2)2(PW9O34)2]13-, contains one Na+ cation and two {NpO2}2+ cations held between two [PW9O34]9- anions – with an additional partial occupancy NH4 + or {NpO2}2+ cation also present. In the analogous uranium (VI) system, under similar reaction conditions that includes an excess of NH4Cl in the parent solution, it was previously shown that [(NH4)2(UVIO2)2(A-PW9O34)2]12- is the dominant species in both solution and the crystallized salt. Spectroscopic studies provide further proof of differences in the observed chemistry for the {NpO2}2+/[PW9O34]9- and {UO2}2+/[PW9O34]9- systems, both in solution and in solid state complexes crystallized from comparable salt solutions. The work revealed that varying the actinide element (Np vs. U) can indeed measurably impact structure and complex stability in the cluster chemistry of actinyl (VI) cations with A-type tri-lacunary heteropolyoxotungstate anions.« less

  12. Gas-phase reactions of polycyclic aromatic hydrocarbon cations and their nitrogen-containing analogs with H atoms

    SciTech Connect (OSTI)

    Demarais, Nicholas J.; Yang, Zhibo; Bierbaum, Veronica M. [Department of Chemistry and Biochemistry, 215 UCB, University of Colorado, Boulder, CO 80309-0215 (United States); Snow, Theodore P., E-mail: Nicholas.Demarais@Colorado.edu, E-mail: Zhibo.Yang@ou.edu, E-mail: Veronica.Bierbaum@Colorado.edu, E-mail: Theodore.Snow@Colorado.edu [Center for Astrophysics and Space Astronomy, 389 UCB, University of Colorado, Boulder, CO 80309-0389 (United States)

    2014-03-20

    We have studied the reactions of polycyclic aromatic hydrocarbon cations and their nitrogen-containing analogs with H atoms. Reaction rate constants are measured at 300 K using a flowing afterglow-selected ion flow tube. We have implemented the laser induced acoustic desorption technique to allow the study of large, non-volatile species in the gas phase. The extension of this work from previous studies shows that the reactivity of polycyclic aromatic hydrocarbon cations with H atoms reaches a constant value for large cations. There is a small difference in reactivity when comparing molecules of different size and geometry; however, no difference in reactivity was found when nitrogen was incorporated into the ring.

  13. Room-temperature ferroelectricity of SrTiO{sub 3} films modulated by cation concentration

    SciTech Connect (OSTI)

    Yang, Fang; Zhang, Qinghua; Yang, Zhenzhong; Gu, Junxing; Liang, Yan; Li, Wentao; Wang, Weihua; Jin, Kuijuan; Gu, Lin; Guo, Jiandong

    2015-08-24

    The room-temperature ferroelectricity of SrTiO{sub 3} is promising for oxide electronic devices controlled by multiple fields. An effective way to control the ferroelectricity is highly demanded. Here, we show that the off-centered antisite-like defects in SrTiO{sub 3} films epitaxially grown on Si (001) play the determinative role in the emergence of room-temperature ferroelectricity. The density of these defects changes with the film cation concentration sensitively, resulting in a varied coercive field of the ferroelectric behavior. Consequently, the room-temperature ferroelectricity of SrTiO{sub 3} films can be effectively modulated by tuning the temperature of metal sources during the molecular beam epitaxy growth. Such an easy and reliable modulation of the ferroelectricity enables the flexible engineering of multifunctional oxide electronic devices.

  14. Phenolic cation exchange resin material for recovery of cesium and strontium

    DOE Patents [OSTI]

    Ebra, Martha A.; Wallace, Richard M.

    1983-01-01

    A phenolic cation exchange resin with a chelating group has been prepared by reacting resorcinol with iminodiacetic acid in the presence of formaldehyde at a molar ratio of about 1:1:6. The material is highly selective for the simultaneous recovery of both cesium and strontium from aqueous alkaline solutions, such as, aqueous alkaline nuclear waste solutions. The organic resins are condensation polymers of resorcinol and formaldehyde with attached chelating groups. The column performance of the resins compares favorably with that of commercially available resins for either cesium or strontium removal. By combining Cs.sup.+ and Sr.sup.2+ removal in the same bed, the resins allow significant reduction of the size and complexity of facilities for processing nuclear waste.

  15. A Hybrid Redox-Supercapacitor System with Anionic Catholyte and Cationic Anolyte

    SciTech Connect (OSTI)

    Wang, B; Macia-Agullo, JA; Prendiville, DG; Zheng, X; Liu, D; Zhang, Y; Boettcher, SW; Ji, X; Stucky, GD

    2014-04-11

    A significant challenge for energy storage technologies is to realize battery-level energy density and capacitor-level durability and power density in one device. By introducing an electrolyte composed of an anionic catholyte and a cationic anolyte into a symmetric carbon-based supercapacitor configuration, a hybrid electrochemical battery-supercapacitor system using soluble redox species delivers significantly improved energy density from 20 to 42 W.h/kg (based on the electrode mass) and stable capacities for > 10(4) cycles. The ionic species formed in the electrolyte are studied by UV-Vis, Raman and mass spectroscopy to probe the energy storage mechanism. The strategy is general and may provide a route to critically-needed fast-charging devices with both high energy density and power. (C) 2014 The Electrochemical Society. All rights reserved.

  16. Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries

    DOE Patents [OSTI]

    Manthiram, Arumugam; Choi, Wonchang

    2010-05-18

    The present invention includes compositions and methods of making cation-substituted and fluorine-substituted spinel cathode compositions by firing a LiMn2-y-zLiyMzO4 oxide with NH4HF2 at low temperatures of between about 300 and 700.degree. C. for 2 to 8 hours and a .eta. of more than 0 and less than about 0.50, mixed two-phase compositions consisting of a spinel cathode and a layered oxide cathode, and coupling them with unmodified or surface modified graphite anodes in lithium ion cells.

  17. Opposite correlations between cation disordering and amorphization resistance in spinels versus pyrochlores

    SciTech Connect (OSTI)

    Uberuaga, Blas Pedro; Tang, Ming; Jiang, Chao; Valdez, James A.; Smith, Roger; Wang, Yongqiang; Sickafus, Kurt E.

    2015-10-29

    Understanding and predicting radiation damage evolution in complex materials is crucial for developing next-generation nuclear energy sources. Here, using a combination of ion beam irradiation, transmission electron microscopy and X-ray diffraction, we show that, contrary to the behaviour observed in pyrochlores, the amorphization resistance of spinel compounds correlates directly with the energy to disorder the structure. Using a combination of atomistic simulation techniques, we ascribe this behaviour to structural defects on the cation sublattice that are present in spinel but not in pyrochlore. Specifically, because of these structural defects, there are kinetic pathways for the relaxation of disorder in spinel that are absent in pyrochlore. This leads to a direct correlation between amorphization resistance and disordering energetics in spinel, the opposite of that observed in pyrochlores. Furthermore, these results provide new insight into the origins of amorphization resistance in complex oxides beyond fluorite derivatives.

  18. Opposite correlations between cation disordering and amorphization resistance in spinels versus pyrochlores

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

    Uberuaga, Blas Pedro; Tang, Ming; Jiang, Chao; Valdez, James A.; Smith, Roger; Wang, Yongqiang; Sickafus, Kurt E.

    2015-10-29

    Understanding and predicting radiation damage evolution in complex materials is crucial for developing next-generation nuclear energy sources. Here, using a combination of ion beam irradiation, transmission electron microscopy and X-ray diffraction, we show that, contrary to the behaviour observed in pyrochlores, the amorphization resistance of spinel compounds correlates directly with the energy to disorder the structure. Using a combination of atomistic simulation techniques, we ascribe this behaviour to structural defects on the cation sublattice that are present in spinel but not in pyrochlore. Specifically, because of these structural defects, there are kinetic pathways for the relaxation of disorder in spinelmore » that are absent in pyrochlore. This leads to a direct correlation between amorphization resistance and disordering energetics in spinel, the opposite of that observed in pyrochlores. Furthermore, these results provide new insight into the origins of amorphization resistance in complex oxides beyond fluorite derivatives.« less

  19. Self-Assembly of Hexanuclear Clusters of 4f and 5f Elements with Cation Specificity

    SciTech Connect (OSTI)

    Diwu, J.; Good, Justin J.; DiStefano, Victoria H.; Albrecht-Schmitt, Thomas E.

    2011-02-10

    Six hexanuclear clusters of 4f and 5f elements were synthesized by room-temperature slow concentration experiments. Cerium(IV), thorium(IV), and plutonium(IV) each form two different hexanuclear clusters, among which the cerium and plutonium clusters are isotypic, whereas the thorium clusters show more diversity. The change in ionic radii of approximately 0.08 Å between these different metal ions tunes the cavity size so that NH{sub 4}{sup +} (1.48 Å) has the right dimensions to assemble the cerium and plutonium clusters, whereas Cs{sup +} (1.69 Å) is necessary to assemble the thorium clusters. If these cations are not used in the reactions, only amorphous material is obtained.

  20. Aqueous precipitation: Population balance modeling and control in multi-cation systems

    SciTech Connect (OSTI)

    Voigt, J.A.

    1996-03-01

    Efficient separation of metal species from aqueous streams by precipitation techniques requires a fundamental understanding of the processes that occur during precipitation. These processes include particle nucleation, particle growth by solute deposition, agglomerate formation, and agglomerate breakup. Population balance method has been used to develop a kinetic model that accounts for these competing kinetic processes. The usefulness of the model is illustrated through its application to precipitation of yttrium hydroxynitrate, YHN. Kinetic parameters calculated from the model equations and system-specific solution chemistry are used to describe several aspects of the effect of pH on YHN precipitation. Implications for simultaneous precipitation of more than one cation type are discussed with examples. Effects of solution chemistry, precipitator design, and solvent choice are considered.

  1. Single-stage separation and esterification of cation salt carboxylates using electrodeionization

    DOE Patents [OSTI]

    Lin, YuPo J.; Henry, Michael; Hestekin, Jamie; Snyder, Seth W.; St. Martin, Edward J.

    2006-11-28

    A method of and apparatus for continuously making an organic ester from a lower alcohol and an organic acid is disclosed. An organic acid or salt is introduced or produced in an electrode ionization (EDI) stack with a plurality of reaction chambers each formed from a porous solid ion exchange resin wafer interleaved between anion exchange membranes or an anion exchange membrane and a cation exchange membrane or an anion exchange membrane and a bipolar exchange membranes. At least some reaction chambers are esterification chambers and/or bioreactor chambers and/or chambers containing an organic acid or salt. A lower alcohol in the esterification chamber reacts with an anion to form an organic ester and water with at least some of the water splitting with the ions leaving the chamber to drive the reaction.

  2. Phenolic cation-exchange resin material for recovery of cesium and strontium. [Patent application

    DOE Patents [OSTI]

    Ebra, M.A.; Wallace, R.M.

    1982-05-05

    A phenolic cation exchange resin with a chelating group has been prepared by reacting resorcinol with iminodiacetic acid in the presence of formaldehyde at a molar ratio of about 1:1:6. The material is highly selective for the simultaneous recovery of both cesium and strontium from aqueous alkaline solutions, such as, aqueous alkaline nuclear wate solutions. The organic resins are condensation polymers of resorcinol and formaldehyde with attached chelating groups. The column performance of the resins compares favorably with that of commercially available resins for either cesium or strontium removal. By combining Cs/sup +/ and Sr/sup 2 +/ removal in the same bed, the resins allow significant reduction of the size and complexity of facilities for processing nuclear waste.

  3. Cationic quaternization of cellulose with methacryloyloxy ethyl trimethyl ammonium chloride via ATRP method

    SciTech Connect (OSTI)

    Supeno; Daik, Rusli; El-Sheikh, Said M.

    2014-09-03

    The synthesis of a cationic cellulose copolymer from cellulose macro-initiator (MCC-BiB) and quaternary compound monomer (METMA) via atom transfer radical polymerization (ATRP) was studied. By using dimethylformamide (DMF), the optimum condition for successful synthesis was at the mole ratio of MCC-BIB:Catalyst:METMA = 1:1:26. The highest copolymer recovery was 93.2 % for 6 h and at 40°C. The copolymer was insoluble in weak polar solvents such as THF and DMF but soluble in methanol and water. The chemistry of cellulose copolymer was confirmed by the FTIR and TGA in which the METMA monomer was used as a reference. The absence of CC bond in the CiB-g-METMA spectrum indicated that graft copolymerization occurred.

  4. Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

    DOE Patents [OSTI]

    Skotheim, Terje A.; Okamoto, Yoshiyuki; Lee, Hung S.

    1989-01-01

    The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10.sup.-4 to 10.sup.-7 S cm.sup.-1 at room temperature.

  5. Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

    DOE Patents [OSTI]

    Skotheim, T.A.; Okamoto, Yoshiyuki; Lee, H.S.

    1989-11-21

    The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10[sup [minus]4] to 10[sup [minus]7] S cm[sup [minus]1] at room temperature.

  6. A theoretical study of the reaction paths for cobalt cation + propane

    SciTech Connect (OSTI)

    Fedorov, D.G.; Gordon, M.S.

    2000-03-23

    The triplet potential energy surface for the reaction of cobalt cation with propane has been studied along the two main reaction pathways leading to the formation of (1) hydrogen and propene and (2) methane and ethene. Effective core potentials for all elements have been used for all calculations. The geometries have been optimized at the complete active space self-consistent field (CASSCF) level of theory, and the final energetics have been refined at the multireference second-order perturbation theory (MRMP2) level with polarization function augmented basis sets. Reasonable agreement with the experimental energetics has been obtained, and the predicted mechanism is consistent with the experimentally determined mechanism of Haynes, Fisher, and Armentrout (J.Phys.Chem. 1996, 100, 18300).

  7. Computational study of the energetics of charge and cation mixing in U1-xCexO₂

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

    Hanken, B. E.; Stanek, C. R.; Grønbech-Jensen, N.; Asta, M.

    2011-08-26

    The formalism of electronic density-functional theory (DFT), with Hubbard-U corrections (DFT+U), is employed in a computational study of the energetics of fluorite-structured U1-xCexO₂ mixtures. The computational approach makes use of a procedure which facilitates convergence of the calculations to multiple self-consistent DFT+U solutions for a given cation arrangement, corresponding to different charge states for the U and Ce ions in several prototypical cation arrangements. Results indicate a significant dependence of the structural and energetic properties on the nature of both charge and cation ordering. With the effective Hubbard-U parameters that reproduce well the measured oxidation-reduction energies for urania and ceria,more » we find that charge transfer between U⁴⁺ and Ce⁴⁺ ions, leading to the formation of U⁵⁺ and Ce³⁺, gives rise to an increase in the mixing energy in the range of 4–14 kJ/mol of the formula unit, depending on the nature of the cation ordering. The results suggest that although charge transfer between uranium and cerium ions is disfavored energetically, it is likely to be entropically stabilized at the high temperatures relevant to the processing and service of urania-based solid solutions.« less

  8. Cation ordering and effect of biaxial strain in double perovskite CsRbCaZnCl6

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

    Pilania, G.; Uberuaga, B. P.

    2015-03-19

    Here, we investigate the electronic structure, energetics of cation ordering, and effect of biaxial strain on double perovskite CsRbCaZnCl6 using first-principles calculations based on density functional theory. The two constituents (i.e., CsCaCl3 and RbZnCl3) forming the double perovskite exhibit a stark contrast. While CsCaCl3 is known to exist in a cubic perovskite structure and does not show any epitaxial strain induced phase transitions within an experimentally accessible range of compressive strains, RbZnCl3 is thermodynamically unstable in the perovskite phase and exhibits ultra-sensitive response at small epitaxial strains if constrained in the perovskite phase. We show that combining the two compositionsmore » in a double perovskite structure not only improves overall stability but also the strain-polarization coupling of the material. Our calculations predict a ground state with P4/nmm space group for the double perovskite, where A-site cations (i.e., Cs and Rb) are layer-ordered and B-site cations (i.e., Ca and Zn) prefer a rocksalt type ordering. The electronic structure and bandgap in this system are shown to be quite sensitive to the B-site cation ordering and is minimally affected by the ordering of A-site cations. We find that at experimentally accessible compressive strains CsRbCaZnCl6 can be phase transformed from its paraelectric ground state to an antiferroelectric state, where Zn atoms contribute predominantly to the polarization. Furthermore, both energy difference and activation barrier for a transformation between this antiferroelectric state and the corresponding ferroelectric configuration are predicted to be small. As a result, the computational approach presented here opens a new pathway towards a rational design of novel double perovskites with improved strain response and functionalities.« less

  9. Colloid-Facilitated Transport of Cations in an Unsaturated Fractured Soil Under Transient Conditions

    SciTech Connect (OSTI)

    Ryan, Joseph

    2015-01-31

    Rainfall experiments were conducted using intact soil cores and an instrumented soil pedon to examine the effect of physical heterogeneity and rainfall characteristics on the mobilization of colloids, organic matter, cesium, and strontium in a fractured soil. To measure the spatial variability of infiltration of colloids and contaminants, samples were collected through a 19-port grid placed below the soil core in laboratory study and in 27 samplers at multiple depths in the soil pedon in the field study. Cesium and strontium were applied to the soil cores and the soil pedon prior to mobilization experiments. Rainwater solutions of multiple ionic strengths and organic matter concentrations were applied to the soil cores and soil pedon to mobilize in situ colloids, cesium, and strontium. The mobilization of colloids and metal cations occurred through preferential flow paths in the soil cores. Compared to steady rainfall, greater amounts of colloids were mobilized during rainfall interrupted by pauses, which indicates that the supply of colloids to be mobilized was replenished during the pauses. A maximum in the amount of mobilized colloids were mobilized during a rainfall following a pause of 2.5 d. Pauses of shorter or longer duration resulted in less colloid mobilization. Freeze-thaw cycles, a transient condition in winter, enhanced colloid mobilization and colloid-facilitated transport of cesium and strontium in the soil cores. The exchange of solutes between the soil matrix and macropores caused a hysteretic mobilization of colloids, cesium, and strontium during changes in ionic strength. Colloid-facilitated mobilization of cesium and strontium was important at low ionic strength in fractures where slow flow allowed greater exchange of flow between the fractures and the surrounding matrix. The release of cesium and strontium by cation exchange occurred at high ionic strength in fractures where there is a little exchange of pore water with the surrounding matrix

  10. A search for the sulphur hexafluoride cation with intense, few cycle laser pulses

    SciTech Connect (OSTI)

    Dota, Krithika; Mathur, Deepak; Centre for Atomic and Molecular Physics, Manipal University, Manipal 576 104 ; Dharmadhikari, Aditya K.; Dharmadhikari, Jayashree A.; Patra, Kaustuv; Tiwari, Ashwani K.

    2013-11-21

    It is well established that upon ionization of sulphur hexafluoride, the SF{sub 6}{sup +} ion is never observed in mass spectra. Recent work with ultrashort intense laser pulses has offered indications that when strong optical field are used, the resulting bond hardening can induce changes in the potential energy surfaces of molecular cations such that molecular ions that are normally unstable may, indeed, become metastable enough to enable their detection by mass spectrometry. Do intense, ultrashort laser pulses permit formation of SF{sub 6}{sup +}? We have utilized intense pulses of 5 fs, 11 fs, and 22 fs to explore this possibility. Our results are negative: no evidence is discovered for SF{sub 6}{sup +}. However, multiply charged sulphur and fluorine ions from highly charged SF{sub 6}{sup q+} ions are observed that enable us to resolve the controversy regarding the kinetic energy release accompanying formation of F{sup +} fragment ions. Quantum chemical computations of field-distorted potential energy curves of SF{sub 6} and its molecular ion enable us to rationalize our non-observation of SF{sub 6}{sup +}. Our findings have implications for high harmonic generation from SF{sub 6} in the few-cycle regime.

  11. Millisecond Kinetics of Nanocrystal Cation Exchange UsingMicrofluidic X-ray Absorption Spectroscopy

    SciTech Connect (OSTI)

    Chan, Emory M.; Marcus, Matthew A.; Fakra, Sirine; Elnaggar,Mariam S.; Mathies, Richard A.; Alivisatos, A. Paul

    2007-05-07

    We describe the use of a flow-focusing microfluidic reactorto measure the kinetics of theCdSe-to-Ag2Se nanocrystal cation exchangereaction using micro-X-ray absorption spectroscopy (mu XAS). The smallmicroreactor dimensions facilitate the millisecond mixing of CdSenanocrystal and Ag+ reactant solutions, and the transposition of thereaction time onto spatial coordinates enables the in situ observation ofthe millisecond reaction with mu XAS. XAS spectra show the progression ofCdSe nanocrystals to Ag2Se over the course of 100 ms without the presenceof long-lived intermediates. These results, along with supporting stoppedflow absorption experiments, suggest that this nanocrystal cationexchange reaction is highly efficient and provide insight into how thereaction progresses in individual particles. This experiment illustratesthe value and potential of in situ microfluidic X-ray synchrotrontechniques for detailed studies of the millisecond structuraltransformations of nanoparticles and other solution-phase reactions inwhich diffusive mixing initiates changes in local bond structures oroxidation states.

  12. Ionic liquids composed of phosphonium cations and organophosphate, carboxylate, and sulfonate as lubricant antiwear additives

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

    Zhou, Yan; Dyck, Jeffrey; Graham, Todd; Luo, Huimin; Leonard, Donovan N.; Qu, Jun

    2014-10-20

    Oil-soluble phosphonium-based ionic liquids (ILs) have recently been reported as potential ashless lubricant additives. This study is to expand the IL chemistry envelope and to achieve fundamental correlations between the ion structures and ILs’ physiochemical and tribological properties. Here we present eight ILs containing two different phosphonium cations and seven different anions from three groups: organophosphate, carboxylate, and sulfonate. The oil solubility of ILs seems largely governed by the IL molecule size and structure complexity. When used as oil additives, the ranking of effectiveness in wear protection for the anions are: organophosphate > carboxylate > sulfonate. All selected ILs outperformedmore » a commercial ashless anti-wear additive. Surface characterization from the top and the cross-section revealed the nanostructures and compositions of the tribo-films formed by the ILs. Some fundamental insights were achieved: branched and long alkyls improve the IL’s oil solubility, anions of a phosphonium-phosphate IL contribute most phosphorus in the tribofilm, and carboxylate anions, though free of P, S, N, or halogen, can promote the formation of an anti-wear tribofilm.« less

  13. Atomistic Studies of Cation Transport in Tetragonal ZrO2 During Zirconium Corrosion

    SciTech Connect (OSTI)

    Xian-Ming Bai; Yongfeng Zhang; Michael R. Tonks

    2013-10-01

    Zirconium alloys are the major fuel cladding materials in current reactors. The water-side corrosion is one of the major degradation mechanisms of these alloys. During corrosion the transport of oxidizing species in zirconium dioxide (ZrO2) determines the corrosion kinetics. Previously it has been argued that the outward diffusion of cation ions is important for forming protective oxides. In this work, the migration of Zr defects in tetragonal ZrO2 is studied with temperature accelerated dynamics and molecular dynamics simulations. The results show that Zr interstitials have anisotropic diffusion and migrate preferentially along the [001] or c direction in tetragonal ZrO2. The compressive stresses can increase the Zr interstitial migration barrier significantly. The migration barriers of some defect clusters can be much lower than those of point defects. The migration of Zr interstitials at some special grain boundaries is much slower than in a bulk oxide. The implications of these atomistic simulation results in the Zr corrosion are discussed.

  14. Independent control of the shape and composition of ionic nanocrystals through sequential cation exchange reactions

    SciTech Connect (OSTI)

    Luther, Joseph Matthew; Zheng, Haimei; Sadtler, Bryce; Alivisatos, A. Paul

    2009-07-06

    Size- and shape-controlled nanocrystal growth is intensely researched for applications including electro-optic, catalytic, and medical devices. Chemical transformations such as cation exchange overcome the limitation of traditional colloidal synthesis, where the nanocrystal shape often reflects the inherent symmetry of the underlying lattice. Here we show that nanocrystals, with established synthetic protocols for high monodispersity, can be templates for independent composition control. Specifically, controlled interconversion between wurtzite CdS, chalcocite Cu2S, and rock salt PbS occurs while preserving the anisotropic dimensions unique to the as-synthesized materials. Sequential exchange reactions between the three sulfide compositions are driven by the disparate solubilites of the metal ion exchange pair in specific coordinating molecules. Starting with CdS, highly anisotropic PbS nanorods are created, which serve as an important material for studying strong 2-dimensional quantum confinement, as well as for optoelectronic applications. Furthermore, interesting nanoheterostructures of CdS|PbS are obtained by precise control over ion insertion and removal.

  15. Ionic liquids composed of phosphonium cations and organophosphate, carboxylate, and sulfonate as lubricant antiwear additives

    SciTech Connect (OSTI)

    Zhou, Yan; Dyck, Jeffrey; Graham, Todd; Luo, Huimin; Leonard, Donovan N.; Qu, Jun

    2014-10-20

    Oil-soluble phosphonium-based ionic liquids (ILs) have recently been reported as potential ashless lubricant additives. This study is to expand the IL chemistry envelope and to achieve fundamental correlations between the ion structures and ILs’ physiochemical and tribological properties. Here we present eight ILs containing two different phosphonium cations and seven different anions from three groups: organophosphate, carboxylate, and sulfonate. The oil solubility of ILs seems largely governed by the IL molecule size and structure complexity. When used as oil additives, the ranking of effectiveness in wear protection for the anions are: organophosphate > carboxylate > sulfonate. All selected ILs outperformed a commercial ashless anti-wear additive. Surface characterization from the top and the cross-section revealed the nanostructures and compositions of the tribo-films formed by the ILs. Some fundamental insights were achieved: branched and long alkyls improve the IL’s oil solubility, anions of a phosphonium-phosphate IL contribute most phosphorus in the tribofilm, and carboxylate anions, though free of P, S, N, or halogen, can promote the formation of an anti-wear tribofilm.

  16. Interaction of the cesium cation with calix[4]arene-bis(t-octylbenzo-18-crown-6): Extraction and DFT study

    SciTech Connect (OSTI)

    Makrlik, Emanuel; Toman, Petr; Vanura, Petr; Moyer, Bruce A

    2013-01-01

    From extraction experiments and c-activity measurements, the extraction constant corresponding to the equilibrium Cs+ (aq) + I (aq) + 1 (org),1Cs+ (org) + I (org) taking place in the two-phase water-phenyltrifluoromethyl sulfone (abbrev. FS 13) system (1 = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, org = FS 13 phase) was evaluated as logKex (1Cs+, I) = 2.1 0.1. Further, the stability constant of the 1Cs+ complex in FS 13 saturated with water was calculated for a temperature of 25 C: log borg (1Cs+) = 9.9 0.1. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complex species 1Cs+ was derived. In the resulting 1Cs+ complex, the central cation Cs+ is bound by eight bond interactions to six oxygen atoms of the respective 18-crown-6 moiety and to two carbons of the corresponding two benzene rings of the parent ligand 1 via cation p interaction.

  17. Gas-Phase Reactions of Doubly Charged Lanthanide Cations with Alkanes and Alkenes. Trends in Metal(2+) Reactivity

    SciTech Connect (OSTI)

    Gibson, John K.; Marcalo, Joaquim; Santos, Marta; Pires de Matos, Antonio; Haire, Richard G.

    2008-12-08

    The gas-phase reactivity of doubly-charged lanthanide cations, Ln2+ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), with alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) was studied by Fourier transform ion cyclotron resonance mass spectrometry. The reaction products consisted of different combinations of doubly-charged organometallic ions?adducts or species formed via metal-ion-induced hydrogen, dihydrogen, alkyl, or alkane eliminations from the hydrocarbons?and singly-charged ions that resulted from electron, hydride, or methide transfers from the hydrocarbons to the metal ions. The only lanthanide cations capable of activating the hydrocarbons to form doubly-charged organometallic ions were La2+, Ce2+, Gd2+, and Tb2+, which have ground-state or low-lying d1 electronic configurations. Lu2+, with an accessible d1 electronic configuration but a rather high electron affinity, reacted only through transfer channels. The remaining Ln2+ reacted via transfer channels or adduct formation. The different accessibilities of d1 electronic configurations and the range of electron affinities of the Ln2+ cations allowed for a detailed analysis of the trends for metal(2+) reactivity and the conditions for occurrence of bond activation, adduct formation, and electron, hydride, and methide transfers.

  18. A theoretical study on the interstellar synthesis of H{sub 2}NCS{sup +} and HNCSH{sup +} cations

    SciTech Connect (OSTI)

    Gronowski, Marcin; Kołos, Robert E-mail: rkolos@ichf.edu.pl

    2014-09-10

    HNCS and NCSH molecules, recently discovered in the interstellar medium, are likely formed via the dissociative recombination of H{sub 2}NCS{sup +} or HNCSH{sup +} isomeric ions. Interstellar synthesis of the latter is discussed on theoretical grounds. The analysis of relevant potential energy surfaces suggests a key role for chemical processes in which CSH{sup +} or HCS{sup +} cations (most likely formed in CS+H{sub 3}{sup +} collisions) react with NH{sub 2} or NH{sub 3}. The astrochemical kinetic database (kida.uva.2011), appended with 7 sulfur-bearing molecules and 48 corresponding reactions, has been applied to model the evolution of HNCS, NCSH, and their cationic precursors in a quiescent molecular cloud. Based on the model and on spectroscopic predictions, for an object like TMC-1, we expect the total intensity of H{sub 2}NCS{sup +} microwave lines to be comparable to that observed for HSCN. Theoretically derived molecular parameters, of interest for radio spectroscopy, are given for the most stable cations sharing the H{sub 2}NCS{sup +} stoichiometry.

  19. Doping against the native propensity of MoS₂: Degenerate hole doping by cation substitution

    SciTech Connect (OSTI)

    Suh, Joonki; Park, Tae-Eon; Lin, Der-Yuh; Fu, Deyi; Park, Joonsuk; Jung, Hee Joon; Chen, Yabin; Ko, Changhyun; Jang, Chaun; Sun, Yinghui; Sinclair, Robert; Chang, Joonyeon; Tongay, Sefaattin; Wu, Junqiao

    2014-12-10

    Layered transition metal dichalcogenides (TMDs) draw much attention as the key semiconducting material for two-dimensional electrical, optoelectronic, and spintronic devices. For most of these applications, both n- and p-type materials are needed to form junctions and support bipolar carrier conduction. However, typically only one type of doping is stable for a particular TMD. For example, molybdenum disulfide (MoS₂) is natively an n-type presumably due to omnipresent electron-donating sulfur vacancies, and stable/controllable p-type doping has not been achieved. The lack of p-type doping hampers the development of charge-splitting p–n junctions of MoS₂, as well as limits carrier conduction to spin-degenerate conduction bands instead of the more interesting, spin-polarized valence bands. Traditionally, extrinsic p-type doping in TMDs has been approached with surface adsorption or intercalation of electron-accepting molecules. However, practically stable doping requires substitution of host atoms with dopants where the doping is secured by covalent bonding. In this work, we demonstrate stable p-type conduction in MoS₂ by substitutional niobium (Nb) doping, leading to a degenerate hole density of ~3 × 10¹⁹ cm⁻³. Structural and X-ray techniques reveal that the Nb atoms are indeed substitutionally incorporated into MoS₂ by replacing the Mo cations in the host lattice. van der Waals p–n homojunctions based on vertically stacked MoS₂ layers are fabricated, which enable gate-tunable current rectification. A wide range of microelectronic, optoelectronic, and spintronic devices can be envisioned from the demonstrated substitutional bipolar doping of MoS₂. From the miscibility of dopants with the host, it is also expected that the synthesis technique demonstrated here can be generally extended to other TMDs for doping against their native unipolar propensity.

  20. Kinetics of ion-ion mutual neutralization: Halide anions with polyatomic cations

    SciTech Connect (OSTI)

    Shuman, Nicholas S.; Wiens, Justin P.; Miller, Thomas M.; Viggiano, Albert A.

    2014-06-14

    The binary mutual neutralization (MN) of a series of 17 cations (O{sub 2}{sup +}, NO{sup +}, NO{sub 2}{sup +}, CO{sup +}, CO{sub 2}{sup +}, Cl{sup +}, Cl{sub 2}{sup +}, SO{sub 2}{sup +}, CF{sub 3}{sup +}, C{sub 2}F{sub 5}{sup +}, NH{sub 3}{sup +}, H{sub 3}{sup +}, D{sub 3}{sup +}, H{sub 2}O{sup +}, H{sub 3}O{sup +}, ArH{sup +}, ArD{sup +}) with 3 halide anions (Cl{sup −}, Br{sup −}, I{sup −}) has been investigated in a flowing afterglow-Langmuir probe apparatus using the variable electron and neutral density attachment mass spectrometry technique. The MN rate constants of atom-atom reactions are dominated by the chemical nature of the system (i.e., the specific locations of curve crossings). As the number of atoms in the system increases, the MN rate constants become dominated instead by the physical nature of the system (e.g., the relative velocity of the reactants). For systems involving 4 or more atoms, the 300 K MN rate constants are well described by 2.7 × 10{sup −7} μ{sup −0.5}, where the reduced mass is in Da and the resulting rate constants in cm{sup 3} s{sup −1}. An upper limit to the MN rate constants appears well described by the complex potential model described by Hickman assuming a cross-section to neutralization of 11 000 Å{sup 2} at 300 K, equivalent to 3.5 × 10{sup −7} μ{sup −0.5}.

  1. Cation substitution in β-tricalcium phosphate investigated using multi-nuclear, solid-state NMR

    SciTech Connect (OSTI)

    Grigg, Andrew T.; Mee, Martin; Mallinson, Phillip M.; Fong, Shirley K.; Gan, Zhehong; Dupree, Ray; Holland, Diane

    2014-04-01

    The substitution of aluminium, gallium and sodium cations into β-tricalcium phosphate (β-TCP; Ca{sub 3}(PO{sub 4}){sub 2}) has been investigated, and the Ca sites involved successfully determined, using a combination of 1D {sup 31}P, {sup 27}Al, {sup 71}Ga, {sup 23}Na and {sup 43}Ca (natural abundance) NMR and 2D {sup 27}Al({sup 31}P), {sup 71}Ga({sup 31}P) and {sup 23}Na({sup 31}P) rotary-resonance-recoupled heteronuclear multiple-quantum correlation (R{sup 3}-HMQC) NMR. Over the compositional range studied, substitution of Ca{sup 2+} by Al{sup 3+} or Ga{sup 3+} was observed only on the Ca(5) site, whilst substitution by Na{sup +} was confined to the Ca(4) site. Some AlPO{sub 4} or GaPO{sub 4} second phase was observed at the highest doping levels in the Al{sup 3+} and Ga{sup 3+} substituted samples. - Graphical abstract: 2D contour plots with skyline projections showing recoupling of {sup 27}Al, {sup 71}Ga and {sup 23}Na to different {sup 31}P sites. - Highlights: • β-Ca{sub 3}(PO{sub 4}){sub 2} has been prepared pure and also with Al{sup 3+}, Ga{sup 3+} and Na{sup +} substituents. • Multi-nuclear 1D NMR and heteronuclear X({sup 31}P) recoupling have been used. • Models for substitution correctly predict site preference and occupancy. • Progressive changes in {sup 31}P spectra have been explained. • Al{sup 3+} and Ga{sup 3+} substitute onto the Ca(5) site, and Na{sup +} onto the Ca(4) site.

  2. Glass-water interactions: Effect of high-valence cations on glass structure and chemical durability

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

    Pierce, Eric M.; Kerisit, Sebastien N.; Charpentier, Thibault; Angeli, Frederic; Icenhower, J. P.; McGrail, B. Pete; Charles F. Windisch; Burton, Sarah D.; Hopf, Juliane

    2016-02-27

    Spectroscopic measurements, dissolution experiments, and Monte Carlo simulations were performed to investigate the effect of high valence cations (HVC) on the mechanisms of glass dissolution under dilute and near-saturated conditions. Raman and NMR spectroscopy were used to determine the structural changes that occur in glass, specifically network formers (e.g., Al, Si, and B), with the addition of the HVC element hafnium in the Na2O Al2O3 B2O3 HfO2 SiO2 system (e.g., Na/(Al+B) = 1.0 and HfO2/SiO2 from 0.0 to 0.42). Spectroscopic measurements revealed that increasing hafnium content decreases N4 and increases the amount of Si–O–Hf moieties in the glass. Results frommore » flow through experiments conducted under dilute and near saturated conditions show a decrease of approximately 100 or more in the dissolution rate over the series from 0 to 20 mol% HfO2. Comparing the average steady-state rates obtained under dilute conditions to the rates obtained for near-saturated conditions reveal a divergence in the magnitude between the average steady state rates measured in these different conditions. The reason for this divergence was investigated more thoroughly using Monte Carlo simulations. Simulations indicate that the divergence in glass dissolution behavior under dilute and near-saturated conditions result from the formation of a low coordination Si sites when Si from the saturated solution adsorbs to Hf on the glass surface. The residence time of the newly formed low coordination Si sites is longer at the glass surface and increases the density of anchor sites from which altered layers with higher Si densities can form than in the absence of Hf. These results illustrate the importance of understanding solid water/solid-fluid interactions by linking macroscopic reaction kinetics to nanometer scale interfacial processes.« less

  3. Carbon-carbon bond formation in cationic aryl-olefin-platinum (II) complexes

    SciTech Connect (OSTI)

    De Felice, V.; Renzi, A.D.; Tesauro, D.; Vitagliano, A.

    1992-11-01

    Cationic five-coordinate [Pt(3-R{sup 1}-4-R{sup 2}-C{sub 6}H{sub 3})(MeCN) (6-Me-py-2-CH=NPh)(C{sub 2}H{sub 4})]{sup +} complexes (R{sup 1}, R{sup 2} = H, Me, OMe) undergo an unexpected rearrangement at 0{degrees}C in chloroform solution, affording, after treatment with aqueous LiCl, the neutral four-coordinate species [Pt(2-Et-4-R{sup 1}-5-R{sup 2}-C{sub 6}H{sub 2})Cl(6-Me-py-1-CH=NPh)]. Pt-C{sub aryl} bond breaking and making is involved in the whole process, resulting in a 1,2-shift of the platinum atom to an adjacent position of the benzene ring. The same compound is obtained, together with products deriving from a typical insertion, when an equimolar amount of ethylene is added to a chloroform solution of [Pt(3-R{sub 1}-4-R{sup 2}-C{sub 6}H{sub 3})(MeCN)(6-Me-py-2-CH=NPh)]{sup +} at 0{degrees}C. When higher ethylene/Pt ratios are used, only five-coordinate [Pt(3-R{sup 1}-4-R{sup 2}-C{sub 6}H{sub 3}CH{sub 2}CH{sub 2})Cl(6-Me-py-2-CH{double_bond}NPh)(C{sub 2}H{sub 4})] complex is isolated. As the experimental data rule out the possibility of a (2-arylethyl)platinum to (2-ethylaryl)platinum rearrangement, different reaction paths are suggested for the two processes. When the two reactions are combined in a {open_quotes}one-pot{close_quotes} sequence, a regiocontrolled double alkylation of the aryl system can be obtained. The behavior substrates containing bidenate nitrogen ligands having different five-coordination stabilizing effects is examined, and data concerning the reactions of propene and styrene are reported. 13 refs., 3 tabs.

  4. Cationic Gold Clusters Ligated with Differently Substituted Phosphines: Effect of Substitution on Ligand Reactivity and Binding

    SciTech Connect (OSTI)

    Johnson, Grant E.; Olivares, Astrid M.; Hill, David E.; Laskin, Julia

    2015-01-01

    We present a systematic study of the effect of the number of methyl (Me) and cyclohexyl (Cy) functional groups in monodentate phosphine ligands on the solution-phase synthesis of ligated sub-nanometer gold clusters and their gas-phase fragmentation pathways. Small mixed ligand cationic gold clusters were synthesized using ligand exchange reactions between pre-formed triphenylphosphine ligated (PPh3) gold clusters and monodentate Me- and Cy-substituted ligands in solution and characterized using electrospray ionization mass spectrometry (ESI-MS) and collision-induced dissociation (CID) experiments. Under the same experimental conditions, larger gold-PPh3 clusters undergo efficient exchange of unsubstituted PPh3 ligands for singly Me- and Cy-substituted PPh2Me and PPh2Cy ligands. The efficiency of ligand exchange decreases with an increasing number of Me or Cy groups in the substituted phosphine ligands. CID experiments performed for a series of ligand-exchanged gold clusters indicate that loss of a neutral Me-substituted ligand is preferred over loss of a neutral PPh¬3 ligand while the opposite trend is observed for Cy-substituted ligands. The branching ratio of the competing ligand loss channels is strongly correlated with the electron donating ability of the phosphorous lone pair as determined by the relative proton affinity of the ligand. The results indicate that the relative ligand binding energies increase in the order PMe3 < PPhMe2 < PPh2Me < PPh3< PPh2Cy < PPhCy2< PCy3. Furthermore, the difference in relative ligand binding energies increases with the number of substituted PPh3-mMem or PPh3-mCym ligands (L) exchanged onto each cluster. This study provides the first experimental determination of the relative binding energies of ligated gold clusters containing differently substituted monophosphine ligands, which are important to controlling their synthesis and reactivity in solution. The results also indicate that ligand substitution is an important

  5. New iodocuprates(I) with N-heterocyclic molecules as the cations

    SciTech Connect (OSTI)

    Zhao, Jin-Jing; Zhang, Xiao; Wang, Yan-Ning; Jia, Hong-Li; Yu, Jie-Hui; Xu, Ji-Qing

    2013-11-15

    Under the hydrothermal conditions, the reactions between CuI, KI and bp/bpp (bp=4,4′-bipiperidine, bpp=1,3-bis(4-piperidyl)propane) in an acidic alcohol solution produced three new organically templated iodocuprates(I) as [H{sub 2}bp]{sub 2}[Cu{sub 2}I{sub 6}] 1, [tmbp][Cu{sub 2}I{sub 4}] 2 and [tmbpp] 2 [Cu{sub 4}I{sub 8}]·2H{sub 2}O 3 (tmbp{sup 2+}=N,N,N′,N′-tetramethyl-4,4′-bipiperidinium; tmbpp{sup 2+}=N,N,N′,N′-tetramethyl-1,3-bis(4-piperidyl)propane dication). X-ray analysis revealed that (i) tmbp{sup 2+} and tmbpp{sup 2+} in compounds 2 and 3 originated from the complete N-alklation of bp/bpp with CH{sub 3}OH; (ii) templated by H{sub 2}bp{sup 2+}, the inorganic anion [Cu{sub 2}I{sub 6}]{sup 2−} of 1 possesses a dinuclear structure, whereas templated by tmbp{sup 2+}, the inorganic anion [Cu{sub 2}I{sub 4}]{sup 2−} of 2 exhibits a one-dimensional (1D) chain structure; (iii) templated by tmbpp{sup 2+}, the inorganic anion [Cu{sub 4}I{sub 8}]{sup 4−} of 3 shows a cubane-like structure modified by four terminal I{sup −} ions. The photoluminescence analysis indicates that compounds 1 and 2 emit blue light, while compound 3 emits green light. - Graphical abstract: By employing hydrothermal in situ N-alkylation of bp/bpp with CH{sub 3}OH, three new organically templated iodocuprates(I) were obtained. Display Omitted - Highlights: • Three new organically templated iodocuprates(I) were reported. • Cations tmbp{sup 2+} and tmbpp{sup 2+} originated from in situ alkylation of bp/bpp with CH{sub 3}OH. • H{sup +} and I{sup −} play a key role in alkylation of bp/bpp with CH{sub 3}OH. • Photoluminescence emission for iodocuprates(I) is related to Cu···Cu interaction.

  6. Dating thermal events at Cerro Prieto using fission-track annealing

    SciTech Connect (OSTI)

    Sanford, S.J.; Elders, W.A.

    1981-01-01

    The duration of heating in the Cerro Prieto reservoir was estimated by relating the fading of spontaneous fission tracks in detrital apatite to observed temperatures. The rate of fading is a function of both time and temperature. The apparent fission track age of the detrital apatites then, is a function of both their source age and their time-temperature history. Data from laboratory experiments and geologic fading studies were compiled from published sources to produce lines of iso-annealing for apatite in time-temperature space. Fission track ages were calculated for samples from two wells at Cerro Prieto, one with an apparently simple and one with an apparently complex thermal history. Temperatures were estimated by empirical vitrinite reflectance geothermometry, fluid inclusion homogenization and oxygen isotope equilibrium. These estimates were compared with logs of measured borehole temperatures. The temperature in well T-366, where complete annealing first occurs, was estimated to be between 160 and 180{sup 0}C. Complete annealing at these temperatures requires 10{sup 4} and 10{sup 3} years, respectively. Well M-94 has an apparently complex thermal history. Geothermometers in this well indicate temperatures some 50 to 100{sup 0}C higher than those measured directly in the borehole. Fission tracks are partially preserved in M-94 where paleotemperatures were as high as 200{sup 0}C and are erased where geothermometers indicate temperatures of 250{sup 0}C. This implies a thermal event less than 10{sup 1} years and greater than 10{sup 0} years in duration.

  7. Chemistry Data for Geothermometry Mapping of Deep Hydrothermal Reservoirs in Southeastern Idaho

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Earl Mattson

    2016-01-18

    This dataset includes chemistry of geothermal water samples of the Eastern Snake River Plain and surrounding area. The samples included in this dataset were collected during the springs and summers of 2014 and 2015. All chemical analysis of the samples were conducted in the Analytical Laboratory at the Center of Advanced Energy Studies in Idaho Falls, Idaho. This data set supersedes #425 submission and is the final submission for AOP 3.1.2.1 for INL. Isotopic data collected by Mark Conrad will be submitted in a separate file.

  8. One-photon mass-analyzed threshold ionization (MATI) spectroscopy of pyridine: Determination of accurate ionization energy and cationic structure

    SciTech Connect (OSTI)

    Lee, Yu Ran; Kang, Do Won; Kim, Hong Lae E-mail: hlkim@kangwon.ac.kr; Kwon, Chan Ho E-mail: hlkim@kangwon.ac.kr

    2014-11-07

    Ionization energies and cationic structures of pyridine were intensively investigated utilizing one-photon mass-analyzed threshold ionization (MATI) spectroscopy with vacuum ultraviolet radiation generated by four-wave difference frequency mixing in Kr. The present one-photon high-resolution MATI spectrum of pyridine demonstrated a much finer and richer vibrational structure than that of the previously reported two-photon MATI spectrum. From the MATI spectrum and photoionization efficiency curve, the accurate ionization energy of the ionic ground state of pyridine was confidently determined to be 73 570 ± 6 cm{sup −1} (9.1215 ± 0.0007 eV). The observed spectrum was almost completely assigned by utilizing Franck-Condon factors and vibrational frequencies calculated through adjustments of the geometrical parameters of cationic pyridine at the B3LYP/cc-pVTZ level. A unique feature unveiled through rigorous analysis was the prominent progression of the 10 vibrational mode, which corresponds to in-plane ring bending, and the combination of other totally symmetric fundamentals with the ring bending overtones, which contribute to the geometrical change upon ionization. Notably, the remaining peaks originate from the upper electronic state ({sup 2}A{sub 2}), as predicted by high-resolution photoelectron spectroscopy studies and symmetry-adapted cluster configuration interaction calculations. Based on the quantitatively good agreement between the experimental and calculated results, it was concluded that upon ionization the pyridine cation in the ground electronic state should have a planar structure of C{sub 2v} symmetry through the C-N axis.

  9. AMENDMENT OF SOLlClTATlONlMODlFlCATION OF CONTRACT 1 I . CONTR"CT ID CODE

    National Nuclear Security Administration (NNSA)

    SOLlClTATlONlMODlFlCATION OF CONTRACT 1 I . CONTR"CT ID CODE BWXT Pantex, LLC Route 726, Mt. Athos Road Lynchburg, VA 24506 PAGE 1 OF 2 PAGES Albuquerque, NM 8718Ii4400 I Amarillo, TX 79120 9B. DATED (SEE m M 11) 10A. MODIFICATION OF CONTRACTIORDER NO. 8. NAME AND ADDRESS OF CONTRACTOR (No., street, county, &ate, ZIP Code) I ( DE-ACOCOOAL66620 10B. DATED (SEE / E M 13) 2. AMENDMENT/MODIFICATION NO. M097 9A. AMENDMENT OF SOLICITATION NO. Offera must a d t n d e d p rsceipt of this m e n

  10. Highly Active Electrolytes for Rechargeable Mg Batteries Based on [Mg2(?-Cl)2]2+ Cation Complex in Dimethoxyethane

    SciTech Connect (OSTI)

    Cheng, Yingwen; Stolley, Ryan M.; Han, Kee Sung; Shao, Yuyan; Arey, Bruce W.; Washton, Nancy M.; Mueller, Karl T.; Helm, Monte L.; Sprenkle, Vincent L.; Liu, Jun; Li, Guosheng

    2015-01-01

    Highly active electrolytes based on a novel [Mg2(?-Cl)2]2+ cation complex for reversible Mg deposition were developed and analyzed in this work. These electrolytes were formulated in dimethoxyethane through dehalodimerization of non-nucleophilic MgCl2 by reacting with either Mg salts (such as Mg(TFSI)2, TFSI= bis(trifluoromethane)sulfonylimide) or Lewis acid salts (such as AlEtCl2 or AlCl3). The cation complex was identified for the first time as [Mg2(?-Cl)2(DME)4]2+ (DME=dimethoxyethane) and its molecular structure was characterized by single crystal X-ray diffraction, Raman spectroscopy and NMR. The electrolyte synthesis process was studied and rational approaches for formulating highly active electrolytes were proposed. Through control of the anions, electrolytes with efficiency close to 100%, wide electrochemical window (up to 3.5V) and high ionic conductivity (> 6 mS/cm) were obtained. The electrolyte synthesis and understandings developed in this work could bring significant opportunities for rational formulation of electrolytes with the general formula [Mg2(?-Cl)2(DME)4][anion]x for practical Mg batteries.

  11. Combined Quantum Chemical/Raman Spectroscopic Analyses of Li+ Cation Solvation: Cyclic Carbonate Solvents - Ethylene Carbonate and Propylene Earbonate

    SciTech Connect (OSTI)

    Allen, Joshua L.; Borodin, Oleg; Seo, D. M.; Henderson, Wesley A.

    2014-12-01

    Combined computational/Raman spectroscopic analyses of ethylene carbonate (EC) and propylene carbonate (PC) solvation interactions with lithium salts are reported. It is proposed that previously reported Raman analyses of (EC)n-LiX mixtures have utilized faulty assumptions. In the present studies, density functional theory (DFT) calculations have provided corrections in terms of both the scaling factors for the solvent's Raman band intensity variations and information about band overlap. By accounting for these factors, the solvation numbers obtained from two different EC solvent bands are in excellent agreement with one another. The same analysis for PC, however, was found to be quite challenging. Commercially available PC is a racemic mixture of (S)- and (R)-PC isomers. Based upon the quantum chemistry calculations, each of these solvent isomers may exist as multiple conformers due to a low energy barrier for ring inversion, making deconvolution of the Raman bands daunting and inherently prone to significant error. Thus, Raman spectroscopy is able to accurately determine the extent of the EC...Li+ cation solvation interactions using the provided methodology, but a similar analysis of PC...Li+ cation solvation results in a significant underestimation of the actual solvation numbers.

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

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

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

    2014-04-23

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

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

    SciTech Connect (OSTI)

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

    2014-04-23

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

  14. Full cell study of Diels Alder poly(phenylene) anion and cation exchange membranes in vanadium redox flow batteries

    SciTech Connect (OSTI)

    Pezeshki, Alan M.; Fujimoto, Cy; Sun, Che -Nan; Mench, Matthew M.; Zawodzinski, Thomas A.; Tang, Z. J.

    2015-11-14

    In this paper, we report on the performance of Diels Alder poly(phenylene) membranes in vanadium redox flow batteries. The membranes were functionalized with quaternary ammonium groups to form an anion exchange membrane (QDAPP) and with sulfonic acid groups to form a cation exchange membrane (SDAPP). Both membrane classes showed similar conductivities in the battery environment, suggesting that the ion conduction mechanism in the material is not strongly affected by the moieties along the polymer backbone. The resistance to vanadium permeation in QDAPP was not improved relative to SDAPP, further suggesting that the polarity of the functional groups do not play a significant role in the membrane materials tested. Both QDAPP and SDAPP outperformed Nafion membranes in cycling tests, with both achieving voltage efficiencies above 85% while maintaining 95% coulombic efficiency while at a current density of 200 mA/cm2.

  15. Full cell study of Diels Alder poly(phenylene) anion and cation exchange membranes in vanadium redox flow batteries

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

    Pezeshki, Alan M.; Fujimoto, Cy; Sun, Che -Nan; Mench, Matthew M.; Zawodzinski, Thomas A.; Tang, Z. J.

    2015-11-14

    In this paper, we report on the performance of Diels Alder poly(phenylene) membranes in vanadium redox flow batteries. The membranes were functionalized with quaternary ammonium groups to form an anion exchange membrane (QDAPP) and with sulfonic acid groups to form a cation exchange membrane (SDAPP). Both membrane classes showed similar conductivities in the battery environment, suggesting that the ion conduction mechanism in the material is not strongly affected by the moieties along the polymer backbone. The resistance to vanadium permeation in QDAPP was not improved relative to SDAPP, further suggesting that the polarity of the functional groups do not playmore » a significant role in the membrane materials tested. Both QDAPP and SDAPP outperformed Nafion membranes in cycling tests, with both achieving voltage efficiencies above 85% while maintaining 95% coulombic efficiency while at a current density of 200 mA/cm2.« less

  16. AMENDMENT OF SOLIr ATI ON/MODIFI CATION OF CONTRACT 1. CONTRACT ID CODE PAGE OF PAGES

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

    SOLIr ATI ON/MODIFI CATION OF CONTRACT 1. CONTRACT ID CODE PAGE OF PAGES 2 AMENDMENT/lIVDDIFICATiON NC 3. EFFECTIVE DATE [4 REDUISITION/PURCHASE REC NO IE PR3JECT NC (if applicable) 09 ISoe Bloo , 16- - ISee Soheoule S ISSUED D> CODE 7 ~ ADMINISTERED BY (if otnertrian ItemS CO DE Of fice of Ri-.er PoDLecOLODn office of Riv'er P-oCQ-ec-.iQ .S. Cet:F O<men of E-nerov,, I.S. Deparo:merio c-' Enrgv P.O. Box 4'5C 0 ... Box 45C .io ao 1 31 W YS: (-876 B. NAME AND ADDRESS CF CONTRACTOR (No seve

  17. Unravelling the low thermal expansion coefficient of cation-substituted YBaCo4O7+δ

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

    Manthiram, Arumugam; Huq, Ashfia; Kan, Wang Hay; Lai, Ke -Yu

    2016-01-12

    With an aim to understand the origin of the low thermal expansion coefficients (TECs), cation substituted YBaCo4O7-type oxides have been investigated by in-situ neutron diffraction, bond valence sum (BVS), thermogravimetric analysis, and dilatometry. The compositions YBaCo4O7+δ, Y0.9ln0.1BaCo3ZnO7+δ, and Y0.9ln0.1BaCo3Zn0.6Fe0.4O7+δ) were synthesized by solid-state reaction at 1200 °C. Here, Rietveld refinement of the joint synchrotron X-ray and neutron diffraction data shows that the Zn and Fe dopants have different preferences to substitute the Co ions in the 6c and 2a sites.

  18. Crystal Structure of an Integron Gene Cassette-Associated Protein from Vibrio cholerae Identifies a Cationic Drug-Binding Module

    SciTech Connect (OSTI)

    Deshpande, Chandrika N.; Harrop, Stephen J.; Boucher, Yan; Hassan, Karl A.; Di Leo, Rosa; Xu, Xiaohui; Cui, Hong; Savchenko, Alexei; Chang, Changsoo; Labbate, Maurizio; Paulsen, Ian T.; Stokes, H.W.; Curmi, Paul M.G.; Mabbutt, Bridget C.

    2012-02-15

    The direct isolation of integron gene cassettes from cultivated and environmental microbial sources allows an assessment of the impact of the integron/gene cassette system on the emergence of new phenotypes, such as drug resistance or virulence. A structural approach is being exploited to investigate the modularity and function of novel integron gene cassettes. We report the 1.8 {angstrom} crystal structure of Cass2, an integron-associated protein derived from an environmental V. cholerae. The structure defines a monomeric beta-barrel protein with a fold related to the effector-binding portion of AraC/XylS transcription activators. The closest homologs of Cass2 are multi-drug binding proteins, such as BmrR. Consistent with this, a binding pocket made up of hydrophobic residues and a single glutamate side chain is evident in Cass2, occupied in the crystal form by polyethylene glycol. Fluorescence assays demonstrate that Cass2 is capable of binding cationic drug compounds with submicromolar affinity. The Cass2 module possesses a protein interaction surface proximal to its drug-binding cavity with features homologous to those seen in multi-domain transcriptional regulators. Genetic analysis identifies Cass2 to be representative of a larger family of independent effector-binding proteins associated with lateral gene transfer within Vibrio and closely-related species. We propose that the Cass2 family not only has capacity to form functional transcription regulator complexes, but represents possible evolutionary precursors to multi-domain regulators associated with cationic drug compounds.

  19. Cation Intermixing And Electronic Deviations At The Insulating LaCrO3/SrTiO3(001) Interface

    SciTech Connect (OSTI)

    Colby, Robert J.; Qiao, Liang; Zhang, Hongliang; Shutthanandan, V.; Ciston, Jim; Kabius, Bernd C.; Chambers, Scott A.

    2013-10-29

    The interface between polar perovskite LaCrO3 (LCO) and non-polar SrTiO3(001) (STO), grown by molecular beam epitaxy, is examined using a combination of electron microscopy, spectroscopy, and Rutherford backscattering spectrometry. The LCO/STO(001) interface is insulating, a potential counter example for the claim that polar/nonpolar perovskite interfaces should be conductive by virtue of an electronic reconstruction to alleviate the polar discontinuity. The A-site cations of these ABO3 perovskites are found to diffuse across the interface to a greater extent than the B-site cations, based on high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), energy dispersive x-ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS). The B-site cation valences are shown to be partially reduced near the interface by analysis of EELS near-edge structures. The location and direction of these electronic modifications do not intuitively compensate the charge imbalance imposed by uneven cation inter-diffusion, and yet both the film and interface are insulating. These results highlight the importance of both the physical and electronic structure of such complex interfaces in determining their characteristics. Furthermore, the extent of inter-diffusion is shown to increase with increasing LCO film thickness, suggesting a potential mechanism behind the critical thickness for interfacial conductivity in other polar/non-polar oxide systems, and a fundamental limitation on the formation of abrupt interfaces in LCO/STO(001).

  20. Coverage Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-selected Ions

    SciTech Connect (OSTI)

    Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

    2012-11-29

    The ionic charge state of monodisperse cationic gold clusters on surfaces may be controlled by selecting the coverage of mass-selected ions soft landed onto a substrate. Polydisperse diphosphine-capped gold clusters were synthesized in solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine in the presence of 1,3-bis(diphenylphosphino)propane. The polydisperse gold clusters were introduced into the gas phase by electrospray ionization and mass selection was employed to select a multiply charged cationic cluster species (Au11L53+, m/z = 1409, L = 1,3-bis(diphenylphosphino)propane) which was delivered to the surfaces of four different self-assembled monolayers on gold (SAMs) at coverages of 1011 and 1012 clusters/mm2. Employing the spatial profiling capabilities of in-situ time-of-flight secondary ion mass spectrometry (TOF-SIMS) it is shown that, in addition to the chemical functionality of the monolayer (as demonstrated previously: ACS Nano, 2012, 6, 573) the coverage of cationic gold clusters on the surface may be used to control the distribution of ionic charge states of the soft-landed multiply charged clusters. In the case of a 1H,1H,2H,2H-perfluorodecanethiol SAM (FSAM) almost complete retention of charge by the deposited Au11L53+ clusters was observed at a lower coverage of 1011 clusters/mm2. In contrast, at a higher coverage of 1012 clusters/mm2, pronounced reduction of charge to Au11L52+ and Au11L5+ was observed on the FSAM. When soft landed onto 16- and 11-mercaptohexadecanoic acid surfaces on gold (16,11-COOH-SAMs), the mass-selected Au11L53+ clusters exhibited partial reduction of charge to Au11L52+ at lower coverage and additional reduction of charge to both Au11L52+ and Au11L5+ at higher coverage. The reduction of charge was found to be more pronounced on the surface of the shorter (thinner) C11 than the longer (thicker) C16-COOH-SAM. On the surface of the 1-dodecanethiol (HSAM) monolayer, the most abundant charge state

  1. Combined Utilization of Cation Exchanger and Neutral Receptor to Volume Reduction of Alkaline Tank Waste by Separation of Sodium Salts

    SciTech Connect (OSTI)

    Levitskaia, Tatiana G.; Lumetta, Gregg J.; Moyer, Bruce A.

    2004-03-29

    In this report, novel approaches to the selective liquid-liquid extraction separation of sodium hydroxide and sodium nitrate from high-level alkaline tank waste will be discussed. Sodium hydroxide can be successfully separated from alkaline tank-waste supernatants by weakly acidic lipophilic hydroxy compounds via a cation-exchange mechanism referred to as pseudo hydroxide extraction. In a multi-cycle process, as sodium hydroxide in the aqueous phase becomes depleted, it is helpful to have a neutral sodium receptor in the extraction system to exploit the high nitrate concentration in the waste solution to promote sodium removal by an ion-pair extraction process. Simultaneous utilization of an ionizable organic hydroxy compound and a neutral extractant (crown ether) in an organic phase results in the synergistic enhancement of ion exchange and improved separation selectivity due to the receptor's strong and selective sodium binding. Moreover, combination of the hydroxy compound and the crown ether provides for mutually increased solubility, even in a non-polar organic solvent. Accordingly, application of Isopar{reg_sign} L, a kerosene-like alkane solvent, becomes feasible. This investigation involves examination of such dual-mechanism extraction phases for sodium extraction from simulated and actual salt cake waste solutions. Sodium salts can be regenerated upon the contact of the loaded extraction phases with water. Finally, conditions of potential extraction/strip cycling will be discussed.

  2. Swelling properties of montmorillonite and beidellite clay minerals from molecular simulation: Comparison of temperature interlayer cation, and charge location effects

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

    Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Jove-Colon, Carlos F.; Cygan, Randall Timothy

    2015-08-27

    In this study, the swelling properties of smectite clay minerals are relevant to many engineering applications including environmental remediation, repository design for nuclear waste disposal, borehole stability in drilling operations, and additives for numerous industrial processes and commercial products. We used molecular dynamics and grand canonical Monte Carlo simulations to study the effects of layer charge location, interlayer cation, and temperature on intracrystalline swelling of montmorillonite and beidellite clay minerals. For a beidellite model with layer charge exclusively in the tetrahedral sheet, strong ion–surface interactions shift the onset of the two-layer hydrate to higher water contents. In contrast, for amore » montmorillonite model with layer charge exclusively in the octahedral sheet, weaker ion–surface interactions result in the formation of fully hydrated ions (two-layer hydrate) at much lower water contents. Clay hydration enthalpies and interlayer atomic density profiles are consistent with the swelling results. Water adsorption isotherms from grand canonical Monte Carlo simulations are used to relate interlayer hydration states to relative humidity, in good agreement with experimental findings.« less

  3. The use Na, Li, K cations for modification of ZSM-5 zewolite to control hydrocarbon cold-start emission

    SciTech Connect (OSTI)

    Golubeva V.; Rohatgi U.; Korableva, A.; Anischenko, O.; Kustov, L.; Nissenbaum, V; Viola, M.B.

    2012-08-29

    This paper addresses the problem of controlling hydrocarbon emissions from cold-start of engines by investigating the adsorbents which could adsorb the hydrocarbons at cold temperatures and hold them to 250-300 ?. The materials, that has been studied, are based on the modification of ZSM-5 (SiO{sub 2}/Al{sub 2}O{sub 3} = 35) zeolite with Li, K, Na cations. It has been shown that the introduction of Li, Na and K in an amount that is equivalent to the content of Al in zeolite results in occurrence of toluene temperature desorption peaks at high-temperatures. The toluene temperature desorption curves for 5%Li-ZSM-5 and 2.3%Na-ZSM-5 zeolites are identical and have peak toluene desorption rate between 200 to 400 ?. Upon analysis of toluene adsorption isotherms for 2.3%Na-ZSM-5 and 5%Li-ZSM-5, it was concluded that the toluene diffusion inside of the modified zeolites channels is extremely slow and the sorption capacity of 2.3%Na-ZSM-5 is higher than with 5%Li-ZSM-5. The 2.3%Na-ZSM-5 didn't change toluene temperature programmed desorption (TPD) rate of curve after the treatment in environment with 10% ?{sub 2}? at 750-800 ? for about 28 h. The 2.3%Na-ZSM-5 zeolite is very promising as adsorbent to control the cold-start hydrocarbon emissions.

  4. Swelling properties of montmorillonite and beidellite clay minerals from molecular simulation: Comparison of temperature interlayer cation, and charge location effects

    SciTech Connect (OSTI)

    Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Jove-Colon, Carlos F.; Cygan, Randall Timothy

    2015-08-27

    In this study, the swelling properties of smectite clay minerals are relevant to many engineering applications including environmental remediation, repository design for nuclear waste disposal, borehole stability in drilling operations, and additives for numerous industrial processes and commercial products. We used molecular dynamics and grand canonical Monte Carlo simulations to study the effects of layer charge location, interlayer cation, and temperature on intracrystalline swelling of montmorillonite and beidellite clay minerals. For a beidellite model with layer charge exclusively in the tetrahedral sheet, strong ion–surface interactions shift the onset of the two-layer hydrate to higher water contents. In contrast, for a montmorillonite model with layer charge exclusively in the octahedral sheet, weaker ion–surface interactions result in the formation of fully hydrated ions (two-layer hydrate) at much lower water contents. Clay hydration enthalpies and interlayer atomic density profiles are consistent with the swelling results. Water adsorption isotherms from grand canonical Monte Carlo simulations are used to relate interlayer hydration states to relative humidity, in good agreement with experimental findings.

  5. Location and valence state of strontium cations on the framework of a carbon dioxide selective porous silicoaluminophosphate

    SciTech Connect (OSTI)

    Zhang, Li; Rivera-Ramos, Milton E.; Hernández-Maldonado, Arturo J.

    2014-05-28

    A Sr{sup 2+}-SAPO-34 material that displays superior CO2 adsorption selectivity and capacity was characterized via XPS and UV-vis spectroscopy to elucidate the valence state of strontium cations and framework silicon environment. Most importantly, the location of the strontium has been estimated from a Rietveld refinement analysis of synchrotron diffraction data. The XPS analysis indicated that the apparent valence state of the strontium is less than 2, an indication of its interaction with the large anionic framework. Furthermore, UV-vis tests pointed to changes in the silicon environment, plausibly related to this valence state or framework faulting. For the refinement, the analysis found that strontium occupied two unique sites: a site Sr1 slightly displaced from six-membered rings and a site Sr2 positioned at the top or bottom of the eight-membered rings. The latter position favors the interaction of the alkaline earth metal with CO{sub 2}, probably resulting in an enhanced electric field-quadrupole moment interaction.

  6. An ab initio study of the electronic structure of the boron oxide neutral (BO), cationic (BO{sup +}), and anionic (BO{sup ?}) species

    SciTech Connect (OSTI)

    Magoulas, Ilias; Kalemos, Apostolos

    2014-09-28

    The BO neutral, cationic, and anionic molecular species have been painstakingly studied through multireference configuration interaction and single reference coupled cluster methods employing basis sets of quintuple cardinality. Potential energy curves have been constructed for 38 (BO), 37 (BO{sup +}), and 12 (BO{sup ?}) states and the usual molecular parameters have been extracted most of which are in very good agreement with the scarce experimental data. Numerous avoided crossings appear on more or less all of the studied states of the neutral and cationic species challenging the validity of the Born Oppenheimer approximation. Finally, all excited states of the anionic system lie above the ground state of the neutral BO system and are therefore resonances.

  7. A comparative study of optical absorption and photocatalytic properties of nanocrystalline single-phase anatase and rutile TiO{sub 2} doped with transition metal cations

    SciTech Connect (OSTI)

    Kernazhitsky, L.; Shymanovska, V.; Gavrilko, T.; Naumov, V.; Kshnyakin, V.; Khalyavka, T.

    2013-02-15

    The effect of nanocrystalline TiO{sub 2} doping with transition metal cations (Cu{sup 2+}, Fe{sup 3+}, Co{sup 2+}, Cr{sup 3+}) on their optical absorption and photocatalytic properties was investigated. The obtained metal-doped TiO{sub 2} samples were characterized by X-ray diffraction, scanning electron microscopy, and UV-vis absorption spectroscopy. It is shown that doping effect on anatase (A) and rutile (R) properties is quite different, being much stronger and complicated on A than on R. Contrary to doped R, doped A revealed a significant red shift of the absorption edge along with the band gap narrowing. Photocatalytic activity of anatase increases upon doping in the order: AR/Co>R/Cu>R/Fe>R/Cr, indicating the inhibitory effect of impurity cations. This fact correlates with the decrease in the UV absorption of the doped rutile in the region of the Hg-lamp irradiation at 4.88 eV. - Graphical abstract: A red shift of the absorption edge of nanocrystalline single-phase anatase after doping with transition metal cations. Highlights: Black-Right-Pointing-Pointer Single-phase anatase and rutile powders surface-doped with transition metal cations. Black-Right-Pointing-Pointer Absorption edge and band gap of rutile do not change with surface doping. Black-Right-Pointing-Pointer Band gap of surface-doped anatase reduces being the lowest for A/Fe. Black-Right-Pointing-Pointer The surface-doping improves photocatalytic activity of anatase. Black-Right-Pointing-Pointer The surface-doping inhibits photocatalytic activity of rutile.

  8. Calix[4]arene-bis(t-octylbenzo-18-crown-6) as an extraordinarily effective macrocyclic receptor for the univalent thallium cation

    SciTech Connect (OSTI)

    Makrlik, Emanuel; Toman, Petr; Vanura, Petr; Moyer, Bruce A

    2013-01-01

    From extraction experiments and -activity measurements, the exchange extraction constant corresponding to the equilibrium Tl+ (aq) + 1 Cs+ (org) 1 Tl+ (org) + Cs+ (aq) taking place in the two-phase water phenyltrifluoromethyl sulfone (abbrev. FS 13) system (1 = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, org = FS 13 phase) was evaluated as log Kex (Tl+, 1 Cs+) = 1.7 0.1. Further, the extraordinarily high stability constant of the 1 Tl+ complex in FS 13 saturated with water was calculated for a temperature of 25 C: log org(1 Tl+) = 13.1 0.2. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complex species 1 Tl+ was derived. In the resulting 1 Tl+ complex, the central cation Tl+ is bound by eight bond interactions to six oxygen atoms from the respective 18-crown-6 moiety and to two carbons of the corresponding two benzene rings of the parent receptor 1 via cation interaction.

  9. Influence of cationic substitutions on the first charge and reversible capacities of lithium-rich layered oxide cathodes

    SciTech Connect (OSTI)

    Wang, Chih-Chieh; Manthiram, Arumugam

    2013-06-24

    The reversible capacity values of lithium-rich layered oxide cathodes depend on the length (capacity) of the plateau region during the first charge. With an aim to understand the factors that control the length of the plateau region and thereby enhance the reversible capacity, the effects of various cationic substitutions in Li1.2Mn0.6Ni0.2O2 have been investigated systematically. Specifically, substitutions of (i) M3+ = Al3+, Cr3+, Fe3+, Co3+, and Ga3+ for equal amounts of Mn4+and Ni2+ in Li1.2Mn0.6-0.5xNi0.2-0.5xMxO2 with x = 0.06, 0.13, and 0.2, (ii) Ti4+ for Mn4+ in Li1.2Mn0.6-xTixNi0.2O2 with x = 0.025, 0.05, and 0.1, and (iii) Mg2+ for Ni2+ in Li1.2Mn0.6Ni0.2-xMgxO2 with x = 0.025, 0.05, and 0.1 have been investigated. The cationic substitutions affect the first charge capacity values both in the sloping region corresponding to the oxidation of the transition-metal ions to the 4+ state and in the plateau region corresponding to the oxidation of O2- ions to O2 and/or transition-metal ions beyond 4+, which control the reversible capacity values in subsequent cycles. While the changes in the sloping-region capacity could be readily understood by considering the redox activities of the transition-metal ions, the plateau-region capacity is found to depend sensitively on the metaloxygen covalence, which is dictated by the relative positions of the metal:3d band with respect to the top of the O2-:2p band, and electron delocalization. For instance, an overlap of the Co3+/4+:t2g band with the top of the O2-:2p band along with a partially filled t 2g band

  10. Unraveling the voltage fade mechanism in layer Li-Mn-rich electrode: formation of the tetrahedral cations for spinel conversion

    SciTech Connect (OSTI)

    Mohanty, Debasish; Li, Jianlin; Abraham, Daniel P; Huq, Ashfia; Payzant, E Andrew; Wood III, David L; Daniel, Claus

    2014-01-01

    Discovery of high-voltage layered lithium-and manganese-rich (LMR) composite oxide electrode has dramatically enhanced the energy density of current Li-ion energy storage systems. However, practical usage of these materials is currently not viable because of their inability to maintain a consistent voltage profile (voltage fading) during subsequent charge-discharge cycles. This report rationalizes the cause of this voltage fade by providing the evidence of layer to spinel-like (LSL) structural evolution pathways in the host Li1.2Mn0.55Ni0.15Co0.1O2 LMR composite oxide. By employing neutron powder diffraction, and temperature dependent magnetic susceptibility, we show that LSL structural rearrangement in LMR oxide occurs through a tetrahedral cation intermediate via: i) diffusion of lithium atoms from octahedral to tetrahedral sites of the lithium layer [(LiLioct LiLitet] which is followed by the dispersal of the lithium ions from the adjacent octahedral site of the metal layer to the tetrahedral sites of lithium layer [LiTM oct LiLitet]; and ii) migration of Mn from the octahedral sites of the transition metal layer to the permanent octahedral site of lithium layer via tetrahedral site of lithium layer [MnTMoct MnLitet MnLioct)]. The findings opens the door to the potential routes to mitigate this atomic restructuring in the high-voltage LMR composite oxide cathodes by manipulating the composition/structure for practical use in high-energy-density lithium-ion batteries.