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Sample records for h2o flow temperature

  1. Species and temperature measurement in H2/O2 rocket flow fields by means of Raman scattering diagnostics

    NASA Technical Reports Server (NTRS)

    Degroot, Wim A.; Weiss, Jonathan M.

    1992-01-01

    Validation of Computational Fluid Dynamics (CFD) codes developed for prediction and evaluation of rocket performance is hampered by a lack of experimental data. Non-intrusive laser based diagnostics are needed to provide spatially and temporally resolved gas dynamic and fluid dynamic measurements. This paper reports the first non-intrusive temperature and species measurements in the plume of a 110 N gaseous hydrogen/oxygen thruster at and below ambient pressures, obtained with spontaneous Raman spectroscopy. Measurements at 10 mm downstream of the exit plane are compared with predictions from a numerical solution of the axisymmetric Navier-Stokes and species transport equations with chemical kinetics, which fully model the combustor-nozzle-plume flowfield. The experimentally determined oxygen number density at the centerline at 10 mm downstream of the exit plane is four times that predicted by the model. The experimental number density data fall between those numerically predicted for the exit and 10 mm downstream planes in both magnitude and radial gradient. The predicted temperature levels are within 10 to 15 percent of measured values. Some of the discrepancies between experimental data and predictions result from not modeling the three dimensional core flow injection mixing process, facility back pressure effects, and possible diffuser-thruster interactions.

  2. Base fluid and temperature effects on the heat transfer characteristics of SiC in ethylene glycol/H2O and H2O nanofluids

    NASA Astrophysics Data System (ADS)

    Timofeeva, Elena V.; Yu, Wenhua; France, David M.; Singh, Dileep; Routbort, Jules L.

    2011-01-01

    Experimental data are presented for the thermal conductivity, viscosity, and turbulent flow heat transfer coefficient of nanofluids with SiC particles suspended in ethylene glycol (EG)/water (H2O) mixture with a 50/50 volume ratio. The results are compared to the analogous suspensions in water for four sizes of SiC particles (16-90 nm). It is demonstrated that the heat transfer efficiency is a function of both the average particle size and the system temperature. The results show that adding SiC nanoparticles to an EG/H2O mixture can significantly improve the cooling efficiency while water-based nanofluids are typically less efficient than the base fluids. This is one of the few times that substantial nanofluid heat transfer enhancement has been reported in the literature based on a realistic comparison basis of constant velocity or pumping power. The trends important for engineering efficient heat transfer nanofluids are summarized.

  3. Influences of H2O mass fraction and chemical kinetics mechanism on the turbulent diffusion combustion of H2-O2 in supersonic flows

    NASA Astrophysics Data System (ADS)

    Huang, Wei; Wang, Zhen-guo; Li, Shi-bin; Liu, Wei-dong

    2012-07-01

    Hydrogen is one of the most promising fuels for the airbreathing hypersonic propulsion system, and it attracts an increasing attention of the researchers worldwide. In this study, a typical hydrogen-fueled supersonic combustor was investigated numerically, and the predicted results were compared with the available experimental data in the open literature. Two different chemical reaction mechanisms were employed to evaluate their effects on the combustion of H2-O2, namely the two-step and the seven-step mechanisms, and the vitiation effect was analyzed by varying the H2O mass fraction. The obtained results show that the predicted mole fraction profiles for different components show very good agreement with the available experimental data under the supersonic mixing and combustion conditions, and the chemical reaction mechanism has only a slight impact on the overall performance of the turbulent diffusion combustion. The simple mechanism of H2-O2 can be employed to evaluate the performance of the combustor in order to reduce the computational cost. The H2O flow vitiation makes a great difference to the combustion of H2-O2, and there is an optimal H2O mass fraction existing to enhance the intensity of the turbulent combustion. In the range considered in this paper, its optimal value is 0.15. The initiated location of the reaction appears far away from the bottom wall with the increase of the H2O mass fraction, and the H2O flow vitiation quickens the transition from subsonic to supersonic mode at the exit of the combustor.

  4. Amphibole stability in primitive arc magmas: effects of temperature, H2O content, and oxygen fugacity

    NASA Astrophysics Data System (ADS)

    Krawczynski, Michael J.; Grove, Timothy L.; Behrens, Harald

    2012-08-01

    The water-saturated phase relations have been determined for a primitive magnesian andesite (57 wt% SiO2, 9 wt% MgO) from the Mt. Shasta, CA region over the pressure range 200-800 MPa, temperature range of 915-1,070 °C, and oxygen fugacities varying from the nickel-nickel oxide (NNO) buffer to three log units above NNO (NNO+3). The phase diagram of a primitive basaltic andesite (52 wt% SiO2, 10.5 wt% MgO) also from the Mt. Shasta region (Grove et al. in Contrib Miner Petrol 145:515-533; 2003) has been supplemented with additional experimental data at 500 MPa. Hydrous phase relations for these compositions allow a comparison of the dramatic effects of dissolved H2O on the crystallization sequence. Liquidus mineral phase stability and appearance temperatures vary sensitively in response to variation in pressure and H2O content, and this information is used to calibrate magmatic barometers-hygrometers for primitive arc magmas. H2O-saturated experiments on both compositions reveal the strong dependence of amphibole stability on the partial pressure of H2O. A narrow stability field is identified where olivine and amphibole are coexisting phases in the primitive andesite composition above 500 MPa and at least until 800 MPa, between 975-1,025 °C. With increasing H2O pressure ({P}_{{H}_2O}), the temperature difference between the liquidus and amphibole appearance decreases, causing a change in chemical composition of the first amphibole to crystallize. An empirical calibration is proposed for an amphibole first appearance barometer-hygrometer that uses Mg# of the amphibole and f_{{O}_2}: P_{{H}2O}(MPa)=[{Mg#/52.7}-0.014 * Updelta NNO]^{15.12} This barometer gives a minimum {P}_{{H}2O} recorded by the first appearance of amphibole in primitive arc basaltic andesite and andesite. We apply this barometer to amphibole antecrysts erupted in mixed andesite and dacite lavas from the Mt. Shasta, CA stratocone. Both high H2O pressures (500-900 MPa) and high pre-eruptive magmatic

  5. Formation of low-temperature cirrus from H2SO4/H2O aerosol droplets.

    PubMed

    Bogdan, A; Molina, M J; Sassen, K; Kulmala, M

    2006-11-23

    We present experimental results obtained with a differential scanning calorimeter (DSC) that indicate the small ice particles in low-temperature cirrus clouds are not completely solid but rather coated with an unfrozen H2SO4/H2O overlayer. Our results provide a new look on the formation, development, and microphysical properties of low-temperature cirrus clouds. PMID:17107102

  6. H2O2 Synthesis Induced by Irradiation of H2O with Energetic H(+) and Ar(+) Ions at Various Temperatures

    NASA Technical Reports Server (NTRS)

    Baragiola, R. A.; Loeffler, M. J.; Raut, U.; Vidal, R. A.; Carlson, R. W.

    2004-01-01

    The detection of H2O2 on Jupiter's icy satellite Europa by the Galileo NIMS instrument presented a strong evidence for the importance of radiation effects on icy surfaces. A few experiments have investigated whether solar flux of protons incident on Europa ice could cause a significant if any H2O2 production. These published results differ as to whether H2O2 can be formed by ions impacting water at temperatures near 80 K, which are appropriate to Europa. This discrepancy may be a result of the use of different incident ion energies, different vacuum conditions, or different ways of processing the data. The latter possibility comes about from the difficulty of identifying the 3.5 m peroxide OH band on the long wavelength wing of the much stronger water 3.1 m band. The problem is aggravated by using straight line baselines to represent the water OH band with a curvature, in the region of the peroxide band, that increases with temperature. To overcome this problem, we use polynomial baselines that provide good fits to the water band and its derivative.

  7. In situ H2O and temperature detection close to burning biomass pellets using calibration-free wavelength modulation spectroscopy

    NASA Astrophysics Data System (ADS)

    Qu, Zhechao; Schmidt, Florian M.

    2015-04-01

    The design and application of an H2O/temperature sensor based on scanned calibration-free wavelength modulation spectroscopy (CF-WMS) and a single tunable diode laser at 1.4 µm is presented. The sensor probes two H2O absorption peaks in a single scan and simultaneously retrieves H2O concentration and temperature by least-squares fitting simulated 1f-normalized 2f-WMS spectra to measured 2f/ 1f-WMS signals, with temperature, concentration and nonlinear modulation amplitude as fitting parameters. Given a minimum detectable absorbance of 1.7 × 10-5 cm-1 Hz-1/2, the system is applicable down to an H2O concentration of 0.1 % at 1,000 K and 20 cm path length (200 ppm·m). The temperature in a water-seeded laboratory-scale reactor (670-1220 K at 4 % H2O) was determined within an accuracy of 1 % by comparison with the reactor thermocouple. The CF-WMS sensor was applied to real time in situ measurements of H2O concentration and temperature time histories (0.25-s time resolution) in the hot gases 2-11 mm above biomass pellets during atmospheric combustion in the reactor. Temperatures between 1,200 and 1,600 K and H2O concentrations up to 40 % were detected above the biofuels.

  8. A high temperature equation of state for the H 2O-CaCl 2 and H 2O-MgCl 2 systems

    NASA Astrophysics Data System (ADS)

    Duan, Zhenhao; Moller, Nancy; Weare, John H.

    2006-08-01

    An equation of state (EOS) is developed for salt-water systems in the high temperature range. As an example of the applications, this EOS is parameterized for the calculation of density, immiscibility, and the compositions of coexisting phases in the CaCl 2-H 2O and MgCl 2-H 2O systems from 523 to 973 K and from saturation pressure to 1500 bar. All available volumetric and phase equilibrium measurements of these binaries are well represented by this equation. This EOS is based on a Helmholtz free energy representation constructed from a reference system containing hard-sphere and polar contributions plus an empirical correction. For the temperature and pressure range in this study, the electrolyte solutes are assumed to be associated. The water molecules are modeled as hard spheres with point dipoles and the solute molecules, MgCl 2 and CaCl 2, as hard spheres with point quadrupoles. The free energy of the reference system is calculated from an analytical representation of the Helmholtz free energy of the hard-sphere contributions and perturbative estimates of the electrostatic contributions. The empirical correction used to account for deviations of the reference system predictions from measured data is based on a virial expansion. The formalism allows generalization to aqueous systems containing insoluble gases (CO 2, CH 4), alkali chlorides (NaCl, KCl), and alkaline earth chlorides (CaCl 2, MgCl 2). The program of this model is available as an electronic annex (see EA1 and EA2) and can also be downloaded at: http://www.geochem-model.org/programs.htm.

  9. Photodissociation Spectroscopy of Ca^+-H_2O in the Temperature-Variable Ion Trap

    NASA Astrophysics Data System (ADS)

    Ishikawa, Haruki; Eguchi, Toru; Nakano, Takumi; Fujihara, Akimasa; Fuke, Kiyokazu

    2011-06-01

    In the last two decades, developments of infrared spectroscopy and theoretical calculations on gas-phase molecular clusters have revealed detailed solvation structures of various systems, especially of hydrogen-bonded systems. One of the remained problems in studies on microscopic solvation or hydration is a temperature dependence of solvation structures. Lisy and coworkers succeeded in interpreting the hydration structures of alkali metal ions by taking temperature- or entropic effect. They utilized Ar vaporization to cool down the temperature of clusters. Another method for controlling temperature of cluster ions is a buffer gas cooling in an ion trap. In the present study, we have measured photodissociation spectra of Ca^+-H_2O in our temperature-variable ion trap In the present study, we examined the temperature of the Ca^+-H_2O in the trap by simulating the rotational profile of the 0-0 band of the ^2B_1 - ^2A_1 transition. The observed rotational profile is similar to that reported by Duncan and coworkers. By changing the trap period from 10 ms to 40 ms, it was confirmed that the trap period of 10 ms is sufficient to get temperature equilibrium in our experimental condition. Details of the experimental results will be presented in the paper. D. J. Miller, J. M. Lisy J. Am. Chem. Soc. 130, 15393 (2008). A. Fujihara, et al. J. Phys. Chem. A 112, 1457 (2008) A. Fujihara, et al. J. Phys. Chem. A 113, 8169 (2009). C. T. Scurlock, S. H. Pullins, J. E. Reddic, M. A. Duncan J. Chem. Phys. 104, 4591 (1996).

  10. Melting Temperature and Partial Melt Chemistry of H2O-Saturated Mantle Peridotite to 11 Gigapascals

    PubMed

    Kawamoto; Holloway

    1997-04-11

    The H2O-saturated solidus of a model mantle composition (Kilborne Hole peridotite nodule, KLB-1) was determined to be just above 1000°C from 5 to 11 gigapascals. Given reasonable H2O abundances in Earth's mantle, an H2O-rich fluid could exist only in a region defined by the wet solidus and thermal stability limits of hydrous minerals, at depths between 90 and 330 kilometers. The experimental partial melts monotonously became more mafic with increasing pressure from andesitic composition at 1 gigapascal to more mafic than the starting peridotite at 10 gigapascals. Because the chemistry of the experimental partial melts is similar to that of kimberlites, it is suggested that kimberlites may be derived by low-temperature melting of an H2O-rich mantle at depths of 150 to 300 kilometers. PMID:9092469

  11. High temperatures and high pressures Brillouin scattering studies of liquid H(2)O+CO(2) mixtures.

    PubMed

    Qin, Junfeng; Li, Min; Li, Jun; Chen, Rongyan; Duan, Zhenhao; Zhou, Qiang; Li, Fangfei; Cui, Qiliang

    2010-10-21

    The Brillouin scattering spectroscopy studies have been conducted in a diamond anvil cell for a liquid mixtures composed of 95 mol % H(2)O and 5 mol % CO(2) under high temperatures and pressures. The sound velocity, refractive index, density, and adiabatic bulk modulus of the H(2)O+CO(2) mixtures were determined under pressures up to the freezing point at 293, 453, and 575 K. It is found from the experiment that sound velocities of the liquid mixture are substantially lower than those of pure water at 575 K, but not at lower temperatures. We presented an empirical relation of the density in terms of pressure and temperature. Our results show that liquid H(2)O+CO(2) mixtures are more compressible than water obtained from an existing equation of state of at 453 and 575 K. PMID:20969409

  12. High-bandwidth scanned-wavelength-modulation spectroscopy sensors for temperature and H2O in a rotating detonation engine

    NASA Astrophysics Data System (ADS)

    Goldenstein, Christopher S.; Almodóvar, Christopher A.; Jeffries, Jay B.; Hanson, Ronald K.; Brophy, Christopher M.

    2014-10-01

    The design and use of two-color tunable diode laser (TDL) absorption sensors for measurements of temperature and H2O in a rotating detonation engine (RDE) are presented. Both sensors used first-harmonic-normalized scanned-wavelength-modulation spectroscopy with second-harmonic detection (scanned-WMS-2f/1f) to account for non-absorbing transmission losses and emission encountered in the harsh combustion environment. One sensor used two near-infrared (NIR) TDLs near 1391.7 nm and 1469.3 nm that were modulated at 225 kHz and 285 kHz, respectively, and sinusoidally scanned across the peak of their respective H2O absorption transitions to provide a measurement rate of 50 kHz and a detection limit in the RDE of 0.2% H2O by mole. The other sensor used two mid-infrared (MIR) TDLs near 2551 nm and 2482 nm that were modulated at 90 kHz and 112 kHz, respectively, and sinusoidally scanned across the peak of their respective H2O transitions to provide a measurement rate of 10 kHz and a detection limit in the RDE of 0.02% H2O by mole. Four H2O absorption transitions with different lower-state energies were used to assess the homogeneity of temperature in the measurement plane. Experimentally derived spectroscopic parameters that enable temperature and H2O sensing to within 1.5-3.5% of known values are reported. The sensor design enabling the high-bandwidth scanned-WMS-2f/1f measurements is presented. The two sensors were deployed across two orthogonal and coplanar lines-of-sight (LOS) located in the throat of a converging-diverging nozzle at the RDE combustor exit. Measurements in the non-premixed H2-fueled RDE indicate that the temperature and H2O oscillate at the detonation frequency (≈3.25 kHz) and that production of H2O is a weak function of global equivalence ratio.

  13. H2O2 assisted room temperature oxidation of Ti2C MXene for Li-ion battery anodes

    NASA Astrophysics Data System (ADS)

    Ahmed, Bilal; Anjum, Dalaver H.; Hedhili, Mohamed N.; Gogotsi, Yury; Alshareef, Husam N.

    2016-03-01

    Herein we demonstrate that a prominent member of the MXene family, Ti2C, undergoes surface oxidation at room temperature when treated with hydrogen peroxide (H2O2). The H2O2 treatment results in opening up of MXene sheets and formation of TiO2 nanocrystals on their surface, which is evidenced by the high surface area of H2O2 treated MXene and X-ray diffraction (XRD) analysis. We show that the reaction time and the amount of hydrogen peroxide used are the limiting factors, which determine the morphology and composition of the final product. Furthermore, it is shown that the performance of H2O2 treated MXene as an anode material in Li ion batteries (LIBs) was significantly improved as compared to as-prepared MXenes. For instance, after 50 charge/discharge cycles, specific discharge capacities of 389 mA h g-1, 337 mA h g-1 and 297 mA h g-1 were obtained for H2O2 treated MXene at current densities of 100 mA g-1, 500 mA g-1 and 1000 mA g-1, respectively. In addition, when tested at a very high current density, such as 5000 mA g-1, the H2O2 treated MXene showed a specific capacity of 150 mA h g-1 and excellent rate capability. These results clearly demonstrate that H2O2 treatment of Ti2C MXene improves MXene properties in energy storage applications, such as Li ion batteries or capacitors.Herein we demonstrate that a prominent member of the MXene family, Ti2C, undergoes surface oxidation at room temperature when treated with hydrogen peroxide (H2O2). The H2O2 treatment results in opening up of MXene sheets and formation of TiO2 nanocrystals on their surface, which is evidenced by the high surface area of H2O2 treated MXene and X-ray diffraction (XRD) analysis. We show that the reaction time and the amount of hydrogen peroxide used are the limiting factors, which determine the morphology and composition of the final product. Furthermore, it is shown that the performance of H2O2 treated MXene as an anode material in Li ion batteries (LIBs) was significantly improved as

  14. Direct numerical simulations of exhaust gas recirculation effect on multistage autoignition in the negative temperature combustion regime for stratified HCCI flow conditions by using H2O2 addition

    NASA Astrophysics Data System (ADS)

    El-Asrag, Hossam A.; Ju, Yiguang

    2013-04-01

    Direct numerical simulations (DNSs) of a stratified flow in a homogeneous compression charge ignition (HCCI) engine are performed to investigate the exhaust gas recirculation (EGR) and temperature/mixture stratification effects on the autoignition of synthetic dimethyl ether (DME) in the negative temperature combustion region. Detailed chemistry for a DME/air mixture is employed and solved by a hybrid multi-time scale (HMTS) algorithm to reduce the computational cost. The effect of ? to mimic the EGR effect on autoignition are studied. The results show that adding ? enhances autoignition by rapid OH radical pool formation (34-46% reduction in ignition delay time) and changes the ignition heat release rates at different ignition stages. Sensitivity analysis is performed and the important reactions pathways affecting the autoignition are specified. The DNS results show that the scales introduced by thermal and mixture stratifications have a strong effect after the low temperature chemistry (LTC) ignition especially at the locations of high scalar dissipation rates. Compared to homogenous ignition, stratified ignitions show similar first autoignition delay times, but 18% reduction in the second and third ignition delay times. The results also show that molecular transport plays an important role in stratified low temperature ignition, and that the scalar mixing time scale is strongly affected by local ignition in the stratified flow. Two ignition-kernel propagation modes are observed: a wave-like, low-speed, deflagrative mode and a spontaneous, high-speed, ignition mode. Three criteria are introduced to distinguish these modes by different characteristic time scales and Damkhöler numbers using a progress variable conditioned by an ignition kernel indicator. The low scalar dissipation rate flame front is characterized by high displacement speeds and high mixing Damkhöler number. The proposed criteria are applied successfully at the different ignition stages and

  15. H2O2 assisted room temperature oxidation of Ti2C MXene for Li-ion battery anodes.

    PubMed

    Ahmed, Bilal; Anjum, Dalaver H; Hedhili, Mohamed N; Gogotsi, Yury; Alshareef, Husam N

    2016-04-14

    Herein we demonstrate that a prominent member of the MXene family, Ti2C, undergoes surface oxidation at room temperature when treated with hydrogen peroxide (H2O2). The H2O2 treatment results in opening up of MXene sheets and formation of TiO2 nanocrystals on their surface, which is evidenced by the high surface area of H2O2 treated MXene and X-ray diffraction (XRD) analysis. We show that the reaction time and the amount of hydrogen peroxide used are the limiting factors, which determine the morphology and composition of the final product. Furthermore, it is shown that the performance of H2O2 treated MXene as an anode material in Li ion batteries (LIBs) was significantly improved as compared to as-prepared MXenes. For instance, after 50 charge/discharge cycles, specific discharge capacities of 389 mA h g(-1), 337 mA h g(-1) and 297 mA h g(-1) were obtained for H2O2 treated MXene at current densities of 100 mA g(-1), 500 mA g(-1) and 1000 mA g(-1), respectively. In addition, when tested at a very high current density, such as 5000 mA g(-1), the H2O2 treated MXene showed a specific capacity of 150 mA h g(-1) and excellent rate capability. These results clearly demonstrate that H2O2 treatment of Ti2C MXene improves MXene properties in energy storage applications, such as Li ion batteries or capacitors. PMID:26984324

  16. 3D CFD Model of High Temperature H2O/CO2 Co-electrolysis

    SciTech Connect

    Grant Hawkes; James O'Brien; Carl Stoots; Stephen Herring; Joe Hartvigsen

    2007-06-01

    3D CFD Model of High Temperature H2O/CO2 Co-Electrolysis Grant Hawkes1, James O’Brien1, Carl Stoots1, Stephen Herring1 Joe Hartvigsen2 1 Idaho National Laboratory, Idaho Falls, Idaho, grant.hawkes@inl.gov 2 Ceramatec Inc, Salt Lake City, Utah INTRODUCTION A three-dimensional computational fluid dynamics (CFD) model has been created to model high temperature co-electrolysis of steam and carbon dioxide in a planar solid oxide electrolyzer (SOE) using solid oxide fuel cell technology. A research program is under way at the Idaho National Laboratory (INL) to simultaneously address the research and scale-up issues associated with the implementation of planar solid-oxide electrolysis cell technology for syn-gas production from CO2 and steam. Various runs have been performed under different run conditions to help assess the performance of the SOE. This paper presents CFD results of this model compared with experimental results. The Idaho National Laboratory (INL), in conjunction with Ceramatec Inc. (Salt Lake City, USA) has been researching for several years the use of solid-oxide fuel cell technology to electrolyze steam for large-scale nuclear-powered hydrogen production. Now, an experimental research project is underway at the INL to produce syngas by simultaneously electrolyzing at high-temperature steam and carbon dioxide (CO2) using solid oxide fuel cell technology. A strong interest exists in the large-scale production of syn-gas from CO2 and steam to be reformed into a usable transportation fuel. If biomass is used as the carbon source, the overall process is climate neutral. Consequently, there is a high level of interest in production of syn-gas from CO2 and steam electrolysis. With the price of oil currently around $60 / barrel, synthetically-derived hydrocarbon fuels (synfuels) have become economical. Synfuels are typically produced from syngas – hydrogen (H2) and carbon monoxide (CO) -- using the Fischer-Tropsch process, discovered by Germany before World

  17. Measurements of Flow Distortion within the IRGASON Integrated Sonic Anemometer and CO_2 /H_2 O Gas Analyzer

    NASA Astrophysics Data System (ADS)

    Horst, T. W.; Vogt, R.; Oncley, S. P.

    2016-02-01

    Wind-tunnel and field measurements are analyzed to investigate flow distortion within the IRGASON integrated sonic anemometer and CO_2 /H_2 O gas analyzer as a function of wind speed, wind direction and attack angle. The wind-tunnel measurements are complimentary to the field measurements, and the dependence of the wind-tunnel mean-wind-component flow-distortion errors on wind direction agrees well with that of the field measurements. The field measurements exhibit significant overestimation of the crosswind variance and underestimation of the momentum flux with respect to an adjacent CSAT3 sonic, as well as a transfer of turbulent kinetic energy from the streamwise wind component to the cross-stream wind components. In contrast, we find attenuation of only a few percent in the vertical velocity variance and the vertical flux of sonic temperature. The attenuation of the fluxes appears to be caused to a large extent by decorrelation between the horizontal and vertical-velocity components and between the vertical velocity and sonic temperature. Additional flow distortion due to transducer shadowing reduces to some extent the overestimation, but also increases the underestimation of the IRGASON turbulence statistics.

  18. Measurements of Flow Distortion within the IRGASON Integrated Sonic Anemometer and CO_2/H_2O Gas Analyzer

    NASA Astrophysics Data System (ADS)

    Horst, T. W.; Vogt, R.; Oncley, S. P.

    2016-07-01

    Wind-tunnel and field measurements are analyzed to investigate flow distortion within the IRGASON integrated sonic anemometer and CO_2/H_2O gas analyzer as a function of wind speed, wind direction and attack angle. The wind-tunnel measurements are complimentary to the field measurements, and the dependence of the wind-tunnel mean-wind-component flow-distortion errors on wind direction agrees well with that of the field measurements. The field measurements exhibit significant overestimation of the crosswind variance and underestimation of the momentum flux with respect to an adjacent CSAT3 sonic, as well as a transfer of turbulent kinetic energy from the streamwise wind component to the cross-stream wind components. In contrast, we find attenuation of only a few percent in the vertical velocity variance and the vertical flux of sonic temperature. The attenuation of the fluxes appears to be caused to a large extent by decorrelation between the horizontal and vertical-velocity components and between the vertical velocity and sonic temperature. Additional flow distortion due to transducer shadowing reduces to some extent the overestimation, but also increases the underestimation of the IRGASON turbulence statistics.

  19. HIGH-TEMPERATURE CO-ELECTROLYSIS OF H2O AND CO2 FOR SYNGAS PRODUCTION

    SciTech Connect

    Stoots, C.M.

    2006-11-01

    Worldwide, the demand for light hydrocarbon fuels like gasoline and diesel oil is increasing. To satisfy this demand, oil companies have begun to utilize oil deposits of lower hydrogen content (an example is the Athabasca Oil Sands). Additionally, the higher contents of sulfur and nitrogen of these resources requires processes such as hydrotreating to meet environmental requirements. In the mean time, with the price of oil currently over $50 / barrel, synthetically-derived hydrocarbon fuels (synfuels) have become economical. Synfuels are typically produced from syngas – hydrogen (H2) and carbon monoxide (CO) -- using the Fischer-Tropsch process, discovered by Germany before World War II. South Africa has used synfuels to power a significant number of their buses, trucks, and taxicabs. The Idaho National Laboratory (INL), in conjunction with Ceramatec Inc. (Salt Lake City, USA) has been researching for several years the use of solid-oxide fuel cell technology to electrolyze steam for large-scale nuclear-powered hydrogen production. Now, an experimental research project is underway at the INL to investigate the feasibility of producing syngas by simultaneously electrolyzing at high-temperature steam and carbon dioxide (CO2) using solid oxide fuel cell technology. The syngas can then be used for synthetic fuel production. This program is a combination of experimental and computational activities. Since the solid oxide electrolyte material is a conductor of oxygen ions, CO can be produced by electrolyzing CO2 sequestered from some greenhouse gas-emitting process. Under certain conditions, however, CO can further electrolyze to produce carbon, which can then deposit on cell surfaces and reduce cell performance. The understanding of the co-electrolysis of steam and CO2 is also complicated by the competing water-gas shift reaction. Results of experiments and calculations to date of CO2 and CO2/H2O electrolysis will be presented and discussed. These will include

  20. Bubble nucleation in H2O-CO2 bearing basaltic melts: results of high temperature decompression experiments

    NASA Astrophysics Data System (ADS)

    Le Gall, N.; Pichavant, M.; Burgisser, A.

    2012-12-01

    Previous experiments have shown that mechanisms of basalt degassing are strongly contrasted when gas bubbles are present or when they are absent. Thus, experimental information on the kinetics of bubble nucleation in basaltic melts is needed, and high temperature decompression experiments have been investigated. All experiments used PST-9 basaltic pumice from Stromboli as starting material. The sample was fused in air at 1400°C for 3h and then cylinders (l up to 10mm, d 2.5 and 5mm) were cored. Synthesis experiments were performed to produce the volatile-bearing melts to be used in the decompression experiments. Glass cores, distilled H2O and Ag2C2O4 were loaded in AuPd capsules. Three different H2O/CO2 were introduced, corresponding to XH2Oin=1 (#1: only H2O dissolved in glass), 0.55 (#2: high dissolved H2O/CO2), 0 (#3: low dissolved H2O/CO2). The synthesis experiments were ran at 1200°C during about 40h in an internally heated vessel pressurized with Ar-H2. The synthesized crystal- and bubble-free glasses were cut in 2 parts: one for the decompression experiments and the other for the analysis. Decompression experiments were conducted at a fast rate of 39kPa/s, exceptionally of 77.8kPa/s, at 1200°C from an initial pressure (Pin) of 200MPa and to final pressures (Pf) of 200, 150, 100 and 50MPa. Experiments to 25MPa are in progress. Each run included 3 capsules, corresponding to the 3 XH2Oin conditions of glass synthesis, allowing results for the 3 H2O/CO2 to be directly compared. Charges were rapid-quenched immediately after attainment of Pf. Textures were analyzed by X-ray microtomography, and volatile concentrations and spatial distributions in pre- and post-decompression glasses were determined by FTIR. Pre-decompression glasses have homogeneous volatile contents and distributions. They divide into 3 compositional groups consistent with their XH2Oin conditions of synthesis: group #1 (average H2O content=4.82wt%, average CO2 content=0ppm), group #2 (2.15wt

  1. Effects of H2O Vapor on Vibrational Relaxation in Expanding and Contracting Flows

    NASA Technical Reports Server (NTRS)

    Meador, Willard E.; Townsend, Lawrence W.; Miner, Gilda A.

    1996-01-01

    As opposed to previous explanations based on the effects of anharmonicity of simple diatomic molecules, traces of water vapor are suggested to be the most likely cause of the anomalously fast vibrational relaxation of such gases observed in supersonic and hypersonic nozzles. The mechanism is the strong V-VR coupling with H2O molecules that dramatically facilitates the collisional transfer of vibrational energy. Slight moisture content is thus a real world aspect of gas dynamics that must be considered in characterizations of shock tubes, reflected shock tunnels, and expansion tubes.

  2. Raman spectroscopic quantitative study of NaCl-CaCl2-H2O system at high temperatures and pressures.

    PubMed

    Li, Jing; Mao, Shi-De; Zheng, Hai-Fei

    2014-07-01

    Raman spectra features of the ternary system NaCl-CaCl2-H2O under high temperatures and high pressures were systematically studied in the present work by using hydrothermal diamond anvil cell (HDAC) and Raman shifts of quartz to determine pressures, and it has been obtained for the quantitative relationship between Raman shifts of the O-H stretching band of water, mass fractions of solutes and pressures was obtained. The mass fractions of salts, where salinity of NaCl equal to that of CaCl2, are 4.0 mass %, 8.0 mass %, and 12.0 mass %, respectively. Experimental results indicate that the standardized Raman frequency shift differences of the O-H stretching vibration (deltav(O0H)) rise with the increasing temperatures when the mass fractions of salts and pressures of the NaCl-CaCl2-H2O system remain constant. deltav(O-H) increases with the increase in mass fractions of salts in the system when the temperatures and pressures are constant. Linear relationship between deltav(O-H) and pressure with similar slopes can be found for the NaCl-CaCl2-H2O system with different salinities. The quantitative relationship between deltav(O-H), temperature (T), pressure (P), and mass fraction of solute (M) is P = -31.892 deltav(O-H) + 10.131T + 222.816M - 3 183.567, where the valid PTM range of the equation is 200 MPa < or = P < or = 1 700 MPa, 273 K < or = T < or = 539 K and M < or = 12 mass %. The equation can be used as a geobarometer in the studies of fluid inclusions of NaCl-CaCl2-H2O system with equal salinities. The method, as a direct geological detecting technique, has a potential application value. PMID:25269273

  3. Room temperature synthesis of K2Mo3O10x3H2O nanowires in minutes.

    PubMed

    Gong, Weiwei; Xue, Jiongwei; Zhang, Kai; Wu, Zhan; Wei, Dapeng; Chen, Qing; Pan, Huayong; Xu, Shengyong

    2009-05-27

    Polyoxometalates have been widely used in the fields of catalysis, analytical chemistry, biochemistry, medicine and synthesis of novel organic-inorganic materials. It is difficult to synthesize pure polymolybdate products from a solution because several kinds of molybdenum-based anions may coexist. As a result, varied acidification methods are commonly used for solution synthesis of polymolybdates. In this paper we report an approach for the synthesis of [001]-oriented K(2)Mo(3)O(10)x3H(2)O nanowires from an aqueous solution of (NH(4))(6)Mo(7)O(24)x4H(2)O and KCl at low temperatures. The reaction occurs even at temperatures as low as 0 degrees C, and at 30-90 degrees C the whole procedure needs only a few minutes. Without any additional acidification treatments, the pH value of the solution is maintained in a narrow range of +/- 0.1 between 4.9 and 5.5 during the whole synthesis procedure. The starting pH depends on the reaction temperature. Crystalline structure and purity of the final products have been characterized with x-ray diffraction, electron diffraction and dehydration measurements. This simple and rapid method provides a unique case for studying the growth mechanism of polymolybdate nanostructures, and has a promising potential in the mass production of low-cost, pure-phase polymolybdates for a variety of applications. PMID:19423934

  4. Microemulsion-enhanced electrochemiluminescence of luminol-H2O2 for sensitive flow injection analysis of antioxidant compounds.

    PubMed

    Xiuhua, Wei; Chao, Liu; Yifeng, Tu

    2012-05-30

    A microemulsion enhanced electrochemiluminescence (ECL) of luminol-H(2)O(2) was studied with the flow-injection (FI) technique. The results revealed that the microemulsion composed with cetyltrimethylammonium bromide (CTAB), n-butanol, n-heptane and water greatly enhanced the ECL especially in acidic medium. The ECL emission increased for 20 to 2 times in this microemulsion medium over the pH range of 5.0-8.0 compared to that in aqueous solution. The mechanism of enhancement of surfactant and microemulsion for luminol-H(2)O(2) ECL was discussed. It is mainly based on the electrostatic interaction between luminol anion and the head group of surfactant, which causes the adsorption and promotes the dissociation of luminol on the surfaces of the microemulsion droplets, favors the oxidation of luminol by the yielded reactive oxygen species (ROSs) during electrolysis. This research is very significant for ECL applications because of the extended practicable pH range which was suitable for environmental and biological systems. As an example, this FI-ECL technique can be applied for determination of oligo proanthocyanidin (OPC) because of its antioxidant property and to evaluate the total antioxidant activity of the grape skin using OPC as an index. PMID:22608450

  5. Water Exchange on [Ln(DO3A)(H2O)2] and [Ln(DTTA-Me)(H2O)2](-) Studied by Variable Temperature, Pressure, and Magnetic Field NMR.

    PubMed

    Karimi, Shima; Helm, Lothar

    2016-05-01

    Water exchange kinetics of [Ln(L)(H2O)2](x) complexes (Ln = Pr, Nd, Dy, Tm, and Yb; L = DO3A and DTTA-Me) were studied by (17)O NMR spectroscopy as a function of temperature, pressure, and frequency and by (1)H nuclear magnetic relaxation dispersion. Water exchange rate constants of both complexes show a maximum at dysprosium. Water exchange on negatively charged complexes of the acyclic DTTA-Me ligand is much faster than on the neutral complexes of the macrocyclic DO3A. Small activation volumes |ΔV(⧧)| < 1 cm(3) mol(-1) measured for water exchange on [Ln(DO3A)(H2O)2] indicate an interchange type of mechanism (I) for the lanthanide complexes studied. In the case of [Ln(DTTA-Me)(H2O)2](-), a change in mechanism is detected from a dissociative mechanism (D, ΔV(⧧) = 7 cm(3) mol(-1)) for complexes with larger ions (Pr to Gd) to an interchange mechanism (Id, I; ΔV(⧧) = +1.8 and +0.4 cm(3) mol(-1)) for complexes with smaller ions (Dy and Tm). PMID:27082861

  6. Temperature-dependent kinetic measurements and quasi-classical trajectory studies for the OH+ + H2/D2 → H2O+/HDO+ + H/D reactions

    NASA Astrophysics Data System (ADS)

    Martinez, Oscar; Ard, Shaun G.; Li, Anyang; Shuman, Nicholas S.; Guo, Hua; Viggiano, Albert A.

    2015-09-01

    We have measured the temperature-dependent kinetics for the reactions of OH+ with H2 and D2 using a selected ion flow tube apparatus. Reaction occurs via atom abstraction to result in H2O+/HDO+ + H/D. Room temperature rate coefficients are in agreement with prior measurements and resulting temperature dependences are T0.11 for the hydrogen and T0.25 for the deuterated reactions. This work is prompted in part by recent theoretical work that mapped a full-dimensional global potential energy surface of H3O+ for the OH+ + H2 → H + H2O+ reaction [A. Li and H. Guo, J. Phys. Chem. A 118, 11168 (2014)], and reported results of quasi-classical trajectory calculations, which are extended to a wider temperature range and initial rotational state specification here. Our experimental results are in excellent agreement with these calculations which accurately predict the isotope effect in addition to an enhancement of the reaction rate constant due to the molecular rotation of OH+. The title reaction is of high importance to astrophysical models, and the temperature dependence of the rate coefficients determined here should now allow for better understanding of this reaction at temperatures more relevant to the interstellar medium.

  7. Effect of mild-temperature H2O2 oxidation on solubilization and anaerobic digestion of waste activated sludge.

    PubMed

    Junga, Heejung; Kim, Jaai; Lee, Seungyong; Lee, Changsoo

    2014-08-01

    Efficient sludge management is among the most challenging issues in wastewater treatment today, and anaerobic digestion is regarded as a viable solution. Mild-temperature H202 oxidation was examined for enhanced solubilization and biogas production of waste activated sludge (WAS). The effects of pretreatment factors (i.e. temperature and H202 concentration) on the degree of WAS disintegration (DD) and biogas yield (BY) were assessed by response surface analysis within the design space of 60-90 degrees C and 0-200mM H202. Significant sludge disintegration (up to 23.0% DD) and visibly enhanced BY (up to 26.9%) were shown in the pretreatment trials. Two response surface models to describe how DD and BY respond to changes in the pretreatment conditions were successfully constructed (R2 > 0.95, p < 0.05). The models showed totally different response surface shapes, indicating the DD and BY were influenced by pretreatment conditions in very different ways. DD was dominantly affected by temperature and showed higher model responses at the high-temperature region, while the BY response peaked in the low-temperature and mid-level H2O2 region. This observation implies that the enhanced solubilization of WAS was not directly translated into an increase in biogas production. Our results showed that WAS can be efficiently disintegrated by H202 oxidation under mild-temperature conditions for enhanced anaerobic digestibility. Within the explored region of pretreatment conditions, the maximum BY was estimated to be 82.1 mL/gCODadded (32.8% greater than the untreated control) at (60.0 degrees C, 74.2 mM H2O2). PMID:24956761

  8. Surface temperatures and retention of H2O frost on Ganymede and Callisto

    NASA Technical Reports Server (NTRS)

    Squyres, S. W.

    1980-01-01

    Surface temperatures and ice evaporation rates are calculated for Ganymede and Callisto as functions of latitude, time of day, and albedo, according to a model that uses surface thermal properties determined by eclipse radiometry and albedos determined from photometrically decalibrated Voyager images. The difference in temperature between Ganymede and Callisto is not great enough to account for the lack of bright polar caps on Callisto, which seems instead to reflect a real deficiency in the amount of available water frost relative to Ganymede. The temperature difference between Ganymede's grooved and cratered terrains also cannot account for the high concentration of bright ray craters in the former, suggesting that an internal geologic process has enriched the grooved terrain in ice content relative to the cratered terrain.

  9. Fabrication of porous silicon nanowires by MACE method in HF/H2O2/AgNO3 system at room temperature.

    PubMed

    Li, Shaoyuan; Ma, Wenhui; Zhou, Yang; Chen, Xiuhua; Xiao, Yongyin; Ma, Mingyu; Zhu, Wenjie; Wei, Feng

    2014-01-01

    In this paper, the moderately and lightly doped porous silicon nanowires (PSiNWs) were fabricated by the 'one-pot procedure' metal-assisted chemical etching (MACE) method in the HF/H2O2/AgNO3 system at room temperature. The effects of H2O2 concentration on the nanostructure of silicon nanowires (SiNWs) were investigated. The experimental results indicate that porous structure can be introduced by the addition of H2O2 and the pore structure could be controlled by adjusting the concentration of H2O2. The H2O2 species replaces Ag(+) as the oxidant and the Ag nanoparticles work as catalyst during the etching. And the concentration of H2O2 influences the nucleation and motility of Ag particles, which leads to formation of different porous structure within the nanowires. A mechanism based on the lateral etching which is catalyzed by Ag particles under the motivation by H2O2 reduction is proposed to explain the PSiNWs formation. PMID:24910568

  10. Fabrication of porous silicon nanowires by MACE method in HF/H2O2/AgNO3 system at room temperature

    PubMed Central

    2014-01-01

    In this paper, the moderately and lightly doped porous silicon nanowires (PSiNWs) were fabricated by the ‘one-pot procedure’ metal-assisted chemical etching (MACE) method in the HF/H2O2/AgNO3 system at room temperature. The effects of H2O2 concentration on the nanostructure of silicon nanowires (SiNWs) were investigated. The experimental results indicate that porous structure can be introduced by the addition of H2O2 and the pore structure could be controlled by adjusting the concentration of H2O2. The H2O2 species replaces Ag+ as the oxidant and the Ag nanoparticles work as catalyst during the etching. And the concentration of H2O2 influences the nucleation and motility of Ag particles, which leads to formation of different porous structure within the nanowires. A mechanism based on the lateral etching which is catalyzed by Ag particles under the motivation by H2O2 reduction is proposed to explain the PSiNWs formation. PMID:24910568

  11. CKA2 functions in H2O2-induced apoptosis and high-temperature stress tolerance by regulating NO accumulation in yeast.

    PubMed

    Liu, Wen-Cheng; Yuan, Hong-Mei; Li, Yun-Hui; Lu, Ying-Tang

    2015-09-01

    Nitric oxide (NO) plays key roles in yeast responses to various environmental factors, such as H2O2 and high temperature. However, the gene encoding NO synthase (NOS) in yeast has not yet been identified, and the mechanism underlying the regulation of NOS-like activity is poorly understood. Here, we report on the involvement of CKA2 in H2O2-induced yeast apoptosis and yeast high-temperature stress tolerance. Our results showed that although Δcka2 mutant had reduced NO accumulation with decreased apoptosis after H2O2 exposure, treatment with a NO donor, sodium nitroprusside, resulted in similar survival rate of Δcka2 mutant compared to that of wild-type yeast when subjected to H2O2 stress. This finding occurred because H2O2-enhanced NOS-like activity in wild-type yeast was significantly repressed in Δcka2. Our additional experiments indicated that both high-temperature-enhanced NO accumulation and NOS-like activity were also suppressed in Δcka2, leading to the hypersensitivity of the mutant to high temperature in terms of changes in survival rate. Thus, our results showed that CKA2 functioned in H2O2-induced apoptosis and high-temperature stress tolerance by regulating NOS-like-dependent NO accumulation in yeast. PMID:26100262

  12. H2/O2 three-body rates at high temperatures

    NASA Technical Reports Server (NTRS)

    Marinelli, William J.; Kessler, William J.; Piper, Lawrence G.; Rawlins, W. Terry

    1990-01-01

    The extraction of thrust from air breathing hypersonic propulsion systems is critically dependent on the degree to which chemical equilibrium is reached in the combustion process. In the combustion of H2/Air mixtures, slow three-body chemical reactions involving H-atoms, O-atoms, and the OH radical play an important role in energy extraction. A first-generation high temperature and pressure flash-photolysis/laser-induced fluorescence reactor was designed and constructed to measure these important three-body rates. The system employs a high power excimer laser to produce these radicals via the photolysis of stable precursors. A novel two-photon laser-induced fluorescence technique is employed to detect H-atoms without optical thickness or O2 absorption problems. To demonstrate the feasibility of the technique the apparatus in the program is designed to perform preliminary measurements on the H + O2 + M reaction at temperatures from 300 to 835 K.

  13. H2/O2 three-body rates at high temperatures

    NASA Technical Reports Server (NTRS)

    Marinelli, William J.; Kessler, William J.; Carleton, Karen L.

    1991-01-01

    Hydrogen atoms are produced in the presence of excess O2, and the first-order decay are studied as a function of temperature and pressure in order to obtain the rate coefficient for the three-body reaction between H-atoms and O2. Attention is focused on the kinetic scheme employed as well as the reaction cell and photolysis and probe laser system. A two-photon laser-induced fluorescence technique is employed to detect H-atoms without optical-thickness or O2-absorption problems. Results confirm measurements reported previously for the H + O2 + N2 reaction at 300 K and extend these measurements to higher temperatures. Preliminary data indicate non-Arrehenius-type behavior of this reaction rate coefficient as a function of temperature. Measurements of the rate coefficient for H + O2 + Ar reaction at 300 K give a rate coefficient of 2.1 +/- 0.1 x 10 to the -32nd cm exp 6/molecule sec.

  14. The low temperature oxidation of lithium thin films on HOPG by O2 and H2O

    NASA Astrophysics Data System (ADS)

    Wulfsberg, Steven M.; Koel, Bruce E.; Bernasek, Steven L.

    2016-09-01

    Lithiated graphite and lithium thin films have been used in fusion devices. In this environment, lithiated graphite will undergo oxidation by background gases. In order to gain insight into this oxidation process, thin (< 15 monolayer (ML)) lithium films on highly ordered pyrolytic graphite (HOPG) were exposed to O2(g) and H2O(g) in an ultra-high vacuum chamber. High resolution electron energy loss spectroscopy (HREELS) was used to identify the surface species formed during O2(g) and H2O(g) exposure. Auger electron spectroscopy (AES) was used to obtain the relative oxidation rates during O2(g) and H2O(g) exposure. AES showed that as the lithium film thickness decreased from 15 to 5 to 1 ML, the oxidation rate decreased for both O2(g) and H2O(g). HREELS showed that a 15 ML lithium film was fully oxidized after 9.7 L (L) of O2(g) exposure and Li2O was formed. HREELS also showed that during initial exposure (< 0.5 L) H2O(g), lithium hydride and lithium hydroxide were formed on the surface of a 15 ML lithium film. After 0.5 L of H2O(g) exposure, the H2O(g) began to physisorb, and after 15 L of H2O(g) exposure, the 15 ML lithium film was not fully oxidized.

  15. Crop responses to elevated CO2 and interactions with H2O, N, and temperature.

    PubMed

    Kimball, Bruce A

    2016-06-01

    About twenty-seven years ago, free-air CO2 enrichment (FACE) technology was developed that enabled the air above open-field plots to be enriched with CO2 for entire growing seasons. Since then, FACE experiments have been conducted on cotton, wheat, ryegrass, clover, potato, grape, rice, barley, sugar beet, soybean, cassava, rape, mustard, coffee (C3 crops), and sorghum and maize (C4 crops). Elevated CO2 (550ppm from an ambient concentration of about 353ppm in 1990) decreased evapotranspiration about 10% on average and increased canopy temperatures about 0.7°C. Biomass and yield were increased by FACE in all C3 species, but not in C4 species except when water was limiting. Yields of C3 grain crops were increased on average about 19%. PMID:27043481

  16. Wavelength-modulation spectroscopy near 1.4 µm for measurements of H2O and temperature in high-pressure and -temperature gases

    NASA Astrophysics Data System (ADS)

    Goldenstein, C. S.; Spearrin, R. M.; Schultz, I. A.; Jeffries, J. B.; Hanson, R. K.

    2014-05-01

    The development, validation and demonstration of a two-color tunable diode laser (TDL) absorption sensor for measurements of temperature and H2O in high-pressure and high-temperature gases are presented. This sensor uses first-harmonic-normalized wavelength-modulation spectroscopy with second-harmonic detection (WMS-2f/1f) to account for non-absorbing transmission losses and emission encountered in harsh, high-pressure environments. Two telecommunications-grade TDLs were used to probe H2O absorption transitions near 1391.7 and 1469.3 nm. The lasers were frequency-multiplexed and modulated at 160 and 200 kHz to enable a measurement bandwidth up to 30 kHz along a single line-of-sight. In addition, accurate measurements are enabled at extreme conditions via an experimentally derived spectroscopic database. This sensor was validated under low-absorbance (<0.05) conditions in shock-heated H2O-N2 mixtures at temperatures and pressures from 700 to 2400 K and 2 to 25 atm. There, this sensor recovered the known temperature and H2O mole fraction with a nominal accuracy of 2.8% and 4.7% RMS, respectively. Lastly, this sensor resolved expected transients with high bandwidth and high precision in a reactive shock tube experiment and a pulse detonation combustor.

  17. H2O activity in concentrated KCl and KCl-NaCl solutions at high temperatures and pressures measured by the brucite-periclase equilibrium

    NASA Astrophysics Data System (ADS)

    Aranovich, L. Y.; Newton, R. C.

    H2O activities in supercritical fluids in the system KCl-H2O-(MgO) were measured at pressures of 1, 2, 4, 7, 10 and 15 kbar by numerous reversals of vapor compositions in equilibrium with brucite and periclase. Measurements spanned the range 550-900°C. A change of state of solute KCl occurs as pressures increase above 2kbar, by which H2O activity becomes very low and, at pressures of 4kbar and above, nearly coincident with the square of the mole fraction (xH2O). The effect undoubtedly results primarily from ionic dissociation as H2O density (ρH2O) approaches 1gm/cm3, and is more pronounced than in the NaCl-H2O system at the same P-T-X conditions. Six values of solute KCl activity were yielded by terminal points of the isobaric brucite-periclase T-xH2O curves where sylvite saturation occurs. The H2O mole fraction of the isobaric invariant assemblage brucite-periclase-sylvite-fluid is near 0.52 at all pressures, and the corresponding temperatures span only 100°C between 1 and 15kbar. This remarkable convergence of the isobaric equilibrium curves reflects the great influence of pressure on lowering of both KCl and H2O activities. The H2O and KCl activities can be expressed by the formulas: aH2O=γH2O[xH2O+(1+(1+α)xKCl)], and aKCL=γKCl[(1+α)xKCl/(xH2O+(1+α)xKCl)](1+α), where α is a degree of dissociation parameter which increases from zero at the lowest pressures to near one at high pressures and the γ's are activity coefficients based on an empirical regular solution parameter W: ln γi=(1-xi)2W. Least squares fitting of our H2O and KCl activity data evaluates the parameters: α=exp(4.166 -2.709/ρH2O) - 212.1P/T, and W=(-589.6-23.10P) /T, with ρH2O in gm/cm3, P in kbar and T in K. The standard deviation from the measured activities is only +/-0.014. The equations define isobaric liquidus curves, which are in perfect agreement with previous DTA liquidus measurements at 0.5-2kbar, but which depart progressively from their extrapolation to higher pressures

  18. Gradual crossover in molecular organization of stable liquid H2O at moderately high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Koga, Yoshikata; Westh, Peter; Yoshida, Koh; Inaba, Akira; Nakazawa, Yasuhiro

    2014-09-01

    Using the literature raw data of the speed of sound and the specific volume, the isothermal compressibility, κT, a second derivative thermodynamic quantity of G, was evaluated for liquid H2O in the pressure range up to 350 MPa and the temperature to 50 °C. We then obtained its pressure derivative, dκT/dp, a third derivative numerically without using a fitting function to the κT data. On taking yet another p-derivative at a fixed T graphically without resorting to any fitting function, the resulting d2κT/dp2, a fourth derivative, showed a weak but clear step anomaly, with the onset of the step named point X and its end point Y. In analogy with another third and fourth derivative pair in binary aqueous solutions of glycerol, dαp/dxGly and d2αp/dxGly2, at 0.1 MPa (αp is the thermal expansivity and xGly the mole fraction of solute glycerol) in our recent publication [J. Solution Chem. 43, 663-674 (2014); DOI:10.1007/s10953-013-0122-7], we argue that there is a gradual crossover in the molecular organization of pure H2O from a low to a high p-regions starting at point X and ending at Y at a fixed T. The crossover takes place gradually spanning for about 100 MPa at a fixed temperature. The extrapolated temperature to zero p seems to be about 70 - 80 °C for points X and 90 - 110 °C for Y. Furthermore, the mid-points of X and Y seem to extrapolate to the triple point of liquid, ice Ih and ice III. Recalling that the zero xGly extrapolation of point X and Y for binary aqueous glycerol at 0.1 MPa gives about the same T values respectively, we suggest that at zero pressure the region below about 70 °C the hydrogen bond network is bond-percolated, while above about 90 °C there is no hydrogen bond network. Implication of these findings is discussed.

  19. Late Holocene hydrous mafic magmatism at the Paint Pot Crater and Callahan flows, Medicine Lake Volcano, N. California and the influence of H2O in the generation of silicic magmas

    USGS Publications Warehouse

    Kinzler, R.J.; Donnelly-Nolan, J. M.; Grove, T.L.

    2000-01-01

    This paper characterizes late Holocene basalts and basaltic andesites at Medicine Lake volcano that contain high pre-eruptive H2O contents inherited from a subduction related hydrous component in the mantle. The basaltic andesite of Paint Pot Crater and the compositionally zoned basaltic to andesitic lavas of the Callahan flow erupted approximately 1000 14C years Before Present (14C years B.P.). Petrologic, geochemical and isotopic evidence indicates that this late Holocene mafic magmatism was characterized by H2O contents of 3 to 6 wt% H2O and elevated abundances of large ion lithophile elements (LILE). These hydrous mafic inputs contrast with the preceding episodes of mafic magmatism (from 10,600 to ~3000 14C years B.P.) that was characterized by the eruption of primitive high alumina olivine tholeiite (HAOT) with low H2O (< 0.2 wt%), lower LILE abundance and different isotopic characteristics. Thus, the mantle-derived inputs into the Medicine Lake system have not always been low H2O, primitive HAOT, but have alternated between HAOT and hydrous subduction related, calc-alkaline basalt. This influx of hydrous mafic magma coincides temporally and spatially with rhyolite eruption at Glass Mountain and Little Glass Mountain. The rhyolites contain quenched magmatic inclusions similar in character to the mafic lavas at Callahan and Paint Pot Crater. The influence of H2O on fractional crystallization of hydrous mafic magma and melting of pre-existing granite crust beneath the volcano combined to produce the rhyolite. Fractionation under hydrous conditions at upper crustal pressures leads to the early crystallization of Fe-Mg silicates and the suppression of plagioclase as an early crystallizing phase. In addition, H2O lowers the saturation temperature of Fe and Mg silicates, and brings the temperature of oxide crystallization closer to the liquidus. These combined effects generate SiO2-enrichment that leads to rhyodacitic differentiated lavas. In contrast, low H2O HAOT

  20. Physicochemical characterization of the dimeric lanthanide complexes [en{Ln(DO3A)(H2O)}2] and [pi{Ln(DTTA)(H2O)}2]2-: a variable-temperature 17O NMR study.

    PubMed

    Lee, Tzu-Ming; Cheng, Tsan-Hwang; Ou, Ming-Hung; Chang, C Allen; Liu, Gin-Chung; Wang, Yun-Ming

    2004-03-01

    The Gd(III) complexes of the two dimeric ligands [en(DO3A)2] {N,N'-bis[1,4,7-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecan-10-yl-methylcarbonyl]-N,N'-ethylenediamine} and [pi(DTTA)2]8- [bisdiethylenetriaminepentaacetic acid (trans-1,2-cyclohexanediamine)] were synthesized and characterized. The 17O NMR chemical shift of H2O induced by [en{Dy(DO3A)}2] and [pi{Dy(DTTA)}2]2- at pH 6.80 proved the presence of 2.1 and 2.2 inner-sphere water molecules, respectively. Water proton spin-lattice relaxation rates for [en{Gd(DO3A)(H2O)}2] and [pi{Gd(DTTA)(H2O)}2]2- at 37.0 +/- 0.1 degrees C and 20 MHz are 3.60 +/- 0.05 and 5.25 +/- 0.05 mM(-1) s(-1) per Gd, respectively. The EPR transverse electronic relaxation rate and 17O NMR transverse relaxation time for the exchange lifetime of the coordinated H2O molecule and the 2H NMR longitudinal relaxation rate of the deuterated diamagnetic lanthanum complex for the rotational correlation time were thoroughly investigated, and the results were compared with those reported previously for other lanthanide(III) complexes. The exchange lifetimes for [en{Gd(DO3A)(H2O)}2] (769 +/- 10 ns) and [pi{Gd(DTTA)(H2O)}2]2- (910 +/- 10 ns) are significantly higher than those of [Gd(DOTA)(H2O)]- (243 ns) and [Gd(DTPA)(H2O)]2- (303 ns) complexes. The rotational correlation times for [en{Gd(DO3A)(H2O)}2] (150 +/- 11 ps) and [pi{Gd(DTTA)(H2O)}2]2- (130 +/- 12 ps) are slightly greater than those of [Gd(DOTA)(H2O)]- (77 ps) and [Gd(DTPA)(H2O)]2- (58 ps) complexes. The marked increase in relaxivity (r1) of [en{Gd(DO3A)(H2O)}2] and [pi{Gd(DTTA)(H2O)}2]2- result mainly from their longer rotational correlation time and higher molecular weight. PMID:14971018

  1. Measured Fluid Flow in an Active H2O-CO2 Geothermal Well as an Analog to Fluid Flow in Fractures on Mars: Preliminary Report

    NASA Technical Reports Server (NTRS)

    Kieffer, Susan W.; Brown, K. L.; Simmons, Stuart F.; Watson, Arnold

    2004-01-01

    Water in the Earth's crust generally contains dissolved gases such as CO2. Models for both 'Blue Mars' (H2O-driven processes) and 'White Mars' (CO2-driven processes) predict liquid H2O with dissolved CO2 at depth. The fate of dissolved CO2 as this mixture rises toward the surface has not been quantitatively explored. Our approach is a variation on NASA's 'Follow the Water' as we 'Follow the Fluid' from depth to the surface in hydrothermal areas on Earth and extrapolate our results to Mars. This is a preliminary report on a field study of fluid flow in a producing geothermal well. For proprietary reasons, the name and location of this well cannot be revealed, so we have named it 'Earth1' for this study.

  2. Melting temperatures of H2O up to 72 GPa measured in a diamond anvil cell using CO2 laser heating technique.

    PubMed

    Kimura, T; Kuwayama, Y; Yagi, T

    2014-02-21

    The melting curve of H2O from 49 to 72 GPa was determined by using a laser-heated diamond anvil cell. Double-sided CO2 laser heating technique was employed in order to heat the sample directly. Discontinuous changes of the heating efficiency attributed to the H2O melting were observed between 49 and 72 GPa. The obtained melting temperatures at 49 and 72 GPa are 1200 and 1410 K, respectively. We found that the slope of the melting curve significantly decreases with increasing pressure, only 5 K/GPa at 72 GPa while 44 K/GPa at 49 GPa. Our results suggest that the melting curve does not intersect with the isentropes of Uranus and Neptune, and hence, H2O should remain in the liquid state even at the pressure and temperature conditions found deep within Uranus and Neptune. PMID:24559351

  3. Results from Boiling Temperature Measurements for Saturated Solutions in the Systems NaCl + Ca(NO3)2 + H2O, NaNO3 + KNO3 + H2O, and NaCl + KNO3 + H2O, and Dry Out Temperatures for NaCl + NaNO3 + KNO3 + Ca(NO3)2 + H2O

    SciTech Connect

    Rard, J A

    2005-11-29

    Boiling temperature measurements have been made for saturated ternary solutions of NaCl + KNO{sub 3} + H{sub 2}O and NaNO{sub 3} + KNO{sub 3} + H{sub 2}O at three selected salt ratios and for NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O over the full composition range. The maximum boiling temperature found for the NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O system is 164.7 {+-} 0.6 C, and the composition is estimated to occur at x(Ca(NO{sub 3}){sub 2}) {approx} 0.25. Experiments were also performed for the five component NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O mixtures with the molar ratio of NaCl:NaNO{sub 3}:KNO{sub 3} held essentially constant at 1:0.9780:1.1468 as the solute mole fraction of Ca(NO{sub 3}){sub 2}, x(Ca(NO{sub 3}){sub 2}), was varied between 0 and 0.25. The NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O system forms low melting mixtures and thus boiling temperatures for saturated were not determined. Instead, the temperatures corresponding to the cessation of boiling (i.e., dry out temperatures) of these liquid mixtures were determined. These dry out temperatures range from {approx} 300 C when x(Ca(NO{sub 3}){sub 2}) = 0 to {ge} 400 C when x(Ca(NO{sub 3}){sub 2}) = 0.20 and 0.25. The investigated mixture compositions correspond to some of the major mineral assemblages that are predicted to control the deliquescence relative humidity of salts formed by leaching dust samples from the proposed nuclear repository at Yucca Mountain, Nevada.

  4. Critical exponents for the coexistence curves for NaCl-H 2O near the critical temperature of H 2O. Reply to comment by A.H. Harvey and J.M.H. Levelt Sengers

    NASA Astrophysics Data System (ADS)

    Pitzer, Kenneth S.; Tanger, John C.

    1989-04-01

    On isotherms close to that of Tc for H 2O, the effective exponent for the liquid-vapor difference in mole fraction differs from that for the density difference. This difference in exponents hasbeen invoked qualitatively to explain certain properties for NaCl-H 2O. This Comment presents quantitative values of this difference in exponents, calculated from a very recent equation of state, and shows that these results are consistent with the experimental coexistence surface.

  5. Simultaneous measurement of 2-dimensional H2O concentration and temperature distribution in premixed methane/air flame using TDLAS-based tomography technology

    NASA Astrophysics Data System (ADS)

    Wang, Fei; Wu, Qi; Huang, Qunxing; Zhang, Haidan; Yan, Jianhua; Cen, Kefa

    2015-07-01

    An innovative tomographic method using tunable diode laser absorption spectroscopy (TDLAS) and algebraic reconstruction technique (ART) is presented in this paper for detecting two-dimensional distribution of H2O concentration and temperature in a premixed flame. The collimated laser beam emitted from a low cost diode laser module was delicately split into 24 sub-beams passing through the flame from different angles and the acquired laser absorption signals were used to retrieve flame temperature and H2O concentration simultaneously. The efficiency of the proposed reconstruction system and the effect of measurement noise were numerically evaluated. The temperature and H2O concentration in flat methane/air premixed flames under three different equivalence ratios were experimentally measured and reconstruction results were compared with model calculations. Numerical assessments indicate that the TDLAS tomographic system is capable for temperature and H2O concentration profiles detecting even the noise strength reaches 3% of absorption signal. Experimental results under different combustion conditions are well demonstrated along the vertical direction and the distribution profiles are in good agreement with model calculation. The proposed method exhibits great potential for 2-D or 3-D combustion diagnostics including non-uniform flames.

  6. Quantitative agreement between [(15) O]H2 O PET and model free QUASAR MRI-derived cerebral blood flow and arterial blood volume.

    PubMed

    Heijtel, D F R; Petersen, E T; Mutsaerts, H J M M; Bakker, E; Schober, P; Stevens, M F; van Berckel, B N M; Majoie, C B L M; Booij, J; van Osch, M J P; van Bavel, E T; Boellaard, R; Lammertsma, A A; Nederveen, A J

    2016-04-01

    The purpose of this study was to assess whether there was an agreement between quantitative cerebral blood flow (CBF) and arterial cerebral blood volume (CBVA) measurements by [(15) O]H2 O positron emission tomography (PET) and model-free QUASAR MRI. Twelve healthy subjects were scanned within a week in separate MRI and PET imaging sessions, after which quantitative and qualitative agreement between both modalities was assessed for gray matter, white matter and whole brain region of interests (ROI). The correlation between CBF measurements obtained with both modalities was moderate to high (r(2) : 0.28-0.60, P < 0.05), although QUASAR significantly underestimated CBF by 30% (P < 0.001). CBVA was moderately correlated (r(2) : 0.28-0.43, P < 0.05), with QUASAR yielding values that were only 27% of the [(15) O]H2 O-derived values (P < 0.001). Group-wise voxel statistics identified minor areas with significant contrast differences between [(15) O]H2 O PET and QUASAR MRI, indicating similar qualitative CBVA and CBF information by both modalities. In conclusion, the results of this study demonstrate that QUASAR MRI and [(15) O]H2 O PET provide similar CBF and CBVA information, but with systematic quantitative discrepancies. Copyright © 2016 John Wiley & Sons, Ltd. PMID:26876426

  7. Role of weakly bound complexes in temperature-dependence and relative rates of MxOy- + H2O (M = Mo, W) reactions

    NASA Astrophysics Data System (ADS)

    Kafader, Jared O.; Ray, Manisha; Raghavachari, Krishnan; Jarrold, Caroline Chick

    2016-02-01

    Results of a systematic comparison of the MoxOy- + H2O and WxOy- + H2O reaction rate coefficients are reported and compared to previous experimental and computational studies on these reactions. WxOy- clusters undergo more direct oxidation by water to yield WxOy+1- + H2, while for MoxOy- clusters, production of MoxOyH2- (trapped intermediates in the oxidation reaction) is comparatively more prevalent. However, MoxOy- clusters generally have higher rate coefficients than analogous WxOy- clusters if MoxOy+1H2- formation is included. Results of calculations on the M2Oy- + H2O (M = Mo, W; y = 4, 5) reaction entrance channel are reported. They include charge-dipole complexes formed from long-range interactions, and the requisite conversion to a Lewis acid-base complex that leads to MxOy+1H2- formation. The results predict that the Lewis acid-base complex is more strongly bound for MoxOy- clusters than for WxOy- clusters. The calculated free energies along this portion of the reaction path are also consistent with the modest anti-Arrhenius temperature dependence measured for most MoxOy- + H2O reactions, and the WxOy- + H2O reaction rate coefficients generally being constant over the temperature range sampled in this study. For clusters that exhibit evidence of both water addition and oxidation reactions, increasing the temperature increases the branching ratio toward oxidation for both species. A more direct reaction path to H2 production may therefore become accessible at modest temperatures for certain cluster stoichiometries and structures.

  8. H2O activity in concentrated NaCl solutions at high pressures and temperatures measured by the brucite-periclase equilibrium

    NASA Astrophysics Data System (ADS)

    Aranovich, L. Y.; Newton, R. C.

    1996-10-01

    H2O activities in concentrated NaCl solutions were measured in the ranges 600° 900° C and 2 15 kbar and at NaCl concentrations up to halite saturation by depression of the brucite (Mg(OH)2) periclase (MgO) dehydration equilibrium. Experiments were made in internally heated Ar pressure apparatus at 2 and 4.2 kbar and in 1.91-cm-diameter piston-cylinder apparatus with NaCl pressure medium at 4.2, 7, 10 and 15 kbar. Fluid compositions in equilibrium with brucite and periclase were reversed to closures of less than 2 mol% by measuring weight changes after drying of punctured Pt capsules. Brucite-periclase equilibrium in the binary system was redetermined using coarsely crystalline synthetic brucite and periclase to inhibit back-reaction in quenching. These data lead to a linear expression for the standard Gibbs free energy of the brucite dehydration reaction in the experimental temperature range: ΔG° (±120J)=73418 134.95 T(K). Using this function as a baseline, the experimental dehydration points in the system MgO-H2O-NaCl lead to a simple systematic relationship of high-temperature H2O activity in NaCl solution. At low pressure and low fluid densities near 2 kbar the H2O activity is closely approximated by its mole fraction. At pressures of 10 kbar and greater, with fluid densities approaching those of condensed H2O, the H2O activity becomes nearly equal to the square of its mole fraction. Isobaric halite saturation points terminating the univariant brucite-periclase curves were determined at each experimental pressure. The five temperature-composition points in the system NaCl-H2O are in close agreement with the halite saturation curves (liquidus curves) given by existing data from differential thermal analysis to 6 kbar. Solubility of MgO in the vapor phase near halite saturation is much less than one mole percent and could not have influenced our determinations. Activity concentration relations in the experimental P-T range may be retrieved for the binary

  9. Electron-temperature dependence of the recombination of H3O+(H2O)n ions with electrons

    NASA Technical Reports Server (NTRS)

    Johnsen, R.

    1993-01-01

    The T(e) dependence of the recombination of H3O+(H2O)n cluster-ions with electrons has been measured in an afterglow experiment in which the electrons were heated by a radio-frequency electric field. The recombination coefficients were found to vary with T(e) as about T(e) exp -1/2 in better agreement with theoretical expectations than earlier results of microwave-afterglow measurements.

  10. Photolysis of H2O-H2O2 Mixtures: The Destruction of H2O2

    NASA Technical Reports Server (NTRS)

    Loeffler, M. J.; Fama, M.; Baragiola, R. A.; Carlson, R. W.

    2013-01-01

    We present laboratory results on the loss of H2O2 in solid H2O + H2O2 mixtures at temperatures between 21 and 145 K initiated by UV photolysis (193 nm). Using infrared spectroscopy and microbalance gravimetry, we measured the decrease of the 3.5 micrometer infrared absorption band during UV irradiation and obtained a photodestruction cross section that varies with temperature, being lowest at 70 K. We use our results, along with our previously measured H2O2 production rates via ionizing radiation and ion energy fluxes from the spacecraft to compare H2O2 creation and destruction at icy satellites by ions from their planetary magnetosphere and from solar UV photons. We conclude that, in many cases, H2O2 is not observed on icy satellite surfaces because the H2O2 photodestruction rate is much higher than the production rate via energetic particles, effectively keeping the H2O2 infrared signature at or below the noise level.

  11. Tunable diode laser absorption spectroscopy-based tomography system for on-line monitoring of two-dimensional distributions of temperature and H2O mole fraction

    NASA Astrophysics Data System (ADS)

    Xu, Lijun; Liu, Chang; Jing, Wenyang; Cao, Zhang; Xue, Xin; Lin, Yuzhen

    2016-01-01

    To monitor two-dimensional (2D) distributions of temperature and H2O mole fraction, an on-line tomography system based on tunable diode laser absorption spectroscopy (TDLAS) was developed. To the best of the authors' knowledge, this is the first report on a multi-view TDLAS-based system for simultaneous tomographic visualization of temperature and H2O mole fraction in real time. The system consists of two distributed feedback (DFB) laser diodes, a tomographic sensor, electronic circuits, and a computer. The central frequencies of the two DFB laser diodes are at 7444.36 cm-1 (1343.3 nm) and 7185.6 cm-1 (1391.67 nm), respectively. The tomographic sensor is used to generate fan-beam illumination from five views and to produce 60 ray measurements. The electronic circuits not only provide stable temperature and precise current controlling signals for the laser diodes but also can accurately sample the transmitted laser intensities and extract integrated absorbances in real time. Finally, the integrated absorbances are transferred to the computer, in which the 2D distributions of temperature and H2O mole fraction are reconstructed by using a modified Landweber algorithm. In the experiments, the TDLAS-based tomography system was validated by using asymmetric premixed flames with fixed and time-varying equivalent ratios, respectively. The results demonstrate that the system is able to reconstruct the profiles of the 2D distributions of temperature and H2O mole fraction of the flame and effectively capture the dynamics of the combustion process, which exhibits good potential for flame monitoring and on-line combustion diagnosis.

  12. Investigation of Methanol Formation Mechanisms in H2O+CH4 Ices Subjected to 5 keV Electrons at a 10-100 K Temperature Range

    NASA Astrophysics Data System (ADS)

    Stelmach, K. B.; Cooper, P. D.

    2014-12-01

    Methane (CH4) and water are one of the most common molecules in both planetary bodies and interstellar dust grains. Another common molecule, methanol (CH3OH), is thought to form in CH4+H2O ices. However, the exact formation mechanisms of methanol from cosmic rays are not well known, especially in the temperatures of interest. Experiments were performed using high energy electrons (5 keV) to irradiate mixtures of 1:10, 1:5, and 1:3 CH4+H2O ices under a temperature range of 10-100 Kelvin with Fourier Transform Infrared (FTIR) spectroscopy being used to identify the products. Isotopologues of the two molecules (D2O and CD4) were used to probe for the mechanisms. Other products were formed as well and their potential mechanisms are identified. The implications of the mechanisms for planetary and interstellar chemistry are discussed.

  13. An assessment of the accuracy of isochore location techniques for H 2O-CO 2-NaCl fluids at granulite facies pressure-temperature conditions

    NASA Astrophysics Data System (ADS)

    Johnson, Eric Lee

    1992-01-01

    Synthetic H 2O-CO 2-NaCl fluid inclusions with XCO2 compositions ranging from 0.10-0.51 and relative salinities ( r-s = wtNaCl/( wt NaCl + wt H 2O )) of 6 to 23.9 wt% have been produced in spontaneously nucleated forsterite, diopside, and orthopyroxene hosts. Molar volumes of the fluids at the pressure and temperature of formation have been calculated using microthermometric data from the fluid inclusions. These P- V- T data are used to compare the accuracy of published methods of isochore location for H 2O-CO 2-NaCl fluids at elevated pressures and temperatures. The results of these analyses show that isochores calculated with the MRK equation of BOWERS and HELGESON ( Geochim. Cosmochim. Acta, vol. 47, 1247-1275, 1983) reproduce the trapping pressures and temperatures well for fluids with XCO2 ≤ 0.3 and up to 23.9 wt% NaCl. For a fluid with XCO2 = 0.49 and relative salinity of 15%, however, the agreement is poor. For these fluid compositions, the observed molar volume is larger than that predicted from the MRK equation of Bowers and Helgeson and, if not corrected, will give isochores that are too low in pressure for a given temperature. The ideal geometric mixing model of BROWN and LAMB ( Geochim. Cosmochim. Acta, vol. 53, 1209-1221, 1989) provides less satisfactory results for the fluid compositions studied.

  14. In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite, FeOH(SO4)·5H2O

    NASA Astrophysics Data System (ADS)

    Ventruti, Gennaro; Ventura, Giancarlo Della; Corriero, Nicola; Malferrari, Daniele; Gualtieri, Alessandro F.; Susta, Umberto; Lacalamita, Maria; Schingaro, Emanuela

    2016-05-01

    The thermal dehydration process of fibroferrite, FeOH(SO4)·5H2O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO4)·4H2O, appearing at about 80 °C due to release of one interstitial H2O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.

  15. A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Semmes, D. H.; Ravishankara, A. R.

    1981-01-01

    Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.

  16. Observation of a remarkable temperature effect in the hydrogen bonding structure and dynamics of the CN-(H2O) cluster

    SciTech Connect

    Wang, Xue B.; Werhahn, Jasper C.; Wang, Lai S.; Kowalski, Karol; Laubereau, Alfred; Xantheas, Sotiris S.

    2009-09-03

    The CN-(H2O) cluster represents a model diatomic monohydrate with multiple solvation sites. We report joint experimental and theoretical studies of its structure and dynamics using temperature-controlled photoelectron spectroscopy (PES) and ab-initio electronic structure calculations. The observed PES spectra of CN-(H2O) display a remarkable temperature effect, namely that the T=12 K spectrum shows an unexpectedly large blue shift of 0.25 eV in the electron binding energy relative to the Room Temperature (RT) spectrum. Extensive theoretical analysis of the potential energy function (PEF) of the cluster at the CCSD(T) level of theory reveal the existence of two nearly isoenergetic isomers corresponding to H2O forming a H-bond with either the C or the N atom, respectively. This results in four topologically distinct minima, i.e., CN-(HaOHb), CN-(HbOHa), NC-(HaOHb) and NC-(HbOHa). There are two main pathways connecting these minima: (i) CN- tumbling relative to water and (ii) water rocking relative to CN-. The relative magnitude of the barriers associated with these two motions reverses between low [pathway (i) is preferred] and high [pathway (ii) is preferred] temperatures. As a result, at T=12 K the cluster adopts a structure that is close to the minimum energy CN-(H2O) configuration, while at RT it can effectively access regions of the PEF close to the transition state for pathway (ii), explaining the surprisingly large spectral shift between the 12 K and RT PES spectra. This work was supported by the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences, US Department of Energy. Battelle operates Pacific Northwest National Laboratory for the US Department of Energy.

  17. Isotope analysis of diamond-surface passivation effect of high-temperature H2O-grown atomic layer deposition-Al2O3 films

    NASA Astrophysics Data System (ADS)

    Hiraiwa, Atsushi; Saito, Tatsuya; Matsumura, Daisuke; Kawarada, Hiroshi

    2015-06-01

    The Al2O3 film formed using an atomic layer deposition (ALD) method with trimethylaluminum as Al precursor and H2O as oxidant at a high temperature (450 °C) effectively passivates the p-type surface conduction (SC) layer specific to a hydrogen-terminated diamond surface, leading to a successful operation of diamond SC field-effect transistors at 400 °C. In order to investigate this excellent passivation effect, we carried out an isotope analysis using D2O instead of H2O in the ALD and found that the Al2O3 film formed at a conventional temperature (100 °C) incorporates 50 times more CH3 groups than the high-temperature film. This CH3 is supposed to dissociate from the film when heated afterwards at a higher temperature (550 °C) and causes peeling patterns on the H-terminated surface. The high-temperature film is free from this problem and has the largest mass density and dielectric constant among those investigated in this study. The isotope analysis also unveiled a relatively active H-exchange reaction between the diamond H-termination and H2O oxidant during the high-temperature ALD, the SC still being kept intact. This dynamic and yet steady H termination is realized by the suppressed oxidation due to the endothermic reaction with H2O. Additionally, we not only observed the kinetic isotope effect in the form of reduced growth rate of D2O-oxidant ALD but found that the mass density and dielectric constant of D2O-grown Al2O3 films are smaller than those of H2O-grown films. This is a new type of isotope effect, which is not caused by the presence of isotopes in the films unlike the traditional isotope effects that originate from the presence of isotopes itself. Hence, the high-temperature ALD is very effective in forming Al2O3 films as a passivation and/or gate-insulation layer of high-temperature-operation diamond SC devices, and the knowledge of the aforementioned new isotope effect will be a basis for further enhancing ALD technologies in general.

  18. Accelerated formation of strontium silicate by solid-state reaction in NaCl-H2O(v) system at lower temperature

    NASA Astrophysics Data System (ADS)

    Zhang, Junhao; Qiu, Yushi; Huang, Man; Zheng, Hongjuan; Yanagisawa, Kazumichi

    2015-08-01

    An environmentally friendly NaCl-H2O system was developed to prepare SrSiO3 nanostructures from commercially available raw materials, SrCO3 and amorphous SiO2 (α-SiO2), by a one-step solid state reaction at 600 °C for 2 h. The formation of SrSiO3 was accelerated by NaCl-H2O(v) system. The results demonstrate that both NaCl and H2O played vital roles to accelerate the formation of SrSiO3 nanostructures at lower temperature. NaCl was considered to enhance the diffusivity of starting materials and the rate of solid state reactions, and promote the crystallization of products at lower temperature. Additionally, two different phases of SrSiO3 (JPDS 00-032-1257) and SrSiO3 (JPDS 00-006-0415) were abtained without or with the addition of NaCl. Water vapor accelerated the decomposition of SrCO3, and absorbed water on the surface of solid materials dissolved NaCl to form an aqueous ionic liquid composed of Na and Cl ions, which was similar to a hydrothermal process, and further increased the diffusivity of components and reduced the reaction temperature.

  19. Natural convection flow of Cu-H2O nanofluid along a vertical wavy surface with uniform heat flux

    NASA Astrophysics Data System (ADS)

    Habiba, Farjana; Molla, Md. Mamun; Khan, M. A. Hakim

    2016-07-01

    A numerical study on natural convection flow of Cu-Water nanofluid along a vertical wavy surface with uniform heat flux has been carried out. The governing boundary layer equations are transformed into parabolic partial differential equations by applying a suitable set of variables. The resulting nonlinear system of equations are then mapped into a regular rectangular computational domain and solved numerically by using an implicit finite difference method. Numerical results are thoroughly discussed in terms of velocity and temperature distributions, surface temperature distribution, skin friction coefficient and Nusselt number coefficient for selected key parameters such as solid volume fraction of nanofluid (ϕ) and amplitude (α) of surface waviness. In addition, velocity vectors, streamlines and isotherms are plotted to visualize momentum and thermal flow pattern within the boundary layer region.

  20. Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature

    PubMed Central

    Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

    2016-01-01

    Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C–O–H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred. PMID:26813580

  1. Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature.

    PubMed

    Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

    2016-01-01

    Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred. PMID:26813580

  2. Stable solid and aqueous H2CO3 from CO2 and H2O at high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Wang, Hongbo; Zeuschner, Janek; Eremets, Mikhail; Troyan, Ivan; Willams, Jonathan

    2016-01-01

    Carbonic acid (H2CO3) forms in small amounts when CO2 dissolves in H2O, yet decomposes rapidly under ambient conditions of temperature and pressure. Despite its fleeting existence, H2CO3 plays an important role in the global carbon cycle and in biological carbonate-containing systems. The short lifetime in water and presumed low concentration under all terrestrial conditions has stifled study of this fundamental species. Here, we have examined CO2/H2O mixtures under conditions of high pressure and high temperature to explore the potential for reaction to H2CO3 inside celestial bodies. We present a novel method to prepare solid H2CO3 by heating CO2/H2O mixtures at high pressure with a CO2 laser. Furthermore, we found that, contrary to present understanding, neutral H2CO3 is a significant component in aqueous CO2 solutions above 2.4 GPa and 110 °C as identified by IR-absorption and Raman spectroscopy. This is highly significant for speciation of deep C-O-H fluids with potential consequences for fluid-carbonate-bearing rock interactions. As conditions inside subduction zones on Earth appear to be most favorable for production of aqueous H2CO3, a role in subduction related phenomena is inferred.

  3. Exit plane H2O concentration measurements correlated with OH PLIF near-injector mixing measurements for scramjet flows

    NASA Technical Reports Server (NTRS)

    Parker, T. E.; Allen, Mark G.; Foutter, R. R.; Sonnenfroh, D. M.; Rawlins, W. T.

    1992-01-01

    Mixing and combusting high enthalpy flows, similar to those encountered in scramjet engines, were investigated using a shock tunnel to produce the flow in conjunction with non-intrusive optical diagnostics which monitored the performance of two injector configurations. The shock tunnel is configured to produce Mach 3 flow and stagnation enthalpies corresponding to flight equivalent Mach numbers between 7 and 11. A pulsed hydrogen injection capability and interchangeable injector blocks provide a means of examining high speed, high enthalpy reacting flows. Planar laser induced fluorescence (PLIF) of OH molecules in the near injector region produced images which show the combusting and mixing zones for the reacting flow. Line-of-sight exit plane measurement of water concentration and temperature were used to provide a unique method of monitoring exit plane products. These results demonstrated that a velocity matched axial injection system produced a fuel jet that lifted off the floor of the duct. Mixing was observed to increase for this system as a velocity mismatch was introduced. Comparison of exit plane water concentrations for a wall jet injection system and a velocity matched injection system indicated similar mixing performance but an accurate pressure measurement is necessary to further validate the result. In addition, exit plane measurements indicated an approximate steady-state condition was achieved during the 1 to 2 ms test times.

  4. CFD convective flow simulation of the varying properties of CO2-H2O mixtures in geothermal systems.

    PubMed

    Yousefi, S; Atrens, A D; Sauret, E; Dahari, M; Hooman, K

    2015-01-01

    Numerical simulation of a geothermal reservoir, modelled as a bottom-heated square box, filled with water-CO2 mixture is presented in this work. Furthermore, results for two limiting cases of a reservoir filled with either pure water or CO2 are presented. Effects of different parameters including CO2 concentration as well as reservoir pressure and temperature on the overall performance of the system are investigated. It has been noted that, with a fixed reservoir pressure and temperature, any increase in CO2 concentration leads to better performance, that is, stronger convection and higher heat transfer rates. With a fixed CO2 concentration, however, the reservoir pressure and temperature can significantly affect the overall heat transfer and flow rate from the reservoir. Details of such variations are documented and discussed in the present paper. PMID:25879074

  5. CFD Convective Flow Simulation of the Varying Properties of CO2-H2O Mixtures in Geothermal Systems

    PubMed Central

    Yousefi, S.; Atrens, A. D.; Sauret, E.; Dahari, M.; Hooman, K.

    2015-01-01

    Numerical simulation of a geothermal reservoir, modelled as a bottom-heated square box, filled with water-CO2 mixture is presented in this work. Furthermore, results for two limiting cases of a reservoir filled with either pure water or CO2 are presented. Effects of different parameters including CO2 concentration as well as reservoir pressure and temperature on the overall performance of the system are investigated. It has been noted that, with a fixed reservoir pressure and temperature, any increase in CO2 concentration leads to better performance, that is, stronger convection and higher heat transfer rates. With a fixed CO2 concentration, however, the reservoir pressure and temperature can significantly affect the overall heat transfer and flow rate from the reservoir. Details of such variations are documented and discussed in the present paper. PMID:25879074

  6. The influence of temperature (20-1000 °C) on binary mixtures of solid solutions of CH 3COOLi·2H 2O-MgHPO 4·3H 2O

    NASA Astrophysics Data System (ADS)

    Umbreit, Michał H.; Paukszta, Dominik

    2009-11-01

    Thermally induced phase transitions (20-1000 °C) in the substrates and binary mixtures of CH 3COOLi·2H 2O(1)-MgHPO 4·3H 2O(11) have been analysed. Changes taking place on dehydration and thermal dissociation of binary mixtures prepared with percent molar ratios of 90-10% were studied by differential thermal analysis (TG, DTG, DTA), IR-spectroscopy and WAXS. The above-mentioned substrates changed their structure when heated for 1 h at 500 or 1000 °C. CH 3COOLi·2H 2O(1) (ID: 23-1171) changed the structure at 500 °C to that of Li 2CO 3 (ID: 22-1141), while at 1000 °C the structure was impossible to analyse as the compound reacted both with porcelain and with platinum (crucible materials). MgHPO 4·3H 2O(11) (Newberyite, ID: 35-780, 19-762) changed its structure at 500 °C to amorphous phase and at 1000 °C to Mg 2P 2O 7 (ID: 32-626). The following compounds were assayed in the respective binary mixtures heated at 500 °C for 1 h: 70% (1)-30%(11): LiMgPO 4 (ID: 18-735), MgO (ID: 4-829); 50%(1)-50%(11): LiMgPO 4 (ID: 18-735), Li 3PO 4 (ID: 25-1030); 30%(1)-70%(11): LiMgPO 4 (ID: 32-574); binary mixtures heated at 1000 °C contained the following compounds: 70%(1)-30%(11): LiMgPO 4 (ID: 32-574,18-735), Li 3PO 4 (ID: 15-760,25-1030), MgO (ID: 4-829); 50%(1)-50%(11): LiMgPO 4 (ID: 32-574, 18-735), MgO (ID: 4-829); 30%(1)-70%(11): LiMgPO 4 (ID: 18-735, 32-574), Mg 2P 2O 7 (ID: 22-1152, 8-38), Li 4SiO 4 (37-1472).

  7. Numerical modeling of two-phase flow in the NaCl-H2O system: Introduction of a numerical method and benchmarking

    NASA Astrophysics Data System (ADS)

    Lewis, K. C.; Lowell, R. P.

    2009-05-01

    In order to facilitate modeling of fluid flow processes in seafloor hydrothermal systems, we introduce a numerical scheme called FISHES that is capable of simulating two-phase fluid flow in the NaCl-H2O system. We discuss the equations governing fluid flow, the thermodynamic relations between various quantities employed, and the coupling of these elements together in a time marching scheme. The thermodynamic relations are expressed in terms of equations of state compiled from lookup tables. These are based on previously published formulations for the density and enthalpy of NaCl-H2O fluid in regions of phase space that are relevant to the study of seafloor hydrothermal systems. We show that the thermodynamic quantities vary both smoothly and physically in P-T-X space. In particular, vapor salinity values near the vapor-liquid-halite coexistence surface are in agreement with recently measured values. We compare code output from an approximately one-dimensional scenario to the analytic solution of the classical one-dimensional thermal advection-diffusion equation and find that the numerical output and analytic solution are in agreement. The numerical code is also benchmarked against previously published results for the Elder problem and for the problem of fluid extraction from a one-dimensional, two-phase horizontal pipe. We find that the results using FISHES are in agreement with previously published results. Finally, we show that results from a one-dimensional vertical salt pipe simulation agree with an analytic solution.

  8. Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures

    NASA Astrophysics Data System (ADS)

    Videla, Pablo E.; Rossky, Peter J.; Laria, D.

    2013-11-01

    We use ring-polymer-molecular-dynamics (RPMD) techniques and the semi-empirical q-TIP4P/F water model to investigate the relationship between hydrogen bond connectivity and the characteristics of nuclear position fluctuations, including explicit incorporation of quantum effects, for the energetically low lying isomers of the prototype cluster [H2O]8 at T = 50 K and at 150 K. Our results reveal that tunneling and zero-point energy effects lead to sensible increments in the magnitudes of the fluctuations of intra and intermolecular distances. The degree of proton spatial delocalization is found to map logically with the hydrogen-bond connectivity pattern of the cluster. Dangling hydrogen bonds exhibit the largest extent of spatial delocalization and participate in shorter intramolecular O-H bonds. Combined effects from quantum and polarization fluctuations on the resulting individual dipole moments are also examined. From the dynamical side, we analyze the characteristics of the infrared absorption spectrum. The incorporation of nuclear quantum fluctuations promotes red shifts and sensible broadening relative to the classical profile, bringing the simulation results in much more satisfactory agreement with direct experimental information in the mid and high frequency range of the stretching band. While RPMD predictions overestimate the peak position of the low frequency shoulder, the overall agreement with that reported using an accurate, parameterized, many-body potential is reasonable, and far superior to that one obtains by implementing a partially adiabatic centroid molecular dynamics approach. Quantum effects on the collective dynamics, as reported by instantaneous normal modes, are also discussed.

  9. Temperature measurements in a rapid compression machine using mid-infrared H2O absorption spectroscopy near 7.6 μm.

    PubMed

    Uddi, Mruthunjaya; Das, Apurba Kumar; Sung, Chih-Jen

    2012-08-01

    A method for measuring the temporal temperature and number density in a rapid compression machine (RCM) using quantum cascade laser absorption spectroscopy near 7.6 μm is developed and presented in this paper. The ratios of H(2)O absorption peaks at 1316.55 cm(-1) and 1316.97 cm(-1) are used for these measurements. In order to isolate the effects of chemical reactions, an inert mixture of argon with 2.87% water vapor is used for the present investigation. The end of compression pressures and temperatures in the RCM measurements are P(C)=10, 15, and 20 bar in the range of T(C)=1000 to 1200 K. The measured temperature history is compared with that calculated based on the adiabatic core assumption and is found to be within ±5 K. The measured temporal number density of H(2)O to an accuracy of 1%, using the absolute absorption of the two rovibrational lines, show that the mixture is highly uniform in temperature. A six-pass, 5.08 cm Herriott cell is used to calibrate the line strengths in air and broadening in an Ar bath gas. PMID:22859037

  10. Subduction Factory 3: An Excel worksheet and macro for calculating the densities, seismic wave speeds, and H2O contents of minerals and rocks at pressure and temperature

    NASA Astrophysics Data System (ADS)

    Hacker, Bradley R.; Abers, Geoffrey A.

    2004-01-01

    An Excel macro to calculate mineral and rock physical properties at elevated pressure and temperature is presented. The workbook includes an expandable database of physical parameters for 52 rock-forming minerals stable at high pressures and temperatures. For these minerals the elastic moduli, densities, seismic velocities, and H2O contents are calculated at any specified P and T conditions, using basic thermodynamic relationships and third-order finite strain theory. The mineral modes of suites of rocks are also specifiable, so that their predicted aggregate properties can be calculated using standard solid mixing theories. A suite of sample rock modes taken from the literature provides a useful starting point. The results of these calculations can be applied to a wide variety of geophysical questions including estimating the alteration of the oceanic crust and mantle; predicting the seismic velocities of lower-crustal xenoliths; estimating the effects of changes in mineralogy, pressure and temperature on buoyancy; and assessing the H2O content and mineralogy of subducted lithosphere from seismic observations.

  11. Oxidation behaviour of ferritic stainless steel grade Crofer 22 APU at 700 °C in flowing Ar-75%CO2-12%H2O

    NASA Astrophysics Data System (ADS)

    Shariff, Nurul Atikah; Othman, Norinsan Kamil; Jalar, Azman

    2013-11-01

    The oxidation of Ferritic Stainless Steel (FSS) grade Crofer 22 APU has been investigated. FSS alloys were exposed to isothermal conditions in a horizontal tube furnace at a 700 °C in flowing Ar-75%CO2-12%H2O at a pressure of approximately 1 atm. The results showed that the growth of non protective Fe2O3 and spinel was observed after 50 h exposure in the presence of 12% H2O. The weight was increased significantly with time of exposure. The formation of different oxides is presented on the interface of the specimen such as MnCr2O4, Fe3O4 and Fe2O3 were revealed by X-ray diffraction and supported by EDAX analysis. FSS did not form a protective Cr2O3 layer due to water vapour accelerates the kinetics oxidation. Data of microstructure observation is presented and discussed in this paper in term of water vapour effects.

  12. Low energy isomers of (H2O)25 from a hierarchical method based on Monte Carlo temperature basin paving and molecular tailoring approaches benchmarked by MP2 calculations

    NASA Astrophysics Data System (ADS)

    Sahu, Nityananda; Gadre, Shridhar R.; Rakshit, Avijit; Bandyopadhyay, Pradipta; Miliordos, Evangelos; Xantheas, Sotiris S.

    2014-10-01

    We report new global minimum candidate structures for the (H2O)25 cluster that are lower in energy than the ones reported previously and correspond to hydrogen bonded networks with 42 hydrogen bonds and an interior, fully coordinated water molecule. These were obtained as a result of a hierarchical approach based on initial Monte Carlo Temperature Basin Paving sampling of the cluster's Potential Energy Surface with the Effective Fragment Potential, subsequent geometry optimization using the Molecular Tailoring Approach with the fragments treated at the second order Møller-Plesset (MP2) perturbation (MTA-MP2) and final refinement of the entire cluster at the MP2 level of theory. The MTA-MP2 optimized cluster geometries, constructed from the fragments, were found to be within <0.5 kcal/mol from the minimum geometries obtained from the MP2 optimization of the entire (H2O)25 cluster. In addition, the grafting of the MTA-MP2 energies yields electronic energies that are within <0.3 kcal/mol from the MP2 energies of the entire cluster while preserving their energy rank order. Finally, the MTA-MP2 approach was found to reproduce the MP2 harmonic vibrational frequencies, constructed from the fragments, quite accurately when compared to the MP2 ones of the entire cluster in both the HOH bending and the OH stretching regions of the spectra.

  13. Room-temperature synthesis and solar photocatalytic performance of MoO3·0.5H2O nanorods

    NASA Astrophysics Data System (ADS)

    Yuan, Xinsong; Yang, Baojun; Hu, Xingming; Dong, Xiongzi; Wei, Yanxin; Zhu, Jinmiao

    2015-12-01

    MoO3·0.5H2O nanorods were synthesized on a large-scale through a room-temperature aqueous chemical method, simply by using sodium molybdate and nitric acid as the reactants. The as-prepared samples were investigated by a variety of techniques, including X-ray powder diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), and high-resolution transmission electron microscopy (HRTEM). The results indicate that the samples are monoclinic phase, and have diameters of 40-200 nm, and lengths up to several micrometers, respectively. The formation mechanism for MoO3·0.5H2O nanorods was proposed as 1D growth of the intrinsically anisotropic crystallographic structure. The as-prepared nanorod samples exhibited much better solar photocatalytic performance on degradation of simulated dyeing wastewater than that of their bulk counterparts. The possible reason for the improved photocatalytic performance of the nanorods is the size and surface effect of nanomaterials.

  14. Keep the Ideas Flowing at Your Water Table! Ideas to Help Children Get to Know H-2-O

    ERIC Educational Resources Information Center

    Church, Ellen Booth

    2006-01-01

    This article provides teachers with ten tips for introducing young children to activities involving water. The 10 tips include: (1) Prepare Your Water Play Space; (2) Use Containers Within Containers; (3) Keep Things Interesting; (4) Explore Ice; (5) Survey the Effects of Salt; (6) Go With the Flow; (7) Extend Exploration with Spray Bottles; (8)…

  15. Measurement of regional cerebral blood flow in cat brain using intracarotid 2H2O and 2H NMR imaging

    SciTech Connect

    Detre, J.A.; Subramanian, V.H.; Mitchell, M.D.; Smith, D.S.; Kobayashi, A.; Zaman, A.; Leigh, J.S. Jr. )

    1990-05-01

    Cerebral blood flow (CBF) was measured in cat brain in vivo at 2.7 T using 2H NMR to monitor the washout of deuterated saline injected into both carotid arteries via the lingual arteries. In anesthetized cats, global CBF varied directly with PaCO{sub 2} over a range of 20-50 mm Hg, and the corresponding global CBF values ranged from 25 to 125 ml.100 g-1.min-1. Regional CBF was measured in a 1-cm axial section of cat brain using intracarotid deuterated saline and gradient-echo 2H NMR imaging. Blood flow images with a maximum pixel resolution of 0.3 x 0.3 x 1.0 cm were generated from the deuterium signal washout at each pixel. Image derived values for CBF agreed well with other determinations, and decreased significantly with hypocapnia.

  16. The RealGas and RealGasH2O options of the TOUGH+ code for the simulation of coupled fluid and heat flow in tight/shale gas systems

    EPA Science Inventory

    We developed two new EOS additions to the TOUGH+ family of codes, the RealGasH2O and RealGas. The RealGasH2O EOS option describes the non-isothermal two-phase flow of water and a real gas mixture in gas reservoirs, with a particular focus in ultra-tight (such as tight-sand and sh...

  17. Temperature dependence of the momentum distribution of positronium in MgF2, SiO2, and H2O

    NASA Astrophysics Data System (ADS)

    Nagai, Y.; Kakimoto, M.; Hyodo, T.; Fujiwara, K.; Ikari, H.; Eldrup, M.; Stewart, A. T.

    2000-09-01

    Temperature dependence of the momentum distribution of delocalized Bloch-positronium in solids is studied. The momentum distribution of the positronium, which is proportional to the energy integration of the spectral function weighted with the Bose distribution, is expressed in terms of the effective mass and the deformation potential of the crystal for positronium. A simple formula for the shape of the positronium peak in the 1D-ACAR spectrum is derived and applied to the analysis of the experimental data for MgF2, SiO2, and H2O in wide temperature ranges. An extraordinary broadening of the peak shape is observed for MgF2. It is interpreted as an effect of the umklapp phonon scattering. The diffusion constants of Ps in these materials are also estimated.

  18. Gibbs free energy of reactions involving SiC, Si3N4, H2, and H2O as a function of temperature and pressure

    NASA Technical Reports Server (NTRS)

    Isham, M. A.

    1992-01-01

    Silicon carbide and silicon nitride are considered for application as structural materials and coating in advanced propulsion systems including nuclear thermal. Three-dimensional Gibbs free energy were constructed for reactions involving these materials in H2 and H2/H2O. Free energy plots are functions of temperature and pressure. Calculations used the definition of Gibbs free energy where the spontaneity of reactions is calculated as a function of temperature and pressure. Silicon carbide decomposes to Si and CH4 in pure H2 and forms a SiO2 scale in a wet atmosphere. Silicon nitride remains stable under all conditions. There was no apparent difference in reaction thermodynamics between ideal and Van der Waals treatment of gaseous species.

  19. Low-Temperature Thermal Reactions Between SO2 and H2O2 and Their Relevance to the Jovian Icy Satellites

    NASA Technical Reports Server (NTRS)

    Loeffler, Mark J.; Hudson, Reggie L.

    2013-01-01

    Here we present first results on a non-radiolytic, thermally-driven reaction sequence in solid H2O +SO2 + H2O2 mixtures at 50-130 K, which produces sulfate (SO(-2)/(4)), and has an activation energy of 53 kJ/mole. We suspect that these results may explain some of the observations related to the presence and distribution of H2O2 across Europa's surface as well as the lack of H2O2 on Ganymede and Callisto.

  20. Probing the formation and evolution of comets via nuclear spin temperatures of C_2H_6, CH_3OH, CH_4, NH_3, and H_2O

    NASA Astrophysics Data System (ADS)

    Villanueva, G.; Mumma, M.; Bonev, B.; DiSanti, M.; Paganini, L.; Magee-Sauer, K.; Gibb, E.

    2014-07-01

    Comets are true remnants of our primordial Solar System, and provide unique clues to its formation and evolution, including the delivery of organics and water to our planet. A key indicator stored in the molecular structure of the nuclear ices is the spin temperature (T_{spin}), derived from spin-isomeric ratios (R_{spin}, e.g., ortho/para). At the time when cometary ices formed, the prevailing temperature defined the relative abundance of the different spin-isomeric species, and herewith R_{spin} and T_{spin} are normally treated as ''remnant thermometers'' probing the formation environments of cometary molecules. Radiative and collisional transitions between the ortho and para states are strongly forbidden and herewith this indicator is preserved over time. Most of our knowledge of this indicator comes from the measurements of the ortho-para ratios in water and NH_2 (a proxy for ammonia), suggesting a common T_{spin} near 30 K. This information is based on a restricted sample of comets, and the measurements are particularly sensitive to the molecular modeling technique and adopted spectral database. Here, we present new methodologies for extracting spin temperatures from ethane (C_2H_6), methane (CH_4), and methanol (CH_3OH), and advanced new models for ortho/para water (H_2O) and ammonia (NH_3). Our H_2O analysis is based on the most complete fluorescence radiative-transfer model to date, which incorporates 1,200 million transitions including those originating from high-energy levels that are activated in comets via a non-resonant cascade. In a similar fashion, we developed non-resonant fluorescence models for NH_3 and HCN, and quantum-band models for the ν_7 band of C_2H_6 and ν_3 band of CH_3OH. All models respect spin-symmetry non-conversion radiative rules, and make use of a realistic solar spectrum for the computation of fluorescence pumps. We applied these new methods to derive spin-isomeric ratios for H_2O, CH_4, C_2H_6, CH_3OH, and NH_3 from three high

  1. Experimental deformation of polycrystalline H2O ice at high pressure and low temperature - Preliminary results. [implications for Ganymede and Callisto

    NASA Technical Reports Server (NTRS)

    Durham, W. B.; Heard, H. C.; Kirby, S. H.

    1983-01-01

    A preliminary study is carried out of involving 70 constant strain deformation tests on pure polycrystalline H2O ice under conditions covering most of the stability field of ice I sub h. Brittle failure of I sub h is found to be promoted by lower P, lower T, and higher strain rates. Ductile flow is found to be promoted by higher P, higher T, and lower strain rates. The brittle failure of ice I sub h is found to be most unusual. The fracture strength is a positive function of P only below 50 MPa. At pressures greater than this, the fracture strength is independent of P, and the fracture plane lies approximately 45 deg from the load axis. It is believed that existing extrapolation based on existing experimental data to Ganymede and Callisto may be badly in error.

  2. Air-Broadening of H2O as a Function of Temperature: 696 - 2163 cm(exp -1)

    NASA Technical Reports Server (NTRS)

    Toth, R. A.; Brown, L. R.; Smith, M. A. H.; Devi, V. Malathy; Benner, D. Chris; Dulick, M.

    2006-01-01

    The temperature dependence of air-broadened halfwidths are reported for some 500 transitions in the (000)-(000) and (010)-(000) bands of H2(16)O using gas sample temperatures ranging from 241 to 388 K. These observations were obtained from infrared laboratory spectra recorded at 0.006 to 0.011 cm(exp-1) resolution with the McMath-Pierce Fourier transform spectrometer located at Kitt Peak. The experimental values of the temperature dependence exponents, eta, were grouped into eight subsets and fitted to empirical functions in a semi-global procedure. Overall, the values of eta were found to decrease with increasing rotational quantum number J. The number of measurements (over 2200) and transitions (586) involved exceeds by a large margin that of any other comparable reported study.

  3. Effects of pH, temperature, and aqueous organic material on the dissolution kinetics of meta-autunite minerals, (Na, Ca)2-1[(UO2)(PO4)]2 • 3H2O

    SciTech Connect

    Wellman, Dawn M; Icenhower, Jonathan P; Gamerdinger, Amy P; Forrester, Steven W

    2006-01-01

    Autunite minerals have been frequently identified in contaminated sediments as the long-term controlling phase of uranium. Under these conditions the mobility of uranium in subsurface pore waters is limited by the rate of dissolution of autunite and meta-autunite group minerals, [(UO2)(PO4)]2 ? xH2O. Single-pass flow-through (SPFT) tests were conducted to quantify the dissolution kinetics of natural calcium meta-autunite, Ca[(UO2)2(PO4)2]2 ? 3H2O, and synthetic sodium meta-autunite, Na2[(UO2)(PO4)]2 ? 3H2O, as a function of pH (7 -10) and temperature (5 ? 70 C) in the presence and absence of aqueous organic material. The data indicate that release of uranium and phosphorus are non-stoichiometric over the range of experimental conditions investigated. In a 0.1 M NH4OH buffer solution, acquisition of valid dissolution rate data was limited by uramphite solubility, NH4[(UO2)(PO4)]2 ? xH2O. Dissolution rates obtained in a 0.01 M TRIS [tris (hydroxymethyl) aminomethane] buffered solution increased by a factor of {approx}100X over the pH interval of 7 to 10 (? = 0.90?0.08), irrespective of temperature. At constant pH the rate data showed a minor increase with temperature. Data from experiments using a more concentrated 0.05 M TRIS buffer exhibited a {approx}35-fold increase in rates compared to those in a 0.01 M TRIS buffer at constant temperature and pH. The difference in rate between interlayer cation (Na+ or Ca2+) and uranium release is {approx}10,000 in neutral solutions; however, the difference diminishes to {approx}10 at higher pH values. The combination of structural dissolution and ion exchange explain these trends in interlayer cation behavior. Data presented here illustrate the significance of pH and dissolved organic material on the dissolution of autunite minerals.

  4. A temperature dependence kinetics study of the reactions of Cl/2-P-3/2/ with O3, CH4, and H2O2

    NASA Technical Reports Server (NTRS)

    Watson, R.; Machado, G.; Fischer, S.; Davis, D. D.

    1976-01-01

    The temperature dependence of two chlorine atom reactions of considerable fundamental importance to stratospheric chemistry was studied using the technique of flash photolysis-resonance fluorescence. The reactions of interest were: (1) Cl + O3 yields ClO + O2 studied at 220-350 K, and (2) Cl + CH4 yields CH3 + HCl studied at 218-401 K. In addition, the reaction Cl + H2O2 yields HCl + HO2 was studied at 300 K. The corresponding rate constants are provided for the three reactions. The new rate data implies the need to revise downward by a factor of 2.4-3 the magnitude of the ozone perturbation due to the presence of ClO/x/ species in the stratosphere, predicted by earlier model calculations.

  5. Interaction of D2 with H2O amorphous ice studied by temperature-programmed desorption experiments.

    PubMed

    Amiaud, L; Fillion, J H; Baouche, S; Dulieu, F; Momeni, A; Lemaire, J L

    2006-03-01

    The gas-surface interaction of molecular hydrogen D2 with a thin film of porous amorphous solid water (ASW) grown at 10 K by slow vapor deposition has been studied by temperature-programmed-desorption (TPD) experiments. Molecular hydrogen diffuses rapidly into the porous network of the ice. The D2 desorption occurring between 10 and 30 K is considered here as a good probe of the effective surface of ASW interacting with the gas. The desorption kinetics have been systematically measured at various coverages. A careful analysis based on the Arrhenius plot method has provided the D2 binding energies as a function of the coverage. Asymmetric and broad distributions of binding energies were found, with a maximum population peaking at low energy. We propose a model for the desorption kinetics that assumes a complete thermal equilibrium of the molecules with the ice film. The sample is characterized by a distribution of adsorption sites that are filled according to a Fermi-Dirac statistic law. The TPD curves can be simulated and fitted to provide the parameters describing the distribution of the molecules as a function of their binding energy. This approach contributes to a correct description of the interaction of molecular hydrogen with the surface of possibly porous grain mantles in the interstellar medium. PMID:16526867

  6. A first principles molecular dynamics study of excess electron and lithium atom solvation in water-ammonia mixed clusters: Structural, spectral, and dynamical behaviors of [(H2O)5NH3]- and Li(H2O)5NH3 at finite temperature

    NASA Astrophysics Data System (ADS)

    Pratihar, Subha; Chandra, Amalendu

    2011-01-01

    First principles molecular dynamics simulations are carried out to investigate the solvation of an excess electron and a lithium atom in mixed water-ammonia cluster (H _2O) _5NH _3 at a finite temperature of 150 K. Both [(H _2O) _5NH _3] ^- and Li(H _2O) _5NH _3 clusters are seen to display substantial hydrogen bond dynamics due to thermal motion leading to many different isomeric structures. Also, the structures of these two clusters are found to be very different from each other and also very different from the corresponding neutral cluster without any excess electron or the metal atom. Spontaneous ionization of Li atom occurs in the case of Li(H _2O) _5NH _3. The spatial distribution of the singly occupied molecular orbital shows where and how the excess (or free) electron is primarily localized in these clusters. The populations of single acceptor (A), double acceptor (AA), and free (NIL) type water and ammonia molecules are found to be significantly high. The dangling hydrogens of these type of water or ammonia molecules are found to primarily capture the free electron. It is also found that the free electron binding motifs evolve with time due to thermal fluctuations and the vertical detachment energy of [(H _2O) _5NH _3] ^- and vertical ionization energy of Li(H _2O) _5NH _3 also change with time along the simulation trajectories. Assignments of the observed peaks in the vibrational power spectra are done and we found a one to one correlation between the time-averaged populations of water and ammonia molecules at different H-bonding sites with the various peaks of power spectra. The frequency-time correlation functions of OH stretch vibrational frequencies of these clusters are also calculated and their decay profiles are analyzed in terms of the dynamics of hydrogen bonded and dangling OH modes. It is found that the hydrogen bond lifetimes in these clusters are almost five to six times longer than that of pure liquid water at room temperature.

  7. Temperature dependent structural variations of OH(-)(H2O)n, n = 4-7: effects on vibrational and photoelectron spectra.

    PubMed

    Lin, Ren-Jie; Nguyen, Quoc Chinh; Ong, Yew-Soon; Takahashi, Kaito; Kuo, Jer-Lai

    2015-07-15

    In this work, we identified a large number of structurally distinct isomers of midsized deprotonated water clusters, OH(-)(H2O)n=4-7, using first-principles methods. The temperature dependence of the structural variation in the solvation shell of OH(-) for these clusters was examined under the harmonic superposition approximation. We simulated the vibrational and photoelectron spectra based on these thermodynamic calculations. We found that the isomers with 3-coordinated hydroxide dominate the population in these midsized clusters. Furthermore, an increase in temperature causes a topological change from compact isomers with many intermolecular hydrogen bonds to open isomers with fewer but more directional intermolecular hydrogen bonds. We showed that this evolution in structure can be observed through the change in the vibrational spectra at 3200-3400 cm(-1). In addition, the increase in directional hydrogen bonded isomers, which have outer hydration shell with OH bonds pointing to the hydroxide, causes the vertical detachment energy to increase at higher temperatures. Lastly, we also performed studies to understand the variation in the aforementioned spectral quantities with the variation in the coordination number of the hydroxide. PMID:26134890

  8. Ionic conductivity measurements of H2O ice at high pressure and temperature and superionic ice in the mantle of ice giants

    NASA Astrophysics Data System (ADS)

    Sugimura, E.; Komabayashi, T.; Ohta, K.; Hirose, K.; Sata, N.; Ohishi, Y.; Shimizu, K.; Dubrovinsky, L. S.

    2011-12-01

    The experimental evidence for the superionic conduction in H2O ice at high pressure (P) and temperature (T) has been long-searched since its theoretical prediction. Melting experiments reported a steep rise of the melting curve at P-T range of 35-43 GP and 1000-1600 K, which could be due to a first-order phase transition in the solid phases, namely the presence of the triple point of water, ice VII, and a high-T phase which was assumed superionic. Nonetheless, there has still been no report on direct experimental evidence for superionic conduction (ca. 0.1 S/cm) in ice at high pressure. Here we examined ionic conductivity and isothermal molar volume of ice at high-P-T based on impedance spectroscopy (IS) and x-ray diffraction measurements in an externally-resistive heated diamond anvil cell. In situ IS measurements up to 62 GPa and 920 K demonstrated that ice exhibits superionic conduction (> 0.1 S/cm) above 580-720 K at 20-60 GPa. This suggests that superionic conduction occurs at sufficiently lower P-T than the triple point. Isothermal P-V data collected at P = 33-101 GPa and T = 873 K revealed that an anomalous volume reduction occurs at P = 50-53 GPa. This compression manner corresponds to the previously reported highly compressible regime at P = 40-60 GPa, T = 300 K, which were attributed to hydrogen bond symmetrization. There is no volume discontinuity in the isothermal compression, which contradicts the proposed first order P-T boundary between ice VII and superionic ice. Furthermore, all the conductivity data is expressed by a single Arrhenius equation so that the superionic conduction occurs regardless of the ongoing hydrogen bond symmetrization upon compression. We suggests that the previously reported steep rise of the melting temperature of ice above 35-43 GPa is independent of superionic transition, and is a consequence of the hydrogen bond symmetrization. Combining above results with the existing planetary isentropes, superionic conduction in H2O ice

  9. The stability and Raman spectra of ikaite, CaCO3·6H2O, at high pressure and temperature

    USGS Publications Warehouse

    Shahar, Anat; Bassett, William A.; Mao, Ho-kwang; Chou, I-Ming; Mao, Wendy

    2005-01-01

    Raman analyses of single crystals of ikaite, CaCO3·6H2O, synthesized in a diamond-anvil cell at ambient temperature yield spectra from 0.14 to 4.08 GPa; the most intense peaks are at 228 and 1081 cm−1 corresponding to Eg(external) and A1g (internal) modes of vibrations in CO2− 3 ions, respectively. These are in good agreement with Raman spectra previously published for ikaite in powder form at ambient temperature and pressure. Visual observations of a sample consisting initially of a mixture of calcite + water in a hydrothermal diamond-anvil cell yielded a P-T phase diagram up to 2 GPa and 120 °C; the boundary for the reaction ikaite ↔ aragonite + water has a positive slope and is curved convexly toward the aragonite + water field similar to typical melt curves. This curvature can be explained in terms of the Clapeyron equation for a boundary between a solid phase and a more compressible liquid phase or largely liquid phase assemblage.

  10. The spectral variability of kieserite (MgSO4·H2O) with temperature and grain size and its application to the Martian surface

    NASA Astrophysics Data System (ADS)

    Jamieson, C. S.; Noe Dobrea, E. Z.; Dalton, J. B.; Pitman, K. M.; Abbey, W. J.

    2014-06-01

    We spectrally characterize (λ = 0.35-10 µm) the low-humidity polymorph of kieserite (MgSO4·H2O), which is abundant on Mars and likely present on Europa, at various grain sizes and temperatures (100-300 K) relevant to the surfaces of Mars and Europa. Compositional analysis of these surfaces often relies on remote sensing using imaging spectrometers such as Mars Reconnaissance Orbiter Compact Reconnaissance Imaging Spectrometer for Mars (CRISM), Mars Express Observatoire pour la Minéralogie, l'Eau, les Glaces et l'Activité, and Galileo Near-Infrared Mapping Spectrometer. To estimate surface abundances from these observations, well-characterized laboratory spectra are required for comparison. Several variables, including temperature and grain size, affect the observed spectra and must be quantified in the laboratory to more confidently evaluate the returned data. Certain spectral features of kieserite exhibit predictable variability with changes in temperature and grain size that may be exploited to better understand the nature of kieserite on the surface of Mars. For instance, trends in our spectral analysis suggest that absorption features centered at λ < 3.0 µm were primarily sensitive to temperature changes, while features at λ > 3.0 µm were additionally sensitive to grain size changes. We compare our laboratory spectra with selected CRISM data of suspected Martian kieserite and assess the inherent uncertainty that exists in using band center minima to determine surface composition. Incorporation of these temperature and grain size-specific spectra into linear mixture models of planetary surface spectra will improve the compositional interpretation and contribute to our understanding of surface geochemistry and chemical evolution.

  11. Corrosion of 310 stainless steel in H2-H2O-H2S gas mixtures: Studies at constant temperature and fixed oxygen potential

    NASA Technical Reports Server (NTRS)

    Rao, D. B.; Jacob, K. T.; Nelson, H. G.

    1981-01-01

    Corrosion of SAE 310 stainless steel in H2-H2O-H2S gas mixtures was studied at a constant temperature of 1150 K. Reactive gas mixtures were chosen to yield a constant oxygen potential of approximately 6 x 10 to the minus 13th power/cu Nm and sulfur potentials ranging from 0.19 x 10 to the minus 2nd power/cu Nm to 33 x 10 to the minus 2nd power/cu Nm. The kinetics of corrosion were determined using a thermobalance, and the scales were analyzed using metallography, scanning electron microscopy, and energy dispersive X-ray analysis. Two corrosion regimes, which were dependent on sulfur potential, were identified. At high sulfur potentials (p sub S sub 2 less than or equal to 2.7 x 10 to the minus 2nd power/cu Nm) the corrosion rates were high, the kinetics obeyed a linear rate equation, and the scales consisted mainly of sulfide phases similar to those observed from pure sulfication. At low sulfur potentials (P sub S sub 2 less than or equal to 0.19 x 10 to the minus 2nd power/cu Nm) the corrosion rates were low, the kinetics obeyed a parabolic rate equation, and scales consisted mainly of oxide phases.

  12. Study of temperature effect on far-infrared spectra of liquid H2O and D2O by analytical theory and molecular dynamic simulations.

    PubMed

    Zasetsky, Alexander Y; Gaiduk, Vladimir I

    2007-06-28

    The results of a combined study of dielectric loss (epsilon"(nu)) and power-absorption coefficient (alpha(nu)) are reported. The epsilon"(nu) and alpha(nu) values are obtained for liquid water (H2O) and heavy water (D2O) using analytical modeling and the molecular dynamics (MD) simulations method. The calculated spectra span the microwave and far-infrared (FIR) region. The temperature range probed is 220-355 K. Appropriate parametrization of the analytical model for liquid water enables the quantitative description of the dielectric spectra over the frequency range of 0-1000 cm-1. An excellent agreement between the calculated spectra and the experimental data demonstrates the accuracy of the applied analytical approximations. The spectra obtained using the MD simulations agree rather qualitatively with the experimental epsilon"(nu) and alpha(nu) dependences. The observed spectra are interpreted in terms of four molecular mechanisms that have been recently described [J. Phys. Chem. A 2006, 110, 9361]. PMID:17552503

  13. Phase relations in the system NaCl-KCl-H2O: V. Thermodynamic-PTX analysis of solid-liquid equilibria at high temperatures and pressures

    USGS Publications Warehouse

    Sterner, S.M.; Chou, I.-Ming; Downs, R.T.; Pitzer, Kenneth S.

    1992-01-01

    The Gibbs energies of mixing for NaCl-KCl binary solids and liquids and solid-saturated NaCl-KCl-H2O ternary liquids were modeled using asymmetric Margules treatments. The coefficients of the expressions were calibrated using an extensive array of binary solvus and solidus data, and both binary and ternary liquidus data. Over the PTX range considered, the system exhibits complete liquid miscibility among all three components and extensive solid solution along the anhydrous binary. Solid-liquid and solid-solid phase equilibria were calculated by using the resulting equations and invoking the equality of chemical potentials of NaCl and KCl between appropriate phases at equilibrium. The equations reproduce the ternary liquidus and predict activity coefficients for NaCl and KCl components in the aqueous liquid under solid-saturation conditions between 673 and 1200 K from vapor saturation up to 5 kbar. In the NaCl-KCl anhydrous binary system, the equations describe phase equilibria and predict activity coefficients of the salt components for all stable compositions of solid and liquid phases between room temperature and 1200 K and from 1 bar to 5 kbar. ?? 1992.

  14. Decomposition and multiphase reactions in the system UO 2(NO 3) 2·6H 2O-Ni(NO 3) 2·6H 2O at elevated temperatures

    NASA Astrophysics Data System (ADS)

    Kalekar, Bhupesh B.; Rajagopalan, K. V.; Ravindran, P. V.

    2009-09-01

    Solid state reactions between uranyl nitrate hexahydrate and nickel nitrate hexahydrate in mixtures of various ratios have been studied at elevated temperatures. The binary system of uranyl nitrate hexahydrate and nickel nitrate hexahydrate was found to form a eutectic of composition 53 mol% uranyl nitrate hexahydrate and 47 mol% nickel nitrate hexahydrate at 40 °C. The overlap of evolution of nitric oxide (NO) and water vapour above 230 °C confirmed the presence of hydroxynitrates of uranium and nickel as intermediate products. These hydroxynitrates began to react above 280 °C to form nickel uranate, NiU 3O 10, in the case of mixtures containing 75 mol% uranyl nitrate hexahydrate. When the proportion of uranyl nitrate hexahydrate in the mixture was higher than 75 mol%, U 3O 8 formed along with nickel uranate. For the mixtures containing uranyl nitrate hexahydrate lower than 75 mol%, NiO was observed to form along with NiU 3O 10.

  15. Effect of H2O and CO2 on The Oxidation Behavior and Durability at High Temperature of ODS-FeCrAl

    SciTech Connect

    Dryepondt, Sebastien N; Rouaix-Vande Put, Aurelie; Pint, Bruce A

    2012-01-01

    Cyclic oxidation testing was conducted on alloy MA956 and two different batches of alloy PM2000 at 1100 and 1200 C in different atmospheres rich in O2, H2O and CO2. Compare to 1h cycle in dry O2, exposure in air + 10 vol.% H2O resulted in an increase of the oxidation rate and a decrease of the time to breakaway for both alloys at 1200 C, and a faster consumption of Al in the MA956 alloy. 1h cyclic testing in 50%CO2/50%H2O+0.75% O2 had less of an impact on the oxidation rate but led to an increased formation of voids for alloy MA956, which had an impact on the alloy creep resistance. At 1100 C, exposure in 50%CO2/50%H2O resulted in significant oxide spallation compared with oxidation in air, but it was not the case when 0.75% O2 was added to the CO2/H2O mixture as a buffer. The control of impurities levels drastically improved the PM2000 oxidation resistance.

  16. Communication: State-to-state dynamics of the Cl + H2O → HCl + OH reaction: Energy flow into reaction coordinate and transition-state control of product energy disposal

    NASA Astrophysics Data System (ADS)

    Zhao, Bin; Sun, Zhigang; Guo, Hua

    2015-06-01

    Quantum state-to-state dynamics of a prototypical four-atom reaction, namely, Cl + H2O → HCl + OH, is investigated for the first time in full dimensionality using a transition-state wave packet method. The state-to-state reactivity and its dependence on the reactant internal excitations are analyzed and found to share many similarities both energetically and dynamically with the H + H2O → H2 + OH reaction. The strong enhancement of reactivity by the H2O stretching vibrational excitations in both reactions is attributed to the favorable energy flow into the reaction coordinate near the transition state. On the other hand, the insensitivity of the product state distributions with regard to reactant internal excitation stems apparently from the transition-state control of product energy disposal.

  17. Neutron diffraction studies of H2O/D2O at supercritical temperatures. A direct determination of gHH(r), gOH(r), and gOO(r)

    NASA Astrophysics Data System (ADS)

    Tromp, R. H.; Postorino, P.; Neilson, G. W.; Ricci, M. A.; Soper, A. K.

    1994-10-01

    Neutron diffraction studies are reported on H2O at temperatures of 300 and 400 °C. The method of isotopic substitution is applied to three mixtures of H2O and D2O, and the diffraction data are used to determine the three radial distribution functions gHH(r), gOH(r), and gOO(r). These results can be used to discuss changes in nearest neighbor structure between water molecules, and to assess the degree of usefulness of representative (usually pairwise) model potentials.

  18. Corrosion of 310 stainless steel in H2- H2O- H2S gas mixtures: Studies at constant temperature and fixed oxygen potential

    NASA Astrophysics Data System (ADS)

    Rao, D. Bhogeswara; Jacob, K. T.; Nelson, Howard G.

    1983-02-01

    Corrosion of SAE 310 stainless steel in H2-H2O-H2S gas mixtures was studied at a constant temperature of 1150 K. Reactive gas mixtures were chosen to yield a constant oxygen potential of approximately 6 × 10-13 Nm-2 and sulfur potentials ranging from 0.19 × 10-2 Nm-2 to 33 × 10-2 Nm-2. The kinetics of corrosion were determined using a thermobalance, and the scales were analyzed using metallography, scanning electron microscopy, and energy dispersive X-ray analysis. Two corrosion regimes, which were dependent on sulfur potential, were identified. At high sulfur potentials ( P S 2 ± 2.7 × 10-2 Nm-2) the corrosion rates were high, the kinetics obeyed a linear rate equation, and the scales consisted mainly of sulfide phases similar to those observed from pure sulfidation. At low sulfur potentials ( P S 2 ± 0.19 × 10-2 Nm-2) the corrosion rates were low, the kinetics obeyed a parabolic rate equation, and scales consisted mainly of oxide phases. Thermochemical diagrams for the Fe-Cr-S-O, Fe-Ni-S-O, Cr-Ni-S-O, and Si-Cr-S-O systems were constructed, and the experimental results are discussed in relation to these diagrams. Based on this comparison, reasonable corrosion mechanisms were developed. At high sulfur potentials, oxide and sulfide phases initially nucleate as separate islands. Overgrowth of the oxide by the sulfide occurs and an exchange reaction governs the corrosion process. Preoxidation at low oxygen potentials and 1150 K is beneficial in suppressing sulfidation at high sulfur potentials.

  19. In-situ Raman spectroscopic study of aluminate speciation in H2O-KOH solutions at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Mookherjee, M.; Keppler, H.; Manning, C. E.

    2009-12-01

    The solubility of corundum in H2O is low even at high pressure and temperatures. Therefore, it is commonly assumed that alumina remains essentially immobile during fluid-rock interaction. However, field and experimental evidence suggests that alumina solubility is strongly enhanced in the presence of silica as well as in alkaline solutions. In order to understand what controls the alumina solubility and how it is enhanced as a function of fluid composition, we conducted Raman-spectroscopic study of Al speciation in aqueous fluids at high pressure and temperature. Experiments were carried out in an externally heated hydrothermal diamond-anvil cell equipped with low-fluorescence diamonds and iridium gaskets. Raman spectra were collected with a Horiba Jobin-Yvon Labram HR spectrometer using the 514 nm line of an argon laser for excitation. In a first series of experiments, the speciation of alumina was studied in a 1 M KOH solution in equilibrium with corundum up to 700 oC and ~1 GPa. The Raman spectra show a prominent band at 618 cm-1 interpreted to arise from Al-O stretching vibrations associated with the tetrahedral [Al(OH)4]1- species. At higher pressure and temperature, an additional vibrational mode appears in the spectra at 374 cm-1 (full width at half maximum ~ 20 cm-1). This feature is tentatively attributed to [(OH)3Al-O-Al(OH)3]2- (Moolenaar et al. 1970, Jour. Phys. Chem., 74, 3629-3636). No evidence for KAl(OH)4 was observed, consistent with piston cylinder experiments at 700 oC and 1 GPa (Wohlers & Manning, 2009, Chem. Geol., 262, 310). Upon cooling from high-pressure and high temperature, slow kinetics of corundum regrowth lead to oversaturation in the solutions, as evidenced by sharp peaks at 930 and 1066 cm-1 observed upon cooling. These features are probably due to colloidal aluminum hydroxide. The results provide the first evidence for aluminate polymerization at high pressure and temperature, and offer insights into the causes for enhancement of

  20. Diffuse reflection infrared Fourier transform (DRIFT) spectra and high-temperature DRIFT spectra of beta-Ni(IO3)2.4H2O, Ni(IO3)2.2H2O, Mg(OH)2, and Zn(OH)F: novel embedding materials.

    PubMed

    Pracht, G; Weckler, B; Lutz, H D

    2003-10-01

    Diffuse reflection infrared Fourier transform (DRIFT) spectra of the hydroxides Mg(OH)2 and Zn(OH)F and the iodate hydrates beta-Ni(IO3)2.4H2O and Ni(IO3)2.2H2O have been recorded at ambient and high temperature. Spectra without shifts of the band maxima compared to those of conventional infrared transmission spectra and without inversion of the bands were obtained by dilution of the compounds to about 2-10% with an appropriate embedding material. alpha-Al2O3, TiO2, ZrO2, PbF2, MgO, BaO, ZnO, Na2SiO3, SiO2 (aerosil), and powdered copper, aluminum, and magnesium were tested as diluents for hydrates and hydroxides, especially at elevated temperatures, as alternatives for the commonly used KBr. Thus, alpha-Al2O3, PbF2, and powdered copper were established as the most favorable diluents. Using these novel embedding materials, high-temperature DRIFT spectra are obtainable at temperatures not accessible with KBr discs. Dehydration and decomposition of the iodate hydrates under study were shown by change or disappearance of the respective water bands. PMID:14639754

  1. Zircon solubility and zirconium complexation in H2O+Na2O+SiO2±Al2O3 fluids at high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Wilke, Max; Schmidt, Christian; Dubrail, Julien; Appel, Karen; Borchert, Manuela; Kvashnina, Kristina; Manning, Craig E.

    2012-10-01

    Zircon is an important host mineral for many high-field strength elements (HFSE), particularly Zr and Hf. Thus, its solubility in geologic fluids at high pressure and temperature plays an important role in terrestrial cycling of these elements during processes in the Earth's crust and mantle. We performed in-situ high-pressure, high-temperature measurements of zircon solubility in H2O-Na2Si3O7, H2O-Na2Si3O7+Al2O3, H2O-Na2Si2O5, H2O-NaAlSi3O8 fluids, as well as of baddeleyite solubility in H2O-NaOH fluids, by in-situ synchrotron radiation X-ray fluorescence analysis using hydrothermal diamond-anvil cells. Zirconium complexation in fluids in equilibrium with zircon was constrained by in-situ X-ray absorption near-edge structure (XANES) spectroscopy. Zircon solubility is strongly enhanced by addition of Na2Si3O7 to H2O. The degree of enhancement increases with Na2Si3O7 concentration. The Zr content of fluids containing 10 wt% Na2Si3O7 reached up to 86±2 ppm Zr at 550 °C and 400 MPa. At 30 wt% Na2Si3O7, the maximum Zr concentration was 997±6 ppm at 600 °C and 440 MPa. Zircon solubility in these fluids decreases considerably with pressure and increases slightly with temperature. Addition of Al2O3 decreases the zircon solubility. In H2O-NaAlSi3O8 fluids, the Zr concentrations are in the sub-ppm to ppm range. Zr concentrations in NaOH solutions in equilibrium with baddeleyite reached up to 390±2 ppm at 600 °C and 930 MPa and increase with pressure and temperature. In-situ XANES spectra collected on Zr in H2O-Na2Si3O7, H2O-Na2Si3O7+Al2O3, H2O-NaOH, and H2O-HCl fluids in equilibrium with zircon provide evidence for strong differences in the Zr complexation between these fluids. Comparison of XANES spectra to those of model compounds and ab-initio simulation of XANES spectra revealed [8]Zr for the HCl solution, [7]Zr for the NaOH solution, and [6]Zr for the Na-Al-silicate-bearing solutions. For the latter solutions, formation of alkali zircono-silicate complexes is

  2. The effects of H2O and SO2 on the behaviour of CuSO4-CeO2/TS for low temperature catalytic reduction of NO with NH3.

    PubMed

    Tong, Hua; Dai, Junhong; He, Yong; Tong, Zhiquan

    2011-01-01

    The catalyst CuSO4-CeO2/TiO2-SiO2 (CuSO4-CeO2/TS), for low temperature catalytic reduction (LT-SCR) of NO with NH was prepared by the impregnation method. The impacts of H2O and SO2 on the catalyst were investigated. Experiments showed that H2O brought down the catalyst's activity at low reaction temperature. However, this negative effect of H2O could be mostly eliminated with a raised temperature of above 220 degrees C. In a 10-hour experiment on the catalyst's resistibility to SO2 poisoning, NO conversion increased slightly by the promoting effect of SO2. The same catalyst underwent continuous examination with both SO2 and H2O in the feed gas; NO conversion of around 90.2% was maintained for 37 hours, showing better performance than CuSO4-CeO2/TiO2. This suggested that SiO2 in the TiO2-SiO2 catalyst supported the supression of the oxidization of SO2 to SO3. Therefore, the formation of ammonium sulphate over the catalyst and the sulphation of CeO2 in the catalyst were greatly alleviated, leading to a better resistibility of the catalyst to SO2 poisioning. After the 37 hours, the catalyst activity began to fall, and an irrecoverable deactivation of the catalyst was observed. PMID:21879564

  3. Quantitative Measurements of HO2 and other products of n-butane oxidation (H2O2, H2O, CH2O, and C2H4) at elevated temperatures by direct coupling of a jet-stirred reactor with sampling nozzle and cavity ring-down spectroscopy (cw-CRDS).

    PubMed

    Djehiche, Mokhtar; Le Tan, Ngoc Linh; Jain, Chaithanya D; Dayma, Guillaume; Dagaut, Philippe; Chauveau, Christian; Pillier, Laure; Tomas, Alexandre

    2014-11-26

    For the first time quantitative measurements of the hydroperoxyl radical (HO2) in a jet-stirred reactor were performed thanks to a new experimental setup involving fast sampling and near-infrared cavity ring-down spectroscopy at low pressure. The experiments were performed at atmospheric pressure and over a range of temperatures (550-900 K) with n-butane, the simplest hydrocarbon fuel exhibiting cool flame oxidation chemistry which represents a key process for the auto-ignition in internal combustion engines. The same technique was also used to measure H2O2, H2O, CH2O, and C2H4 under the same conditions. This new setup brings new scientific horizons for characterizing complex reactive systems at elevated temperatures. Measuring HO2 formation from hydrocarbon oxidation is extremely important in determining the propensity of a fuel to follow chain-termination pathways from R + O2 compared to chain branching (leading to OH), helping to constrain and better validate detailed chemical kinetics models. PMID:25381864

  4. Solubilities of corundum, wollastonite and quartz in H 2O-NaCl solutions at 800 °C and 10 kbar: Interaction of simple minerals with brines at high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Newton, Robert C.; Manning, Craig E.

    2006-11-01

    Solubilities of corundum (Al 2O 3) and wollastonite (CaSiO 3) were measured in H 2O-NaCl solutions at 800 °C and 10 kbar and NaCl concentrations up to halite saturation by weight-loss methods. Additional data on quartz solubility at a single NaCl concentration were obtained as a supplement to previous work. Single crystals of synthetic corundum, natural wollastonite or natural quartz were equilibrated with H 2O and NaCl at pressure ( P) and temperature ( T) in a piston-cylinder apparatus with NaCl pressure medium and graphite heater sleeves. The three minerals show fundamentally different dissolution behavior. Corundum solubility undergoes large enhancement with NaCl concentration, rising rapidly from Al 2O 3 molality (mO) of 0.0013(1) (1 σ error) in pure H 2O and then leveling off to a maximum of ˜0.015 at halite saturation ( XNaCl ≈ 0.58, where X is mole fraction). Solubility enhancement relative to that in pure H 2O, XO/XAlO°, passes through a maximum at XNaCl ≈ 0.15 and then declines towards halite saturation. Quenched fluids have neutral pH at 25 °C. Wollastonite has low solubility in pure H 2O at this P and T(m=0.0167(6)). It undergoes great enhancement, with a maximum solubility relative to that in H 2O at XNaCl ≈ 0.33, and solubility >0.5 molal at halite saturation. Solute silica is 2.5 times higher than at quartz saturation in the system H 2O-NaCl-SiO 2, and quenched fluids are very basic (pH 11). Quartz shows monotonically decreasing solubility from m=1.248 in pure H 2O to 0.202 at halite saturation. Quenched fluids are pH neutral. A simple ideal-mixing model for quartz-saturated solutions that requires as input only the solubility and speciation of silica in pure H 2O reproduces the data and indicates that hydrogen bonding of molecular H 2O to dissolved silica species is thermodynamically negligible. The maxima in XO/XAlO° for corundum and wollastonite indicate that the solute products include hydrates and Na + and/or Cl - species produced by

  5. Effect of H2O, and combined effects of H2O + F, H2O + CO2, and H2O + F + CO2 on the viscosity of a natural basalt from Fuego volcano, Guatemala

    NASA Astrophysics Data System (ADS)

    Robert, G.; Whittington, A. G.; Knipping, J.; Scherbarth, S.; Stechern, A.; Behrens, H.

    2012-12-01

    We measured the viscosity of 5 series of remelted natural basalt from Fuego volcano, Guatemala. These series include single and multiple volatile species: H2O, F, H2O-F, H2O-CO2, and H2O-CO2-F. The hydrous glasses were synthesized at 3 kbar and 1250°C in Internally Heated Pressure Vessels. The multiple volatile series were synthesized at 5 kbar and 1250°C. CO2 was added as Ag2C2O4, F as AlF3, and H2O as distilled water. The anhydrous, F-bearing series was synthesized at 1 atm by simply remelting the Fuego basalt and adding F as CaF2.The natural, dry, remelted Fuego basalt has an NBO/T of 0.64. The following comparisons are based on parallel-plate viscosity measurements in the range ~108 to 1012 Pa s. The temperature at which the viscosity is 1012 Pa s (T12) is taken to be the viscosimetric glass transition temperature (Tg). The addition of 2 wt.% H2O results in a decrease of T12 of ~150°C for basalt. Fluorine on its own has a measurable, but much smaller effect, than the equivalent amount of water. Indeed, ~2 wt.% F results in a T12 depression of only ~30°C. When H2O and F are both present, their effects are approximately additive. For example, the viscosity of a basalt with 1.44 wt.% H2O is very similar to the viscosity of a basalt with ~1 wt.% H2O and ~1.25 wt.% F, and the viscosities of a basalt with 2.29 wt.% H2O and a basalt with ~1.65 wt.% H2O and ~1.3 wt.% F are also very similar. The effect of CO2 is somewhat ambiguous. The viscosity of a basalt with ~1.7 wt.% H2O, ~1.3 wt.% F and ~0.2 wt.% CO2 is essentially the same as the viscosity of a basalt with 2.29 wt.% H2O, so CO2 seems to have a negligible or even viscosity-increasing effect when F and H2O are also present. However, a basalt with ~0.84 wt.% H2O and ~0.09 wt.% CO2 has about the same viscosity as a basalt with 1.34 wt.% H2O, which could suggest a strong (viscosity-decreasing) effect of very small amounts of CO2. These results suggest that the effects on viscosity of F in basaltic systems are

  6. CO Diffusion into Amorphous H2O Ices

    NASA Astrophysics Data System (ADS)

    Lauck, Trish; Karssemeijer, Leendertjan; Shulenberger, Katherine; Rajappan, Mahesh; Öberg, Karin I.; Cuppen, Herma M.

    2015-03-01

    The mobility of atoms, molecules, and radicals in icy grain mantles regulates ice restructuring, desorption, and chemistry in astrophysical environments. Interstellar ices are dominated by H2O, and diffusion on external and internal (pore) surfaces of H2O-rich ices is therefore a key process to constrain. This study aims to quantify the diffusion kinetics and barrier of the abundant ice constituent CO into H2O-dominated ices at low temperatures (15-23 K), by measuring the mixing rate of initially layered H2O(:CO2)/CO ices. The mixed fraction of CO as a function of time is determined by monitoring the shape of the infrared CO stretching band. Mixing is observed at all investigated temperatures on minute timescales and can be ascribed to CO diffusion in H2O ice pores. The diffusion coefficient and final mixed fraction depend on ice temperature, porosity, thickness, and composition. The experiments are analyzed by applying Fick’s diffusion equation under the assumption that mixing is due to CO diffusion into an immobile H2O ice. The extracted energy barrier for CO diffusion into amorphous H2O ice is ˜160 K. This is effectively a surface diffusion barrier. The derived barrier is low compared to current surface diffusion barriers in use in astrochemical models. Its adoption may significantly change the expected timescales for different ice processes in interstellar environments.

  7. The interaction of H(2)O(2) with ice surfaces between 203 and 233 K.

    PubMed

    Pouvesle, N; Kippenberger, M; Schuster, G; Crowley, J N

    2010-12-21

    The interaction of H(2)O(2) with ice surfaces at temperatures between 203 and 233 K was investigated using a low pressure, coated-wall flow tube equipped with a chemical ionisation/electron impact mass spectrometer. Equilibrium surface coverages of H(2)O(2) on ice were measured at various concentrations and temperatures to derive Langmuir-type adsorption isotherms. H(2)O(2) was found to be strongly partitioned to the ice surface at low temperatures, with a partition coefficient, K(linC), equal to 2.1 × 10(-5) exp(3800/T) cm. At 228 K, this expression results in values of K(linC) which are orders of magnitude larger than the single previous determination and suggests that H(2)O(2) may be significantly partitioned to the ice phase in cirrus clouds. The partition coefficient for H(2)O(2) was compared to several other trace gases which hydrogen-bond to ice surfaces and a good correlation with the free energy of condensation found. For this class of trace gas a simple parameterisation for calculating K(linC)(T) from thermodynamic properties was established. PMID:20976362

  8. Hydrogen bonding system in euchroite, Cu2(AsO4)(OH)(H2O)3: low-temperature crystal-structure refinement and solid-state density functional theory modeling

    NASA Astrophysics Data System (ADS)

    Krivovichev, Sergey V.; Zolotarev, Andrey A.; Pekov, Igor V.

    2016-06-01

    Hydrogen bonding in euchroite has been studied by means of low-temperature single-crystal X-ray diffraction (XRD) and solid-state density functional theory (DFT) calculations. The mineral is orthorhombic, P212121, a = 10.0350(8), b = 10.4794(8), c = 6.1075(5) Å, V = 642.27(9) Å3, and Z = 4. The structure has been refined to R 1 = 0.036 for 2436 unique observed reflections with |F o| ≥ 4σ F . DFT calculations were performed with the CRYSTAL14 software package. The basic features of the crystal structure of euchroite are the same as described by previous authors. There are two symmetrically-independent Cu sites octahedrally coordinated by O atoms. The CuO6 octahedra are strongly distorted containing four short (1.927-2.012 Å) and two long (2.360-2.797 Å) bonds each, in agreement with the expected Jahn-Teller distortion of an octahedrally-coordinated Cu2+ cation. There is one symmetrically-independent As site that is tetrahedrally coordinated by four O atoms to form an arsenate oxyanion, AsO4 3-. The structure is based upon chains of edge-sharing CuO6 octahedra running parallel to [001]. The chains are linked by AsO4 tetrahedra into a three-dimensional framework, which is stabilized by hydrogen bonds formed from OH and H2O groups. The coordinates of H atoms determined by single-crystal X-ray diffraction and those calculated using DFT are very similar. The distance Δ between experimental and theoretical H positions does not exceed 0.250 Å, except for the H72 site, for which Δ = 0.609 Å. The hydrogen bonding scheme in euchroite is rather complex and involves a combination of relatively strong two-center hydrogen bonds as well as few three-center (bifurcated) hydrogen bonds. The largest difference between the XRD and DFT results involves the H72 atom of the H2O7 molecule and can be assigned to the effect of temperature, which favors a strong linear hydrogen bond at 0 K (calculated) and a bifurcated three-center bond at 100 K (measured). The Cu-H2O

  9. Isentropic advection and convective lifting of water vapor in the UT - LS as observed over Brazil (22° S) in February 2004 by in situ high-resolution measurements of H2O, CH4, O3 and temperature

    NASA Astrophysics Data System (ADS)

    Durry, G.; Huret, N.; Hauchecorne, A.; Marecal, V.; Pommereau, J.-P.; Jones, R. L.; Held, G.; Larsen, N.; Renard, J.-B.

    2006-12-01

    The micro-SDLA balloonborne diode laser spectrometer was flown twice from Bauru (22° S, Brazil) in February 2004 during HIBISCUS to yield in situ H2O measurements in the Upper Troposphere (UT) and Lower Stratosphere (LS) and in particular in the Tropical Tropopause Layer (TTL). The overall TTL was found warmer (with a subsaturated cold point near -79°C) and the LS moister compared to former measurements obtained in tropical oceanic conditions. The use of specific balloons with a slow descent, combined with the high-resolution of the laser sensor, allowed us to observe in situ in the UT, the TTL and the LS several thin layers correlated on H2O, CH4, O3, temperature and PV. A component of these layers is associated with the isentropic transport into the UT- LS of extratropical stratospheric air masses. Moreover, the examination of temperature and tracer (CH4, O3) profiles gives insights on the potential contribution of convective transport of H2O in the TTL.

  10. Stepwise formation of H3O+(H2O)n in an ion drift tube: Empirical effective temperature of association/dissociation reaction equilibrium in an electric field

    NASA Astrophysics Data System (ADS)

    Nakai, Yoichi; Hidaka, Hiroshi; Watanabe, Naoki; Kojima, Takao M.

    2016-06-01

    We measured equilibrium constants for H3O+(H2O)n-1 + H2O↔H3O+(H2O)n (n = 4-9) reactions taking place in an ion drift tube with various applied electric fields at gas temperatures of 238-330 K. The zero-field reaction equilibrium constants were determined by extrapolation of those obtained at non-zero electric fields. From the zero-field reaction equilibrium constants, the standard enthalpy and entropy changes, Δ Hn , n - 1 0 and Δ Sn , n - 1 0 , of stepwise association for n = 4-8 were derived and were in reasonable agreement with those measured in previous studies. We also examined the electric field dependence of the reaction equilibrium constants at non-zero electric fields for n = 4-8. An effective temperature for the reaction equilibrium constants at non-zero electric field was empirically obtained using a parameter describing the electric field dependence of the reaction equilibrium constants. Furthermore, the size dependence of the parameter was thought to reflect the evolution of the hydrogen-bond structure of H3O+(H2O)n with the cluster size. The reflection of structural information in the electric field dependence of the reaction equilibria is particularly noteworthy.

  11. Stepwise formation of H3O(+)(H2O)n in an ion drift tube: Empirical effective temperature of association/dissociation reaction equilibrium in an electric field.

    PubMed

    Nakai, Yoichi; Hidaka, Hiroshi; Watanabe, Naoki; Kojima, Takao M

    2016-06-14

    We measured equilibrium constants for H3O(+)(H2O)n-1 + H2O↔H3O(+)(H2O)n (n = 4-9) reactions taking place in an ion drift tube with various applied electric fields at gas temperatures of 238-330 K. The zero-field reaction equilibrium constants were determined by extrapolation of those obtained at non-zero electric fields. From the zero-field reaction equilibrium constants, the standard enthalpy and entropy changes, ΔHn,n-1 (0) and ΔSn,n-1 (0), of stepwise association for n = 4-8 were derived and were in reasonable agreement with those measured in previous studies. We also examined the electric field dependence of the reaction equilibrium constants at non-zero electric fields for n = 4-8. An effective temperature for the reaction equilibrium constants at non-zero electric field was empirically obtained using a parameter describing the electric field dependence of the reaction equilibrium constants. Furthermore, the size dependence of the parameter was thought to reflect the evolution of the hydrogen-bond structure of H3O(+)(H2O)n with the cluster size. The reflection of structural information in the electric field dependence of the reaction equilibria is particularly noteworthy. PMID:27306006

  12. Thermal studies on the interaction behavior of ternary nitrate mixtures of UO2(NO3)2ṡ6H2O-NaNO3-Sr(NO3)2 at elevated temperatures

    NASA Astrophysics Data System (ADS)

    Kalekar, Bhupesh; Raje, Naina; Reddy, A. V. R.

    2015-04-01

    Thermal and X-ray diffraction measurements have been used to study the formation of various nitrato-complexes as intermediates and mixed oxides as end products using different mol ratios of the ternary mixtures of UO2(NO3)2ṡ6H2O, NaNO3 and Sr(NO3)2 at high temperatures. These results indicate the interaction of UO2(NO3)2ṡ6H2O and NaNO3 in equimolar ratio to form sodium uranyl nitrate monohydrate (Na[UO2(NO3)3]ṡH2O), dimerized sodium uranyl oxynitrate (Na2[(UO2NO3)2(O)2]) and sodium diuranate (Na2U2O7). The decomposition temperature of Sr(NO3)2 decreased by 60 °C in the presence of in-situ formed Na2U2O7. The uranium of Na2U2O7 intermediate reacts with Sr(NO3)2 to form various strontium uranium mixed oxides depending on Sr to U ratio in the initial mixtures. During the interaction of Sr(NO3)2 with Na2U2O7, sodium separates out as amorphous Na2O in the mixtures, containing Sr to U ratio ⩾1. Na2O phase is not formed in the uranium rich ternary mixture.

  13. Aerosol chamber study of optical constants and N2O5 uptake on supercooled H2SO4/H2O/HNO3 solution droplets at polar stratospheric cloud temperatures.

    PubMed

    Wagner, Robert; Naumann, Karl-Heinz; Mangold, Alexander; Möhler, Ottmar; Saathoff, Harald; Schurath, Ulrich

    2005-09-15

    The mechanism of the formation of supercooled ternary H(2)SO(4)/H(2)O/HNO(3) solution (STS) droplets in the polar winter stratosphere, i.e., the uptake of nitric acid and water onto background sulfate aerosols at T < 195 K, was successfully mimicked during a simulation experiment at the large coolable aerosol chamber AIDA of Forschungszentrum Karlsruhe. Supercooled sulfuric acid droplets, acting as background aerosol, were added to the cooled AIDA vessel at T = 193.6 K, followed by the addition of ozone and nitrogen dioxide. N(2)O(5), the product of the gas phase reaction between O(3) and NO(2), was then hydrolyzed in the liquid phase with an uptake coefficient gamma(N(2)O(5)). From this experiment, a series of FTIR extinction spectra of STS droplets was obtained, covering a broad range of different STS compositions. This infrared spectra sequence was used for a quantitative test of the accuracy of published infrared optical constants for STS aerosols, needed, for example, as input in remote sensing applications. The present findings indicate that the implementation of a mixing rule approach, i.e., calculating the refractive indices of ternary H(2)SO(4)/H(2)O/HNO(3) solution droplets based on accurate reference data sets for the two binary H(2)SO(4)/H(2)O and HNO(3)/H(2)O systems, is justified. Additional model calculations revealed that the uptake coefficient gamma(N(2)O(5)) on STS aerosols strongly decreases with increasing nitrate concentration in the particles, demonstrating that this so-called nitrate effect, already well-established from uptake experiments conducted at room temperature, is also dominant at stratospheric temperatures. PMID:16834200

  14. Room temperature synthesis of rod-like FeC2O4·2H2O and its transition to maghemite, magnetite and hematite nanorods through controlled thermal decomposition

    NASA Astrophysics Data System (ADS)

    Zhou, Weiwei; Tang, Kaibin; Zeng, Suyuan; Qi, Yunxia

    2008-02-01

    FeC2O4·2H2O nanorods with diameter of about 50 nm and length of up to several micrometers were synthesized at room temperature in a surfactant-assisted system, which was obtained by dissolving bis(2-ethylhexyl)sodium sulfosuccinate (AOT) in a mixed solution composed of water and ethylene glycol (EG). The influence of reaction conditions on the morphology of FeC2O4·2H2O is discussed in detail. Through direct thermal decomposition of FeC2O4·2H2O under different calcination conditions, maghemite (γ-Fe2O3), magnetite (Fe3O4) and hematite (α-Fe2O3) can be selectively obtained, preserving the rod-like morphology. Transmission electron microscope (TEM) and high-resolution transmission electron microscope (HRTEM) characterizations showed that the as-obtained iron oxide nanorods were composed of fine particles with different crystal orientations. The magnetic properties of the as-obtained iron oxide nanorods were systematically investigated.

  15. Experimental Analysis of the Effects of Vapor Flow Characteristics on Falling Film Absorption Rate in NH3-H2O Systems

    NASA Astrophysics Data System (ADS)

    Kang, Yong Tae; Fujita, Yasushi; Akisawa, Atsushi; Kashiwagi, Takao

    In this paper, experimental analysis was performed for ammonia-water falling film absorption process in a plate heat exchanger with enhanced surfaces such as offset strip fin. This paper examined the effect of vapor flow characteristics, inlet subcooling of the liquid flow and inlet concentration difference on heat and mass transfer performance. The inlet liquid concentration was kept constant at 0% while the inlet vapor concentration was varied from70. 36 to 77.31% It was found that before absorption started there was rectification process at the top of the test section by the inlet subcooling effect. Water desorption phenomenon was found near the bottom of test section. The lower inlet liquid temperature, the higher Nusselt and Sherwood numbers were obtained. NusseIt and Sherwood correlations were developed as functions of vapor Reynolds number ReV, inlet subcooling and inlet concentration difference with ±10% and ±5% error bands, respectively.

  16. Dissolved, Exsolved and Re-dissolved H2O in Volcanology: Rheology, Glass Transition, and Thermodynamics

    NASA Astrophysics Data System (ADS)

    Russell, K.; kennedy, B.; Giordano, D.; Friedlander, E. A.

    2012-12-01

    All natural magmas originate with dissolved H2O. All such magmas degas during transport and eruption. The presence, abundance, and state of H2O in magmas control phase relations and the transport properties of melts and magmas. For example, dissolved H2O lowers viscosity, lowers glass transition temperatures (Tg), and controls the temperature and nature of crystallization. The effects of exsolved water are also substantial in terms of modifying the bulk transport properties of the magma, facilitating egress of volatiles and, thus, promoting crystallization. Of great interest is the coupling this component (H2O) creates between the thermodynamic processes (i.e. cooling, crystallization, vesiculation) and the properties (i.e. density, viscosity) controlling the mechanical behaviour (i.e. flow and fracture) of magma during transport and eruption. The coupling allows for strong feedbacks between system variables. The component H2O also has a retrograde solubility in silicate melts wherein H2O solubility in the melt increases with decreasing T. Here, we explore some of the consequences of retrograde solubility of H2O for volcanic systems using a new preliminary experimental dataset. These data establish the 1-atmosphere solubility limits of H2O in silicic melt at volcanic temperatures and are complementary to the growing literature on the low pressure (<50 MPa) solubility of volatiles in silicate melts (e.g., Behrens et al. 2009; DiMatteo et al. 2004; Liu et al. 2005; Zhang 1999). We specifically look at the implications of these data, especially the retrograde solubility limits, for welding of pyroclastic deposits (e.g. ignimbrites, conduit fill, fall out). The cessation of welding and compaction processes in pyroclastic deposits is reached when deposits cool below Tg. However, the fact that H2O has a retrograde solubility means that inter- and intraclast water will be resorbed by vitric pyroclasts as the deposit cools (regardless of load). This has the immediate

  17. Experimental multi-phase H2O-CO2 brine interactions at elevated temperature and pressure: Implications for CO2 sequestration in deep-saline aquifers

    USGS Publications Warehouse

    Rosenbauer, R.; Koksalan, T.

    2004-01-01

    The burning of fossil fuel and other anthropogenic activities have caused a continuous and dramatic 30% increase of atmospheric CO2 over the past 150 yr. CO2 sequestration is increasingly being viewed as a tool for managing these anthropogenic CO2 emissions to the atmosphere. CO2-saturated brine-rock experiments were carried out to evaluate the effects of multiphase H2O-CO2 fluids on mineral equilibria and the potential for CO2 sequestration in mineral phases within deep-saline aquifers. Experimental results were generally consistent with theoretical thermodynamic calculations. The solubility of CO2 was enhanced in brines in the presence of both limestone and sandstone relative to brines alone. Reactions between CO2 saturated brines and arkosic sandstones were characterized by desiccation of the brine and changes in the chemical composition of the brine suggesting fixation of CO2 in mineral phases. These reactions were occurring on a measurable but kinetically slow time scale at 120??C.

  18. Quantum mechanical reaction rate constants by vibrational configuration interaction: the OH + H2->H2O + H reaction as a function of temperature.

    PubMed

    Chakraborty, Arindam; Truhlar, Donald G

    2005-05-10

    The thermal rate constant of the 3D OH + H(2)-->H(2)O + H reaction was computed by using the flux autocorrelation function, with a time-independent square-integrable basis set. Two modes that actively participate in bond making and bond breaking were treated by using 2D distributed Gaussian functions, and the remaining (nonreactive) modes were treated by using harmonic oscillator functions. The finite-basis eigenvalues and eigenvectors of the Hamiltonian were obtained by solving the resulting generalized eigenvalue equation, and the flux autocorrelation function for a dividing surface optimized in reduced-dimensionality calculations was represented in the basis formed by the eigenvectors of the Hamiltonian. The rate constant was obtained by integrating the flux autocorrelation function. The choice of the final time to which the integration is carried was determined by a plateau criterion. The potential energy surface was from Wu, Schatz, Lendvay, Fang, and Harding (WSLFH). We also studied the collinear H + H(2) reaction by using the Liu-Siegbahn-Truhlar-Horowitz (LSTH) potential energy surface. The calculated thermal rate constant results were compared with reported values on the same surfaces. The success of these calculations demonstrates that time-independent vibrational configuration interaction can be a very convenient way to calculate converged quantum mechanical rate constants, and it opens the possibility of calculating converged rate constants for much larger reactions than have been treated until now. PMID:15774583

  19. 50-kHz-rate 2D imaging of temperature and H2O concentration at the exhaust plane of a J85 engine using hyperspectral tomography.

    PubMed

    Ma, Lin; Li, Xuesong; Sanders, Scott T; Caswell, Andrew W; Roy, Sukesh; Plemmons, David H; Gord, James R

    2013-01-14

    This paper describes a novel laser diagnostic and its demonstration in a practical aero-propulsion engine (General Electric J85). The diagnostic technique, named hyperspectral tomography (HT), enables simultaneous 2-dimensional (2D) imaging of temperature and water-vapor concentration at 225 spatial grid points with a temporal response up to 50 kHz. To our knowledge, this is the first time that such sensing capabilities have been reported. This paper introduces the principles of the HT techniques, reports its operation and application in a J85 engine, and discusses its perspective for the study of high-speed reactive flows. PMID:23389008

  20. H2O2: a dynamic neuromodulator.

    PubMed

    Rice, Margaret E

    2011-08-01

    Increasing evidence implicates hydrogen peroxide (H(2)O(2)) as an intracellular and intercellular signaling molecule that can influence processes from embryonic development to cell death. Most research has focused on relatively slow signaling, on the order of minutes to days, via second messenger cascades. However, H(2)O(2) can also mediate subsecond signaling via ion channel activation. This rapid signaling has been examined most thoroughly in the nigrostriatal dopamine (DA) pathway, which plays a key role in facilitating movement mediated by the basal ganglia. In DA neurons of the substantia nigra, endogenously generated H(2)O(2) activates ATP-sensitive K(+) (K-ATP) channels that inhibit DA neuron firing. In the striatum, H(2)O(2) generated downstream from glutamatergic AMPA receptor activation in medium spiny neurons acts as a diffusible messenger that inhibits axonal DA release, also via K-ATP channels. The source of dynamically generated H(2)O(2) is mitochondrial respiration; thus, H(2)O(2) provides a novel link between activity and metabolism via K-ATP channels. Additional targets of H(2)O(2) include transient receptor potential (TRP) channels. In contrast to the inhibitory effect of H(2)O(2) acting via K-ATP channels, TRP channel activation is excitatory. This review describes emerging roles of H(2)O(2) as a signaling agent in the nigrostriatal pathway and basal ganglia neurons. PMID:21666063

  1. Carbonate mineral solubility at low temperatures in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system

    NASA Astrophysics Data System (ADS)

    Marion, Giles M.

    2001-06-01

    Carbonate minerals have played an important role in the geochemical evolution of Earth, and may have also played an important role in the geochemical evolution of Mars and Europa. Several models have been published in recent years that describe chloride and sulfate mineral solubilities in concentrated brines using the Pitzer equations. Few of these models are parameterized for subzero temperatures, and those that are do not include carbonate chemistry. The objectives of this work are to estimate Pitzer-equation bicarbonate-carbonate parameters and carbonate mineral solubility products and to incorporate them into the FREZCHEM model to predict carbonate mineral solubilities in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system at low temperatures (≤25°C) with a special focus on subzero temperatures. Most of the Pitzer-equation parameters and equilibrium constants are taken from the literature and extrapolated into the subzero temperature range. Solubility products for 14 sodium, potassium, magnesium, and calcium bicarbonate and carbonate minerals are included in the model. Most of the experimental data are at temperatures ≥ -8°C; only for the NaHCO 3-NaCl-H 2O and Na 2CO 3-NaCl-H 2O systems are there bicarbonate and carbonate data to temperatures as low as -21.6°C. In general, the fit of the model to the experimental data is good. For example, calculated eutectic temperatures and compositions for NaHCO 3, Na 2CO 3, and their mixtures with NaCl and Na 2SO 4 salts are in good agreement with experimental data to temperatures as low as -21.6°C. Application of the model to eight saline, alkaline carbonate waters give predicted pHs ranging from 9.2 to 10.2, in comparison with measured pHs that range from 8.7 to 10.2. The model suggests that the CaCO 3 mineral that precipitates during seawater freezing is probably calcite and not ikaite. The model demonstrates that a proposed salt assemblage for the icy surface of Europa consisting of highly hydrated MgSO 4

  2. Reconstructing Final H2O Contents of Hydrated Rhyolitic Glasses: Insights into H2O Degassing and Eruptive Style of Silicic Submarine Volcanoes

    NASA Astrophysics Data System (ADS)

    McIntosh, I. M.; Nichols, A. R.; Tani, K.; Llewellin, E. W.

    2015-12-01

    H2O degassing influences the evolution of magma viscosity and vesicularity during ascent through the crust, and ultimately the eruptive style. Investigating H2O degassing requires data on both initial and final H2O contents. Initial H2O contents are revealed by melt inclusion data, while final H2O contents are found from dissolved H2O contents of volcanic glass. However volcanic glasses, particularly of silicic composition, are susceptible to secondary hydration i.e. the addition of H2O from the surrounding environment at ambient temperature during the time following pyroclast deposition. Obtaining meaningful final H2O data therefore requires distinguishing between the original final dissolved H2O content and the H2O added subsequently during hydration. Since H2O added during hydration is added as molecular H2O (H2Om), and the species interconversion between H2Om and hydroxyl (OH) species is negligible at ambient temperature, the final OH content of the glass remains unaltered during hydration. By using H2O speciation models to find the original H2Om content that would correspond to the measured OH content of the glass, the original total H2O (H2Ot) content of the glass prior to hydration can be reconstructed. These H2O speciation data are obtained using FTIR spectroscopy. In many cases, particularly where vesicular glasses necessitate thin wafers, OH cannot be measured directly and instead is calculated indirectly as OH = H2Ot - H2Om. Here we demonstrate the importance of using a speciation-dependent H2Ot molar absorptivity coefficient to obtain accurate H2Ot and H2O speciation data and outline a methodology for calculating such a coefficient for rhyolite glasses, with application to hydrated silicic pumice from submarine volcanoes in the Japanese Izu-Bonin Arc. Although hydrated pumice from Kurose Nishi and Oomurodashi now contain ~1.0 - 2.5 wt% H2Ot, their pre-hydration final H2O contents were typically ~0.3 - 0.4 wt% H2Ot. Furthermore, we show that pre

  3. H(2)O--N(2) collision-induced absorption band intensity in the region of the N(2) fundamental: ab initio investigation of its temperature dependence and comparison with laboratory data.

    PubMed

    Baranov, Yu I; Buryak, I A; Lokshtanov, S E; Lukyanchenko, V A; Vigasin, A A

    2012-06-13

    The present paper aims at ab initio and laboratory evaluation of the N(2) collision-induced absorption band intensity arising from interactions between N(2) and H(2)O molecules at wavelengths of around 4 μm. Quantum chemical calculations were performed in the space of five intermolecular coordinates and varying N--N bond length using Møller-Plesset perturbation and CCSD(T) methods with extrapolation of the electronic energy to the complete basis set. This made it possible to construct the intermolecular potential energy surface and to define the surface of the N--N dipole derivative with respect to internal coordinate. The intensity of the nitrogen fundamental was then calculated as a function of temperature using classical integration. Experimental spectra were recorded with a BOMEM DA3-002 FTIR spectrometer and 2 m base-length multipass White cell. Measurements were conducted at temperatures of 326, 339, 352 and 363 K. The retrieved water-nitrogen continuum significantly deviates from the MT_CKD model because the relatively strong nitrogen absorption induced by H(2)O was not included in this model. Substantial uncertainties in the measurements of the H(2)O-N(2) continuum meant that quantification of any temperature dependence was not possible. The comparison of the integrated N(2) fundamental band intensity with our theoretical estimates shows reasonably good agreement. Theory indicates that the intensity as a function of temperature has a minimum at approximately 500 K. PMID:22547239

  4. A comparison of ice VII formed in the H2O, NaCl-H2O, and CH3OH-H2O systems: Implications for H2O-rich planets

    NASA Astrophysics Data System (ADS)

    Frank, Mark R.; Aarestad, Elizabeth; Scott, Henry P.; Prakapenka, Vitali B.

    2013-02-01

    High-pressure H2O polymorphs, namely ice VI, ice VII, and ice X, are hypothesized to make up a considerable portion of the interiors of large icy satellites and select extra-solar planets. The incorporation of foreign ions or molecules into these high-pressure phases is possible through ocean-ice interaction, rock-ice interaction at depth, or processes that occurred during accretion. Recent research concerning the effects charged ions have on ice VII has shown that these ions notably affect the structure of ice VII (Frank et al., 2006; Klotz et al., 2009). This study was designed to determine the effects of a molecular impurity on ice VII and compare those effects to both pure H2O ice and ice with an ionic impurity. Ice samples were formed in this study via compression in a diamond anvil cell from either H2O, a 1.60 mol% NaCl aqueous solution, a 1.60 mol% CH3OH aqueous solution, or a 5.00 mol% CH3OH aqueous solution and were compressed up to 71 GPa at room temperature. Ice formed from pure H2O had no impurities whereas ices formed in the NaCl-H2O and CH3OH-H2O systems contained the impurities Na+ and Cl- and CH3OH, respectively. Pressure-volume relations were observed in situ by using synchrotron based X-ray diffraction and were used to determine the equations of state for ices formed in the H2O, NaCl-H2O and CH3OH-H2O systems. The data illustrate that ice VII formed from a NaCl-bearing aqueous solution exhibited a depressed volume when compared to that of H2O-only ice VII at any given pressure, whereas ice VII formed from CH3OH-bearing aqueous solutions showed an opposite trend, with an increase in volume relative to that of pure ice VII. The ices within planetary bodies will most likely have both ionic and molecular impurities and the trends outlined in this study can be used to improve density profiles of H2O-rich planetary bodies.

  5. The RealGas and RealGasH2O options of the TOUGH+ code for the simulation of coupled fluid and heat flow in tight/shale gas systems

    NASA Astrophysics Data System (ADS)

    Moridis, George J.; Freeman, Craig M.

    2014-04-01

    We developed two new EOS additions to the TOUGH+ family of codes, the RealGasH2O and RealGas. The RealGasH2O EOS option describes the non-isothermal two-phase flow of water and a real gas mixture in gas reservoirs, with a particular focus in ultra-tight (such as tight-sand and shale gas) reservoirs. The gas mixture is treated as either a single-pseudo-component having a fixed composition, or as a multicomponent system composed of up to 9 individual real gases. The RealGas option has the same general capabilities, but does not include water, thus describing a single-phase, dry-gas system. In addition to the standard capabilities of all members of the TOUGH+ family of codes (fully-implicit, compositional simulators using both structured and unstructured grids), the capabilities of the two codes include coupled flow and thermal effects in porous and/or fractured media, real gas behavior, inertial (Klinkenberg) effects, full micro-flow treatment, Darcy and non-Darcy flow through the matrix and fractures of fractured media, single- and multi-component gas sorption onto the grains of the porous media following several isotherm options, discrete and fracture representation, complex matrix-fracture relationships, and porosity-permeability dependence on pressure changes. The two options allow the study of flow and transport of fluids and heat over a wide range of time frames and spatial scales not only in gas reservoirs, but also in problems of geologic storage of greenhouse gas mixtures, and of geothermal reservoirs with multi-component condensable (H2O and CH4) and non-condensable gas mixtures. The codes are verified against available analytical and semi-analytical solutions. Their capabilities are demonstrated in a series of problems of increasing complexity, ranging from isothermal flow in simpler 1D and 2D conventional gas reservoirs, to non-isothermal gas flow in 3D fractured shale gas reservoirs involving 4 types of fractures, micro-flow, non-Darcy flow and gas

  6. The RealGas and RealGasH2O Options of the TOUGH+ Code for the Simulation of Coupled Fluid and Heat Flow in Tight/Shale Gas Systems

    SciTech Connect

    Moridis, George; Freeman, Craig

    2013-09-30

    We developed two new EOS additions to the TOUGH+ family of codes, the RealGasH2O and RealGas . The RealGasH2O EOS option describes the non-isothermal two-phase flow of water and a real gas mixture in gas reservoirs, with a particular focus in ultra-tight (such as tight-sand and shale gas) reservoirs. The gas mixture is treated as either a single-pseudo-component having a fixed composition, or as a multicomponent system composed of up to 9 individual real gases. The RealGas option has the same general capabilities, but does not include water, thus describing a single-phase, dry-gas system. In addition to the standard capabilities of all members of the TOUGH+ family of codes (fully-implicit, compositional simulators using both structured and unstructured grids), the capabilities of the two codes include: coupled flow and thermal effects in porous and/or fractured media, real gas behavior, inertial (Klinkenberg) effects, full micro-flow treatment, Darcy and non-Darcy flow through the matrix and fractures of fractured media, single- and multi-component gas sorption onto the grains of the porous media following several isotherm options, discrete and fracture representation, complex matrix-fracture relationships, and porosity-permeability dependence on pressure changes. The two options allow the study of flow and transport of fluids and heat over a wide range of time frames and spatial scales not only in gas reservoirs, but also in problems of geologic storage of greenhouse gas mixtures, and of geothermal reservoirs with multi-component condensable (H2O and CH4) and non-condensable gas mixtures. The codes are verified against available analytical and semi-analytical solutions. Their capabilities are demonstrated in a series of problems of increasing complexity, ranging from isothermal flow in simpler 1D and 2D conventional gas reservoirs, to non-isothermal gas flow in 3D fractured shale gas reservoirs involving 4 types of fractures, micro-flow, non-Darcy flow and gas

  7. Experimental study of the dehydration reactions gypsum-bassanite and bassanite-anhydrite at high pressure: Indication of anomalous behavior of H2O at high pressure in the temperature range of 50-300 °C

    NASA Astrophysics Data System (ADS)

    Mirwald, Peter W.

    2008-02-01

    The system CaSO4-H2O, characterized by the three dehydration reactions gypsum-anhydrite, gypsum-bassanite, and bassanite-anhydrite, was reexamined by in situ differential pressure analysis in the temperature range of 60-350°C up to 3.5GPa pressure. The investigation revealed a fine structure in the dehydration boundaries of gypsum-bassanite and bassanite-anhydrite, each characterized by three inflections at 0.9-1.0, 1.9-2.0, and 2.6-28GPa. In addition, the phase transition of anhydrite high pressure anhydrite (monazite structure) was established for the first time at high P-T conditions intersecting the bassanite-anhydrite dehydration boundary at 2.15GPa /250°C. Furthermore, the triple point gypsum-bassanite-anhydrite was redetermined with 235MPa/80.5°C. The evaluation of the gypsum-bassanite dehydration boundary with respect to the volume and entropy change of the reaction, ΔVreact and ΔSreact, by means of the Clausius-Clapeyron relation yields for the entropy parameter an unusually large increase over the range of the noted inflections. This is interpreted as anomalous entropy behavior of H2O related presumably to a dramatic increase in fluctuations of the hydrogen network of the liquid leading possibly into a new structural state. The effect is strongly related to the three noted pressure levels of 0.9-1.0, 1.9-2.0, and 2.6-28GPa. In a synopsis of data including also a previous high pressure study in the temperature range between 0 and 80°C, a tentative P-T diagram of H2O is proposed.

  8. LiOH - H2O2 - H2O trinary system study for the selection of optimal conditions of lithium peroxide synthesis

    NASA Astrophysics Data System (ADS)

    Nefedov, R. A.; Ferapontov, Yu A.; Kozlova, N. P.

    2016-01-01

    Using solubility method the decay kinetics of peroxide products contained in liquid phase of LiOH - H2O2 - H2O trinary system with 2 to 6% by wt hydrogen peroxide content in liquid phase in 21 to 33 °C temperature range has been studied. Conducted studies have allowed to determine temperature and concentration limits of solid phase existence of Li2O2·H2O content, distinctness of which has been confirmed using chemical and qualitative X- ray phase analysis. Stabilizing effect of solid phase of Li2O2·H2O content on hydrogen peroxide decay contained in liquid phase of LiOH - H2O2 - H2O trinary system under conditions of experiments conducted has been shown.

  9. Diode-laser measurements of linestrength and temperature-dependent lineshape parameters for H2O transitions near 1.4 μm using Voigt, Rautian, Galatry, and speed-dependent Voigt profiles

    NASA Astrophysics Data System (ADS)

    Goldenstein, Christopher S.; Hanson, Ronald K.

    2015-02-01

    Linestrengths and lineshapes for 7 H2O absorption transitions in the ν1 +ν3 combination band near 1.4 μm were measured at high resolution using tunable diode laser absorption. H2O- and N2-perturbed lineshapes were measured at 300-1300 K and 2-760 Torr and Voigt, Galatry, Rautian, and quadratic-speed-dependent-Voigt profiles were least-squares fit to measured spectra using a multi-spectrum fitting routine. Transitions with J ″ of 6-18 were studied to highlight the importance of collisional resonance and illustrate how the best-fit lineshape parameters varied with J ″. The accuracy of the Voigt profile decreased as J ″ increased (especially for J =Kc doublets). For transitions in N2, the collisional-broadening temperature exponents varied from ≈ 0.8 to -0.4 (for the Voigt profile) as J ″ increased and this behavior coincided with increasing speed-dependent collisional-broadening coefficients. The quadratic-speed-dependent Voigt profile was found to offer the best combination of accuracy and robust lineshape parameters; however, Rautian and Galatry profiles provided similar performance.

  10. Structural refinement of Nd[Fe(CN) 6]·4H 2O and study of NdFeO 3 obtained by its oxidative thermal decomposition at very low temperatures

    NASA Astrophysics Data System (ADS)

    Navarro, M. Carolina; Pannunzio-Miner, Elisa V.; Pagola, Silvina; Gómez, M. Inés; Carbonio, Raúl E.

    2005-03-01

    The crystal structure of Nd[Fe(CN) 6]·4H 2O has been refined by Rietveld analysis using high resolution synchrotron powder X-ray diffraction data. It belonged to the orthorhombic crystal system, Cmcm space group, with cell parameters: a=7.473952(1) Å, b=12.919104(2) Å and c=13.800549(2) Å. The change in space group from P6 3/ m which is observed in the pentahydrates (LnFe(CN) 6·5H 2O) to Cmcm in the tetrahydrates has been analyzed to be a consequence of the change in 9-fold coordination of Nd 3+ in the pentahydrates to 8-fold coordination in the tetrahydrates, which changes the Nd 3+ environment from tricapped trigonal prism to a distorted tricapped trigonal prism or square antiprism. Its decomposition process in air to produce NdFeO 3 has been followed by thermogravimetric and differential thermal analysis, IR spectroscopy and laboratory powder XRD. We found that it is possible to synthesize crystalline NdFeO 3 at temperatures as low as 380 °C and refine the structure of single phase crystalline NdFeO 3 synthesized by this method at 600 °C.

  11. Shocking H2O Ice: The Role of Phase Changes during Impact Crater Formation

    NASA Astrophysics Data System (ADS)

    Stewart, S. T.; Senft, L. E.; Seifter, A.; Obst, A. W.

    2008-12-01

    New experimental data and cratering calculations illustrate the complex response of H2O ice to shock compression. We present peak and post-shock temperature measurements from shocked H2O ice. In experiments with shock pressures between 8 and 14 GPa, initially ~150 K ice is compressed to a supercritical state. In the time frame of the experiment, the supercritical H2O releases to the saturation vapor curve and does not achieve full decompression. Further decompression requires a significant volume expansion. In general, the time scale of expansion will depend on the internal energy and the surrounding conditions (e.g., confined or unconfined). The temperature data validate a new 5-Phase hydrocode equation of state model for H2O, which includes ice Ih, VI, VII, liquid, and vapor. Using the 5-Phase EOS, we model impact cratering onto icy satellites. After passage of the impact-generated shock wave, material beneath the growing transient crater has a layered composition: vapor, liquid, high- pressure phases (ices VII and VI), and ice Ih. The high pressure phases cannot fully decompress without a large volume increase. Thus, these phases initially unload to the pressure along the phase boundary; this pressurized region affects the excavation flow field. The changes in crater excavation lead to differences in crater size and amount of ejecta compared to excavation in a homogeneous target. The differences are significant for large craters (e.g., complex craters on Ganymede and Callisto). The modified excavation flow field also concentrates highly shocked material in the crater floor. In cases where a large, hot plug is buried during crater collapse, explosions occur as the material cools by transforming to vapor, producing features similar to central pits observed on Ganymede, Callisto, and Mars. The behavior of shocked H2O ice during decompression should lead to a variety of features that depend on the ambient conditions specific to each icy planetary body.

  12. Synthesis, crystal structure and high temperature phase transition in the new organic-inorganic hybrid [N(C4H9)4]3Zn2Cl7H2O crystals

    NASA Astrophysics Data System (ADS)

    Ben Gzaiel, Malika; Oueslati, Abderrazek; Lhoste, Jérôme; Gargouri, Mohamed; Bulou, Alain

    2015-06-01

    The present paper accounts for the synthesis, crystal structure, differential scanning calorimetry and vibrational spectroscopy of a new compound tri-tetrabutylammonium heptachloro-dizincate (I) grown at room temperature by slow evaporation of aqueous solution. From X-ray diffraction data collected at room temperature, it is concluded that it crystallizes in the monoclinic system (P21/n space group) containing ZnCl42- and ZnCl3H2O1- tetrahedra. The atomic arrangement can be described by an alternation of organic and organic-inorganic layers stacked along the c direction. Differential scanning calorimetry (DSC) in the range 250-450 K disclosed a reversible structural phase transition of order-disorder type at 358 K, prior to the melting at 395 K. The temperature dependence of the Raman spectra of [N(C4H9)4]3Zn2Cl7H2O single crystals was studied in the spectral range 100-3500 cm-1 and for temperatures between 300 and 386 K. The most important changes are observed for the line at 261 cm-1 issued from ν1(ZnCl4). The analysis of the wavenumber, intensity and the line width based on an order-disorder model allowed to obtain information relative to the activation energy and the correlation length. The decrease of the activation energy with increasing temperature has been interpreted in term of a change in the re-orientation motion of the anionic parts. The assumption of cluster fluctuations also allowed the critical exponents to be obtained for the transition δ = 0.011 and the correlation length ξ0 = 598 Å.

  13. The airborne mass spectrometer AIMS - Part 1: AIMS-H2O for UTLS water vapor measurements

    NASA Astrophysics Data System (ADS)

    Kaufmann, S.; Voigt, C.; Jurkat, T.; Thornberry, T.; Fahey, D. W.; Gao, R.-S.; Schlage, R.; Schäuble, D.; Zöger, M.

    2015-12-01

    In the upper troposphere and lower stratosphere (UTLS), the accurate quantification of low water vapor concentrations has presented a significant measurement challenge. The instrumental uncertainties are passed on to estimates of H2O transport, cloud formation and the H2O role in the UTLS energy budget and resulting effects on surface temperatures. To address the uncertainty in UTLS H2O determination, the airborne mass spectrometer AIMS-H2O, with in-flight calibration, has been developed for fast and accurate airborne water vapor measurements. We present the new setup to measure water vapor by direct ionization of ambient air. Air is sampled via a backward facing inlet that includes a bypass flow to assure short residence times (< 0.2 s) in the inlet line, which allows the instrument to achieve a time resolution of ∼ 4 Hz. From the main inlet flow, a smaller flow is extracted into the novel pressure-controlled gas discharge ion source of the mass spectrometer. The air is directed through the gas discharge region where water molecules react to form hydronium ion clusters, H3O+(H2O)n (n= 0, 1, 2), in a complex reaction scheme similar to the reactions in the D-region of the ionosphere. These ions are counted to quantify the ambient water vapor mixing ratio. The instrument is calibrated during flight using a new calibration source based on the catalytic reaction of H2 and O2 on a Pt surface to generate a calibration standard with well defined and stable H2O mixing ratios. In order to increase data quality over a range of mixing ratios, two data evaluation methods are presented for lower and higher H2O mixing ratios respectively, using either only the H3O+(H2O) ions or the ratio of all water vapor dependent ions to the total ion current. Altogether, a range of water vapor mixing ratios from 1 to 500 ppmv (mole ratio, 10-6 mol mol-1) can be covered with an accuracy between 7 and 15 %. AIMS-H2O was deployed on two DLR research aircraft, the Falcon during CONCERT

  14. The airborne mass spectrometer AIMS - Part 1: AIMS-H2O for UTLS water vapor measurements

    NASA Astrophysics Data System (ADS)

    Kaufmann, Stefan; Voigt, Christiane; Jurkat, Tina; Thornberry, Troy; Fahey, David W.; Gao, Ru-Shan; Schlage, Romy; Schäuble, Dominik; Zöger, Martin

    2016-03-01

    In the upper troposphere and lower stratosphere (UTLS), the accurate quantification of low water vapor concentrations has presented a significant measurement challenge. The instrumental uncertainties are passed on to estimates of H2O transport, cloud formation and the role of H2O in the UTLS energy budget and resulting effects on surface temperatures. To address the uncertainty in UTLS H2O determination, the airborne mass spectrometer AIMS-H2O, with in-flight calibration, has been developed for fast and accurate airborne water vapor measurements. We present a new setup to measure water vapor by direct ionization of ambient air. Air is sampled via a backward facing inlet that includes a bypass flow to assure short residence times (< 0.2 s) in the inlet line, which allows the instrument to achieve a time resolution of ˜ 4 Hz, limited by the sampling frequency of the mass spectrometer. From the main inlet flow, a smaller flow is extracted into the novel pressure-controlled gas discharge ion source of the mass spectrometer. The air is directed through the gas discharge region where ion-molecule reactions lead to the production of hydronium ion clusters, H3O+(H2O)n (n = 0, 1, 2), in a complex reaction scheme similar to the reactions in the D-region of the ionosphere. These ions are counted to quantify the ambient water vapor mixing ratio. The instrument is calibrated during flight using a new calibration source based on the catalytic reaction of H2 and O2 on a Pt surface to generate a calibration standard with well-defined and stable H2O mixing ratios. In order to increase data quality over a range of mixing ratios, two data evaluation methods are presented for lower and higher H2O mixing ratios respectively, using either only the H3O+(H2O) ions or the ratio of all water vapor dependent ions to the total ion current. Altogether, a range of water vapor mixing ratios from 1 to 500 parts per million by volume (ppmv) can be covered with an accuracy between 7 and 15 %. AIMS-H

  15. Amorphous and Crystalline H2O-Ice

    NASA Astrophysics Data System (ADS)

    Mastrapa, Rachel M. E.; Grundy, William M.; Gudipati, Murthy S.

    On the surfaces of Solar System objects, H2O-ice can form in several different phases, including amorphous and crystalline. The stability of these phases as a function of thermal and radiation history is an active area of laboratory research. Meanwhile, remote detection of H2O-ice depends on the interpretation of infrared absorptions that are also dependent on phase and temperature. Surface processes, such as surface chemistry, micrometeorite gardening, and cryovolcanic resurfacing, on the surfaces of objects are linked to H2O-ice phase. We review the current state of laboratory measurements in the context of observations of Solar System objects and list the areas where new measurements are needed.

  16. Conductivity measurements on H2O-bearing CO2-rich fluids

    DOE PAGESBeta

    Capobianco, Ryan M.; Miroslaw S. Gruszkiewicz; Bodnar, Robert J.; Rimstidt, J. Donald

    2014-09-10

    Recent studies report rapid corrosion of metals and carbonation of minerals in contact with carbon dioxide containing trace amounts of dissolved water. One explanation for this behavior is that addition of small amounts of H2O to CO2 leads to significant ionization within the fluid, thus promoting reactions at the fluid-solid interface analogous to corrosion associated with aqueous fluids. The extent of ionization in the bulk CO2 fluid was determined using a flow-through conductivity cell capable of detecting very low conductivities. Experiments were conducted from 298 to 473 K and 7.39 to 20 MPa with H2O concentrations up to ~1600 ppmwmore » (xH2O ≈ 3.9 x 10-3), corresponding to the H2O solubility limit in liquid CO2 at ambient temperature. All solutions showed conductivities <10 nS/cm, indicating that the solutions were essentially ion-free. Furthermore, this observation suggests that the observed corrosion and carbonation reactions are not the result of ionization in CO2-rich bulk phase, but does not preclude ionization in the fluid at the fluid-solid interface.« less

  17. Destruction and Sequestration of H2O on Mars

    NASA Astrophysics Data System (ADS)

    Clark, Benton

    2016-07-01

    The availability of water in biologically useable form on any planet is a quintessential resource, even if the planet is in a zone habitable with temperature regimes required for growth of organisms (above -18 °C). Mars and most other planetary objects in the solar system do not have sufficient liquid water at their surfaces that photosynthesis or chemolithoautotrophic metabolism could occur. Given clear evidence of hydrous mineral alteration and geomorphological constructs requiring abundant supplies of liquid water in the past, the question arises whether this H2O only became trapped physically as ice, or whether there could be other, more or less accessible reservoirs that it has evolved into. Salts containing S or Cl appear to be ubiquitous on Mars, having been measured in soils by all six Mars landed missions, and detected in additional areas by orbital investigations. Volcanoes emit gaseous H2S, S, SO2, HCl and Cl2. A variety of evidence indicates the geochemical fate of these gases is to be transformed into sulfates, chlorides, chlorates and perchlorates. Depending on the gas, the net reaction causes the destruction of between one and up to eight molecules of H2O per atom of S or Cl (although hydrogen atoms are also released, they are lost relatively rapidly to atmospheric escape). Furthermore, the salt minerals formed often incorporate H2O into their crystalline structures, and can result in the sequestration of up to yet another six (sometimes, more) molecules of H2O. In addition, if the salts are microcrystalline or amorphous, they are potent adsorbents for H2O. In certain cases, they are even deliquescent under martian conditions. Finally, the high solubility of the vast majority of these salts (with notable exception of CaSO4) can result in dense brines with low water activity, aH, as well as cations which can be inimical to microbial metabolism, effectively "poisoning the well." The original geologic materials on Mars, igneous rocks, also provide some

  18. Interaction between sulphide and H 2O in silicate melts

    NASA Astrophysics Data System (ADS)

    Stelling, Jan; Behrens, Harald; Wilke, Max; Göttlicher, Jörg; Chalmin-Aljanabi, Emilie

    2011-06-01

    Reaction between dissolved water and sulphide was experimentally investigated in soda-lime-silicate (NCS) and sodium trisilicate (NS3) melts at temperatures from 1000 to 1200 °C and pressures of 100 or 200 MPa in internally heated gas pressure vessels. Diffusion couple experiments were conducted at water-undersaturated conditions with one half of the couple being doped with sulphide (added as FeS or Na 2S; 1500-2000 ppm S by weight) and the other with H 2O (˜3.0 wt.%). Additionally, two experiments were performed using a dry NCS glass cylinder and a free H 2O fluid. Here, the melt was water-saturated at least at the melt/fluid interface. Profiling by electron microprobe (sulphur) and infrared microscopy (H 2O) demonstrate that H 2O diffusion in the melts is faster by 1.5-2.3 orders of magnitude than sulphur diffusion and, hence, H 2O can be considered as a rapidly diffusing oxidant while sulphur is quasi immobile in these experiments. In Raman spectra a band at 2576 cm -1 appears in the sulphide - H 2O transition zone which is attributed to fundamental S-H stretching vibrations. Formation of new IR absorption bands at 5025 cm -1 (on expense of the combination band of molecular H 2O at 5225 cm -1) and at 3400 cm -1 was observed at the front of the in-diffusing water in the sulphide bearing melt. The appearance and intensity of these two IR bands is correlated with systematic changes in S K-edge XANES spectra. A pre-edge excitation at 2466.5 eV grows with increasing H 2O concentration while the sulphide peak at 2474.0 eV decreases in intensity relative to the peak at 2477.0 eV and the feature at 2472.3 eV becomes more pronounced (all energies are relative to the sulphate excitation, calibrated to 2482.5 eV). The observations by Raman, IR and XANES spectroscopy indicate a well coordinated S 2- - H 2O complex which was probably formed in the glasses during cooling at the glass transition. No oxidation of sulphide was observed in any of the diffusion couple

  19. Syngas production by thermochemical conversion of CO2 and H2O mixtures using a high-temperature heat pipe based reactor

    NASA Astrophysics Data System (ADS)

    Pearlman, Howard; Chen, Chien-Hua

    2012-10-01

    The design of a new high-temperature, solar-based reactor for thermochemical production of syngas using water and carbon dioxide will be discussed. The reactor incorporates the use of high-temperature heat pipe(s) that efficiently transfer the heat from a solar collector to a porous metal oxide material. Special attention is given to the thermal characteristics of the reactor, which are key factors affecting the overall system efficiency and amount of fuel produced. The thermochemical cycle that is considered is that for ceria based material. Preliminary data acquired from an early stage reactor, operated at temperatures up to 1100oC, is presented and efforts are now underway to increase the operating temperature of the reactor to 1300oC to further increase the efficiency of the thermochemical fuel production process.

  20. H2O2 space shuttle APU

    NASA Technical Reports Server (NTRS)

    1975-01-01

    A cryogenic H2-O2 auxiliary power unit (APU) was developed and successfully demonstrated. It has potential application as a minimum weight alternate to the space shuttle baseline APU because of its (1) low specific propellant consumption and (2) heat sink capabilities that reduce the amount of expendable evaporants. A reference system was designed with the necessary heat exchangers, combustor, turbine-gearbox, valves, and electronic controls to provide 400 shp to two aircraft hydraulic pumps. Development testing was carried out first on the combustor and control valves. This was followed by development of the control subsystem including the controller, the hydrogen and oxygen control valves, the combustor, and a turbine simulator. The complete APU system was hot tested for 10 hr with ambient and cryogenic propellants. Demonstrated at 95 percent of design power was 2.25 lb/hp-hr. At 10 percent design power, specific propellant consumption was 4 lb/hp-hr with space simulated exhaust and 5.2 lb/hp-hr with ambient exhaust. A 10 percent specific propellant consumption improvement is possible with some seal modifications. It was demonstrated that APU power levels could be changed by several hundred horsepower in less than 100 msec without exceeding allowable turbine inlet temperatures or turbine speed.

  1. Effect of Process Temperature and Reaction Cycle Number on Atomic Layer Deposition of TiO2 Thin Films Using TiCl4 and H2O Precursors: Correlation Between Material Properties and Process Environment

    NASA Astrophysics Data System (ADS)

    Chiappim, W.; Testoni, G. E.; de Lima, J. S. B.; Medeiros, H. S.; Pessoa, Rodrigo Sávio; Grigorov, K. G.; Vieira, L.; Maciel, H. S.

    2016-02-01

    The effect of process temperature and reaction cycle number on atomic layer-deposited TiO2 thin films onto Si(100) using TiCl4 and H2O precursors was investigated in order to discuss the correlation between the growth per cycle (GPC), film structure (crystallinity), and surface roughness as well as the dependence of some of these properties with gas phase environment such as HCl by-product. In this work, these correlations were studied for two conditions: (i) process temperatures in the range of 100-500 °C during 1000 reaction cycles and (ii) number of cycles in the range of 100-2000 for a fixed temperature of 250 °C. To investigate the material properties, Rutherford backscattering spectrometry (RBS), grazing incidence X-ray diffraction (GIXRD), and atomic force microscopy (AFM) techniques were used. Mass spectrometry technique was used to investigate the time evolution of gas phase species HCl and H2O during ALD process. Results indicate that the GPC does not correlate well with film crystallinity and surface roughness for the evaluated process parameters. Basically, the film crystallinity relies solely on grain growth kinetics of the material. This occurs due to higher HCl by-product content during each purge step. Furthermore, for films deposited at variable cycle number, the evolution of film thickness and elemental composition is altered from an initial amorphous structure to a near stoichiometric TiO2-x and, subsequently, becomes fully stoichiometric TiO2 at 400 cycles or above. At this cycle value, the GIXRD spectrum indicates the formation of (101) anatase orientation.

  2. Differential regulation of TRPV1 channels by H2O2: implications for diabetic microvascular dysfunction

    PubMed Central

    DelloStritto, Daniel J.; Connell, Patrick J.; Dick, Gregory M.; Fancher, Ibra S.; Klarich, Brittany; Fahmy, Joseph N.; Kang, Patrick T.; Chen, Yeong-Renn; Damron, Derek S.; Thodeti, Charles K.

    2016-01-01

    We demonstrated previously that TRPV1-dependent coupling of coronary blood flow (CBF) to metabolism is disrupted in diabetes. A critical amount of H2O2 contributes to CBF regulation; however, excessive H2O2 impairs responses. We sought to determine the extent to which differential regulation of TRPV1 by H2O2 modulates CBF and vascular reactivity in diabetes. We used contrast echocardiography to study TRPV1 knockout (V1KO), db/db diabetic, and wild type C57BKS/J (WT) mice. H2O2 dose-dependently increased CBF in WT mice, a response blocked by the TRPV1 antagonist SB366791. H2O2-induced vasodilation was significantly inhibited in db/db and V1KO mice. H2O2 caused robust SB366791-sensitive dilation in WT coronary microvessels; however, this response was attenuated in vessels from db/db and V1KO mice, suggesting H2O2-induced vasodilation occurs, in part, via TRPV1. Acute H2O2 exposure potentiated capsaicin-induced CBF responses and capsaicin-mediated vasodilation in WT mice, whereas prolonged luminal H2O2 exposure blunted capsaicin-induced vasodilation. Electrophysiology studies re-confirms acute H2O2 exposure activated TRPV1 in HEK293A and bovine aortic endothelial cells while establishing that H2O2 potentiate capsaicin-activated TRPV1 currents, whereas prolonged H2O2 exposure attenuated TRPV1 currents. Verification of H2O2-mediated activation of intrinsic TRPV1 specific currents were found in isolated mouse coronary endothelial cells from WT mice and decreased in endothelial cells from V1KO mice. These data suggest prolonged H2O2 exposure impairs TRPV1-dependent coronary vascular signaling. This may contribute to microvascular dysfunction and tissue perfusion deficits characteristic of diabetes. PMID:26907473

  3. Preformance Analysis of NH3-H2O Absorption Cycle

    NASA Astrophysics Data System (ADS)

    Tsujimori, Atsushi; Ozaki, Eiichi

    Different from H2O-LiBr absorption cycle, it is necessary to have rectifier between generator and condenser in NH3-H2O absorption cycle, because there mixes some steam in refrigerant vapor in the process of regenerating refrigerant from the ammonia strong aqueous solution. And in some case ex. partial load or heating, the efficiency of rectifier might decrease, if the flow rate of refrigerant vapor and ammonia aqueous solution decrease. As a result, steam flow into condenser with ammonia refrigerant vapor, which reduces cycle COPs of cooling and heating. Accordingly in order to evaluate the effect of ammonia concentration in refrigerant for the performance of NH3-H2O absorption heat pump, the simple design approach of modeling condenser and evaporator is introduced in this paper. In the model, the calculation of heat rate in condenser and evaporator was simplified considering the characteristic of NH3-H2O liquid-vapor equilibrium. Then the simulation for cycle perforance based on GAX absorption cycle was made using the efficiency of rectifier that established the ammonia concentration in refrigerant and it was derived that 3 [%] decrease of ammonia concentration in refrigerant induced 15 [%] decrcase of cooling COP and 7 [%] decrease of heating COP and that there existed the most suitable circulation ratio for each ammonia concentration in refrigerant.

  4. Microchannel Reactor System Design & Demonstration For On-Site H2O2 Production by Controlled H2/O2 Reaction

    SciTech Connect

    Adeniyi Lawal

    2008-12-09

    We successfully demonstrated an innovative hydrogen peroxide (H2O2) production concept which involved the development of flame- and explosion-resistant microchannel reactor system for energy efficient, cost-saving, on-site H2O2 production. We designed, fabricated, evaluated, and optimized a laboratory-scale microchannel reactor system for controlled direct combination of H2 and O2 in all proportions including explosive regime, at a low pressure and a low temperature to produce about 1.5 wt% H2O2 as proposed. In the second phase of the program, as a prelude to full-scale commercialization, we demonstrated our H2O2 production approach by ‘numbering up’ the channels in a multi-channel microreactor-based pilot plant to produce 1 kg/h of H2O2 at 1.5 wt% as demanded by end-users of the developed technology. To our knowledge, we are the first group to accomplish this significant milestone. We identified the reaction pathways that comprise the process, and implemented rigorous mechanistic kinetic studies to obtain the kinetics of the three main dominant reactions. We are not aware of any such comprehensive kinetic studies for the direct combination process, either in a microreactor or any other reactor system. We showed that the mass transfer parameter in our microreactor system is several orders of magnitude higher than what obtains in the macroreactor, attesting to the superior performance of microreactor. A one-dimensional reactor model incorporating the kinetics information enabled us to clarify certain important aspects of the chemistry of the direct combination process as detailed in section 5 of this report. Also, through mathematical modeling and simulation using sophisticated and robust commercial software packages, we were able to elucidate the hydrodynamics of the complex multiphase flows that take place in the microchannel. In conjunction with the kinetics information, we were able to validate the experimental data. If fully implemented across the whole

  5. The condensation and vaporization behavior of H2O:CO ices and implications for interstellar grains and cometary activity

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.; Allamandola, Louis J.

    1988-01-01

    IR spectroscopy has been used to ascertain several parameters associated with CO, H2O, and H2O:CO ices' physical behavior. Since CO is noted to be capable of condensing into H2O-rich ices at temperatures that are twice as high as those required for condensation in pure CO, CO is able to condense onto H2O-rich ice grains at temperatures of up to 50 K. CO's presence in H2O ice modestly enhances the effective volatility of the H2O. Attention is given to the implications of these results for cometary models generally and the question of cometary formation specifically.

  6. H2O beams for zinc oxide film growth produced by a Pt-catalyzed H2-O2 reaction at various divergent aperture angles of a de Laval nozzle

    NASA Astrophysics Data System (ADS)

    Teraguchi, Yusuke; Ishidzuka, Yuki; Nakamura, Tomoki; Takahashi, Kazumasa; Tamayama, Yasuhiro; Harada, Nobuhiro; Yasui, Kanji

    2016-02-01

    High-energy H2O beams generated by a de Laval nozzle, meant for the growth of zinc oxide thin films through chemical vapor deposition, were assessed based on compressible flow theory at various divergent aperture angles. In this process, high temperature H2O was generated by a catalytic reaction between H2 and O2 on Pt nanoparticles and effused through the nozzle into the reaction zone. The theoretical beam temperature distributions, reduced scaling parameters and mean cluster sizes of the H2O beams generated at angles between 50 and 90° were evaluated. The reduced scaling parameters of the H2O beams for all angles were calculated to be less than 200 and the mean cluster sizes were estimated to be less than one irrespective of the divergent aperture angle of the nozzle, suggesting that clusters are not formed in the H2O beam in our apparatus. The crystallinity and electrical properties of the zinc oxide films grown using various divergent aperture angles were also evaluated.

  7. A HIFI view on circumstellar H2O in M-type AGB stars: radiative transfer, velocity profiles, and H2O line cooling

    NASA Astrophysics Data System (ADS)

    Maercker, M.; Danilovich, T.; Olofsson, H.; De Beck, E.; Justtanont, K.; Lombaert, R.; Royer, P.

    2016-06-01

    Aims: We aim to constrain the temperature and velocity structures, and H2O abundances in the winds of a sample of M-type asymptotic giant branch (AGB) stars. We further aim to determine the effect of H2O line cooling on the energy balance in the inner circumstellar envelope. Methods: We use two radiative-transfer codes to model molecular emission lines of CO and H2O towards four M-type AGB stars. We focus on spectrally resolved observations of CO and H2O from HIFI aboard the Herschel Space Observatory. The observations are complemented by ground-based CO observations, and spectrally unresolved CO and H2O observations with PACS aboard Herschel. The observed line profiles constrain the velocity structure throughout the circumstellar envelopes (CSEs), while the CO intensities constrain the temperature structure in the CSEs. The H2O observations constrain the o-H2O and p-H2O abundances relative to H2. Finally, the radiative-transfer modelling allows to solve the energy balance in the CSE, in principle including also H2O line cooling. Results: The fits to the line profiles only set moderate constraints on the velocity profile, indicating shallower acceleration profiles in the winds of M-type AGB stars than predicted by dynamical models, while the CO observations effectively constrain the temperature structure. Including H2O line cooling in the energy balance was only possible for the low-mass-loss-rate objects in the sample, and required an ad hoc adjustment of the dust velocity profile in order to counteract extreme cooling in the inner CSE. H2O line cooling was therefore excluded from the models. The constraints set on the temperature profile by the CO lines nevertheless allowed us to derive H2O abundances. The derived H2O abundances confirm previous estimates and are consistent with chemical models. However, the uncertainties in the derived abundances are relatively large, in particular for p-H2O, and consequently the derived o/p-H2O ratios are not well constrained.

  8. Low-Temperature Polymorphic Phase Transition in a Crystalline Tripeptide l-Ala-l-Pro-Gly·H2O Revealed by Adiabatic Calorimetry

    PubMed Central

    Markin, Alexey V.; Markhasin, Evgeny; Sologubov, Semen S.; Ni, Qing Zhe; Smirnova, Natalia N.; Griffin, Robert G.

    2015-01-01

    We demonstrate application of precise adiabatic vacuun calorimetry to observation of phase transition in the tripeptide l-alanyl-l-prolyl-glycine monohydrate (APG) from 6 to 320 K and report the standard thermodynamic properties of the tripeptide in the entire range. Thus, the heat capacity of APG was measured by adiabatic vacuun calorimetry in the above temperature range. The tripeptide exhibits a reversible first-order solid-to-solid phase transition characterized by strong thermal hysteresis. We report the standard thermodynamic characteristics of this transition and show that differential scanning calorimetry can reliably characterize the observed phase transition with <5 mg of the sample. Additionally, the standard entropy of formation from the elemental substances and the standard entropy of hypothetical reaction of synthesis from the amino acids at 298.15 K were calculated for the studied tripeptide. PMID:25588051

  9. Absolute linestrengths in the H2O2 nu6 band

    NASA Technical Reports Server (NTRS)

    May, Randy D.

    1991-01-01

    Absolute linestrengths at 295 K have been measured for selected lines in the nu6 band of H2O2 using a tunable diode-laser spectrometer. H2O2 concentrations in a flowing gas mixture were determined by ultraviolet (uv) absorption at 254 nm using a collinear infrared (ir) and uv optical arrangement. The measured linestrengths are approx. 60 percent larger than previously reported values when absorption by hot bands in H2O2 is taken into account.

  10. Microwave-assisted wet digestion with H2O2 at high temperature and pressure using single reaction chamber for elemental determination in milk powder by ICP-OES and ICP-MS.

    PubMed

    Muller, Edson I; Souza, Juliana P; Muller, Cristiano C; Muller, Aline L H; Mello, Paola A; Bizzi, Cezar A

    2016-08-15

    In this work a green digestion method which only used H2O2 as an oxidant and high temperature and pressure in the single reaction chamber system (SRC-UltraWave™) was applied for subsequent elemental determination by inductively coupled plasma-based techniques. Milk powder was chosen to demonstrate the feasibility and advantages of the proposed method. Samples masses up to 500mg were efficiently digested, and the determination of Ca, Fe, K, Mg and Na was performed by inductively coupled plasma optical emission spectrometry (ICP-OES), while trace elements (B, Ba, Cd, Cu, Mn, Mo, Pb, Sr and Zn) were determined by inductively coupled plasma mass spectrometry (ICP-MS). Residual carbon (RC) lower than 918mgL(-1) of C was obtained for digests which contributed to minimizing interferences in determination by ICP-OES and ICP-MS. Accuracy was evaluated using certified reference materials NIST 1549 (non-fat milk powder certified reference material) and NIST 8435 (whole milk powder reference material). The results obtained by the proposed method were in agreement with the certified reference values (t-test, 95% confidence level). In addition, no significant difference was observed between results obtained by the proposed method and conventional wet digestion using concentrated HNO3. As digestion was performed without using any kind of acid, the characteristics of final digests were in agreement with green chemistry principles when compared to digests obtained using conventional wet digestion method with concentrated HNO3. Additionally, H2O2 digests were more suitable for subsequent analysis by ICP-based techniques due to of water being the main product of organic matrix oxidation. The proposed method was suitable for quality control of major components and trace elements present in milk powder in consonance with green sample preparation. PMID:27260458

  11. Global Flux Balance in the Terrestrial H2O Cycle: Reconsidering the Post-Arc Subducted H2O Flux

    NASA Astrophysics Data System (ADS)

    Parai, R.; Mukhopadhyay, S.

    2010-12-01

    Quantitative estimates of H2O fluxes between the mantle and the exosphere (i.e., the atmosphere, oceans and crust) are critical to our understanding of the chemistry and dynamics of the solid Earth: the abundance and distribution of water in the mantle has dramatic impacts upon mantle melting, degassing history, structure and style of convection. Water is outgassed from the mantle is association with volcanism at mid-ocean ridges, ocean islands and convergent margins. H2O is removed from the exosphere at subduction zones, and some fraction of the subducted flux may be recycled past the arc into the Earth’s deep interior. Estimates of the post-arc subducted H2O flux are primarily based on the stability of hydrous phases at subduction zone pressures and temperatures (e.g. Schmidt and Poli, 1998; Rüpke et al., 2004; Hacker, 2008). However, the post-arc H2O flux remains poorly quantified, in part due to large uncertainties in the water content of the subducting slab. Here we evaluate estimated post-arc subducted fluxes in the context of mantle-exosphere water cycling, using a Monte Carlo simulation of the global H2O cycle. Literature estimates of primary magmatic H2O abundances and magmatic production rates at different tectonic settings are used with estimates of the total subducted H2O flux to establish the parameter space under consideration. Random sampling of the allowed parameter space affords insight into which input and output fluxes satisfy basic constraints on global flux balance, such as a limit on sea-level change over time. The net flux of H2O between mantle and exosphere is determined by the total mantle output flux (via ridges and ocean islands, with a small contribution from mantle-derived arc output) and the input flux subducted beyond the arc. Arc and back-arc output is derived mainly from the slab, and therefore cancels out a fraction of the trench intake in an H2O subcycle. Limits on sea-level change since the end of the Archaean place

  12. The Successive H2O Binding Energies for Fe(H2O)n(+)

    NASA Technical Reports Server (NTRS)

    Ricca, Alessandra; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R. (Technical Monitor)

    1994-01-01

    The binding energy, computed using density functional theory (DFT), are in good agreement with experiment. The bonding is electrostatic (charge-dipole) in origin for all systems. The structures are therefore determined mostly by metal-ligand and ligand-ligand repulsion. The computed structure for FeH2O(+) is C(2v) where sp hybridization is important in reducing the Fe-H2O repulsion. Fe(H2O)2(+) has D2d symmetry where sdo hybridization is the primary factor leading to the linear O-Fe-O geometry. The bonding in Fe(H2O)3(+) and Fe(H2O)4(+) are very complex because ligand-ligand and metal-ligand repulsion, both for the in-plane and out-of-plane water lone-pair orbitals, are important.

  13. EPA H2O User Manual

    EPA Science Inventory

    EPA H2O is a software tool designed to support research being conducted in the Tampa Bay watershed to provide information, data, and approaches and guidance that communities can use to examine alternatives when making strategic decisions to support a prosperous and environmentall...

  14. EPA H2O Software Tool

    EPA Science Inventory

    EPA H2O allows user to: Understand the significance of EGS in Tampa Bay watershed; visually analyze spatial distribution of the EGS in Tampa Bay watershed; obtain map and summary statistics of EGS values in Tampa Bay watershed; analyze and compare potential impacts of development...

  15. The Formation and Spatiotemporal Progress of the pH Wave Induced by the Temperature Gradient in the Thin-Layer H2O2-Na2S2O3-H2SO4-CuSO4 Dynamical System.

    PubMed

    Jędrusiak, Mikołaj; Orlik, Marek

    2016-03-31

    The H2O2-S2O3(2-)-H(+)-Cu(2+) dynamical system exhibits sustained oscillations under flow conditions but reveals only a single initial peak of the indicator electrode potential and pH variation under batch isothermal conditions. Thus, in the latter case, there is no possibility of the coupling of the oscillations and diffusion which could lead to formation of sustained spatiotemporal patterns in this process. However, in the inhomogeneous temperature field, due to dependence of the local reaction kinetics on temperature, spatial inhomogeneities of pH distribution can develop which, in the presence of an appropriate indicator, thymol blue, manifest themselves as the color front traveling along the quasi-one-dimensional reactor. In this work, we describe the experimental conditions under which the above-mentioned phenomena can be observed and present their numerical model based on thermokinetic coupling and spatial coordinate introduced to earlier isothermal homogeneous kinetic mechanism. PMID:26938427

  16. The prediction of mineral solubilities in natural waters: A chemical equilibrium model for the NaKCaMgClSO 4H 2O system at temperatures below 25°C

    NASA Astrophysics Data System (ADS)

    Spencer, Ronald J.; Møller, Nancy; Weare, John H.

    1990-03-01

    A low temperature thermochemical model for the system NaKCaMgClSO 4H 2O is presented. Aqueous species and standard chemical potentials of solid-solution reactions are modeled from published data for binary and ternary solutions. The temperature range below 25°C (to near -60°C) is emphasized, although the model parameters are fitted to merge smoothly with those of higher temperature models at temperatures between 25 and 100°C. Binary and ternary specific ion interaction terms vary independently with temperature and are modeled using freezing point depression and mineral solubility measurements. The standard chemical potential of the ice-water reaction is fitted independent of the model (from vapor pressure and free energy data). Remaining standard chemical potentials of solidsolution reactions are fitted along with the specific ion interaction terms. Model predictions are tested against published data for minerals formed and brine compositions obtained by chilling seawater to the eutectic (about -54°C). The model predicts the sequence of solid phases observed to precipitate from chilled seawater (mice-mirabilite-hydrohalite-sylvite-MgCl 2 · 12H 2Oantarcticite). For all but mirabilite model temperatures are within the uncertainty of the measured temperature. The compositions of brines predicted by the model also closely follow the observed compositions. The model allows accurate predictions of the freezing points of simple and complex solutions in the system. Low temperature phase equilibria and mineral solubilities may also be predicted. The model may be used to determine the composition of brines in fluid inclusions in the multicomponent system based on low temperature phase equilibria.

  17. Crystal structures of hydrates of simple inorganic salts. II. Water-rich calcium bromide and iodide hydrates: CaBr2 · 9H2O, CaI2 · 8H2O, CaI2 · 7H2O and CaI2 · 6.5H2O.

    PubMed

    Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

    2014-09-01

    Single crystals of calcium bromide enneahydrate, CaBr(2) · 9H2O, calcium iodide octahydrate, CaI(2) · 8H2O, calcium iodide heptahydrate, CaI(2) · 7H2O, and calcium iodide 6.5-hydrate, CaI(2) · 6.5H2O, were grown from their aqueous solutions at and below room temperature according to the solid-liquid phase diagram. The crystal structure of CaI(2) · 6.5H2O was redetermined. All four structures are built up from distorted Ca(H2O)8 antiprisms. The antiprisms of the iodide hydrate structures are connected either via trigonal-plane-sharing or edge-sharing, forming dimeric units. The antiprisms in calcium bromide enneahydrate are monomeric. PMID:25186361

  18. Mesospheric H2O Concentrations Retrieved from SABER/TIMED Measurements

    NASA Technical Reports Server (NTRS)

    Feofilov, A. G.; Marshall, B. T.; Garcia-Comas, M.; Kutepov, A. A.; Lopez-Puertas, M.; Manuilova, R. O.; Yankovsky, V.A.; Goldberg, R. A.; Gordley, L. L.; Petelin, S.; Russell, J. M., III

    2008-01-01

    The SABER instrument on board the TIMED Satellite is a limb scanning infrared radiometer designed to measure temperature and minor constituent vertical profiles and energetics parameters in the mesosphere and lower thermosphere (MLT). The H2O concentrations are retrieved from 6.3 micron band radiances. The populations of H2O(v2) vibrational levels are in non-Local Thermodynamic Equilibrium (non-LTE) above approximately 55 km altitude and the interpretation of 6.3 micron radiance requires utilizing non-LTE H2O model that includes various energy exchange processes in the system of H2O vibrational levels coupled with O2, N2, and CO2 vibrational levels. We incorporated these processes including kinetics of O2/O3 photolysis products to our research non-LTE H2O model and applied it for the development and optimization of SABER operational model. The latter has been validated using simultaneous SCISAT1/ACE occultation measurements. This helped us to estimate CO2(020)-O2(X,v=I), O2(X,v=I)- H2O(010), and O2(X,v=1) O rates at mesopause temperatures that is critical for an adequate interpretation of non-LTE H2O radiances in the MLT. The first distributions of seasonal and meridional H2O concentrations retrieved from SABER 6.3 micron radiances applying an updated non-LTE H2O model are demonstrated and discussed.

  19. Silicate-H2O Systems at High Pressure Conditions

    NASA Astrophysics Data System (ADS)

    Tailby, N.; Mavrogenes, J. A.; Hermann, J.; O'Neill, H. S.

    2008-12-01

    Since the discovery of the second critical endpoint (CP2) in the albite-water system, numerous attempts have been made to determine the pressure and temperature of this CP2 and the mutual solubilities within more complex systems. The P-T position of the CP2 has been estimated for many systems: SiO2 (<10 kb/900 °C, Newton and Manning, 2008); NaAlSi3O8 (15 kb/800 °C, Burnham and Davis, 1974; Shen and Keppler, 1997); Pelite (50 kb/1,000 °C, Schmidt et al., 2004), basalt (50 kb/ 1000 °C, Kessel et al., 2004), Peridotite (38 kb/1000 °C, Mibe et al., 2007). A number of experimental techniques have been used to determine phase relations and H2O solubility in experiments. These include in-situ experimental techniques (e.g., HYDAC; Shen and Keppler, 1997), fluid trap techniques (e.g., diamond traps; Stalder et al., 2000), and single crystal weight-loss techniques (e.g., SiO2-H2O techniques employed by Newton and Manning, 2008). None of these techniques is without difficulties, as H2O rich experiments need to overcome huge retrograde fluid solubilities upon quench in order to determine mutual solubilities at experimental conditions. We have developed a new technique to determine "rock"-H2O relationships at high-P conditions, with particular focus on the shape and locus of solvi in pressure temperature space. In this series of experiments, an oxygen fugacity buffer (Re-ReO2) and a sliding H-fugacity sensor (NiO-Ni-Pd mixture) are combined to monitor H2O activity over the entire range of pressure and temperature. Unlike other techniques, the use of sensor capsules does not require textural interpretation of experiments. H2O activity is related to oxygen and hydrogen fugacity by the reaction: H2O = H2 + ½O2 NiO-Ni-Pd mixtures were placed within a ZrO2 jacket and sealed within a welded 2.3 mm Pt capsule. This 2.3 mm Pt sensor capsule was then encased within a larger, thick walled 6 mm diameter Ag capsule. Pelite-H2O mixtures and oxygen buffers were held within this larger

  20. Crystalline and amorphous H2O on Charon

    NASA Astrophysics Data System (ADS)

    Dalle Ore, Cristina M.; Cruikshank, Dale P.; Grundy, Will M.; Ennico, Kimberly; Olkin, Catherine B.; Stern, S. Alan; Young, Leslie A.; Weaver, Harold A.

    2015-11-01

    Charon, the largest satellite of Pluto, is a gray-colored icy world covered mostly in H2O ice, with spectral evidence for NH3, as previously reported (Cook et al. 2007, Astrophys. J. 663, 1406-1419 Merlin, et al. 2010, Icarus, 210, 930; Cook, et al. 2014, AAS/Division for Planetary Sciences Meeting Abstracts, 46, #401.04). Images from the New Horizons spacecraft reveal a surface with terrains of widely different ages and a moderate degree of localized coloration. The presence of H2O ice in its crystalline form (Brown & Calvin 2000 Science 287, 107-109; Buie & Grundy 2000 Icarus 148, 324-339; Merlin et al, 2010) along with NH3 is consistent with a fresh surface.The phase of H2O ice is a key tracer of variations in temperature and physical conditions on the surface of outer Solar System objects. At Charon’s surface temperature H2O is expected to be amorphous, but ground-based observations (e.g., Merlin et al. 2010) show a clearly crystalline signature. From laboratory experiments it is known that amorphous H2O ice becomes crystalline at temperatures of ~130 K. Other mechanisms that can change the phase of the ice from amorphous to crystalline include micro-meteoritic bombardment (Porter et al. 2010, Icarus, 208, 492) or resurfacing processes such as cryovolcanism.New Horizons observed Charon with the LEISA imaging spectrometer, part of the Ralph instrument (Reuter, D.C., Stern, S.A., Scherrer, J., et al. 2008, Space Science Reviews, 140, 129). Making use of high spatial resolution (better than 10 km/px) and spectral resolving power of 240 in the wavelength range 1.25-2.5 µm, and 560 in the range 2.1-2.25 µm, we report on an analysis of the phase of H2O ice on parts of Charon’s surface with a view to investigate the recent history and evolution of this small but intriguing object.This work was supported by NASA’s New Horizons project.

  1. Effects of H2O and H2O2 on Thermal Desorption of Tritium from Stainless Steel

    SciTech Connect

    Quinlan, M.J.; Shmayda, W.T.; Lim, S.; Salnikov, S.; Chambers, Z.; Pollock, E.; Schroder, W.U.

    2010-03-12

    Tritiated stainless steel was subjected to thermal desorption at various temperatures, different temperature profiles, and in the presence of different helium carrier gas additives. In all cases the identities of the desorbing tritiated species were characterized as either water-soluble or insoluble. The samples were found to contain 1.1 mCi±0.4 mCi. Approximately ninety-five percent of this activity was released in molecular water-soluble form. Additives of H2O or H2O2 to dry helium carrier gas increase the desorption rate and lower the maximum temperature to which the sample must be heated, in order to remove the bulk of the tritium. The measurements validate a method of decontamination of tritiated steel and suggest a technique that can be used to further explore the mechanisms of desorption from tritiated metals.

  2. Near Infrared Spectra of H2O/HCN Mixtures

    NASA Technical Reports Server (NTRS)

    Mastrapa, R. M.; Bernstein, M. P.; Sanford, S. A.

    2006-01-01

    Cassini's VIMS has already returned exciting results interpreting spectra of Saturn's icy satellites. The discovery of unidentified features possibly due to CN compounds inspired the work reported here. We wanted to test HCN as a possibility for explaining these features, and also explore how the features of HCN change when mixed with H2O. We have previously noted that mixing H20 and CO2 produces new spectral features and that those features change with temperature and mixing ratio.

  3. The system NaCl-H2O: relations of vapor-liquid near the critical temperature of water and of vapor-liquid-halite from 300° to 500°C

    USGS Publications Warehouse

    Bischoff, James L.; Rosenbauer, Robert J.; Pitzer, Kenneth S.

    1986-01-01

    Vapor-liquid relations (P-T-x) for the system NaCl-H2O were determined experimentally at temperatures spanning the critical temperature of water (Tc), the lowest temperature in the system at which critical behavior occurs. In addition, vapor-liquid-halite P-T-x(vapor) relations were determined from 300° to 500°C. Results show that at 373.0°C, immediately below Tc, the vapor side of the isothermal vaporliquid P-x boundary has a shape quite different from that previously conceived. The NaCl content of the vapor increases with pressure in a smooth manner from the pressure of the three-phase assemblage (135 bars, 0.0029% NaCl), to a pressure just below that of the vapor pressure of pure water (0.012% NaCl at 184 bars). Above this pressure the boundary abruptly reverses and projects asymptotically to 0% NaCl in a beak-like shape at 218 bars, the vapor pressure of pure water. At 375.5°, slightly above Tc, the asymptote disappears, and is replaced by a rounded nose. At progressively higher temperatures, the nose disappears and by 380°C the familiar symmetrical bell-shaped curve predominates with the critical point defined by the top of the bell. The P-T curve of the three-phase assemblage determined in the present study is in agreement with previous workers. The NaCl content of the three-phase vapor, however, is much higher than some literature values at temperatures above 410°C.

  4. H2O Adsorption on Smectites: Application to the Diurnal Variation of H2O in the Martian Atmosphere

    NASA Technical Reports Server (NTRS)

    Zent, Aaron P.; Howard, J.; Quinn, R. C.

    2000-01-01

    Observations of the Martian planetary boundary layer lead to interpretations that are baffling and contradictory. In this paper, we specifically address the question of whether or not water vapor finds a substantial diurnal reservoir in the Martian regolith. To address this issue, we have measured H2O adsorption kinetics on SWy-1, a Na-rich montmorillonite from Wyoming. The highest-temperature (273 K) data equilibrates rapidly. Data gathered at realistic H2O partial pressures and temperatures appropriate to early morning show two phenomena that preclude a significant role for smectites in diurnally exchanging a large column abundance. First, the equilibration timescale is longer than a sol. Second, the equilibrium abundances are a small fraction of that predicted by earlier adsorption isotherms. The explanation for this phenomenon is that smectite clay actually increases its surface area as a function of adsorptive coverage. At Mars-like conditions, we show that the interlayer sites of smectites are likely to be unavailable.

  5. The effect of H2O and CO2 on planetary mantles

    NASA Technical Reports Server (NTRS)

    Wyllie, P. J.

    1978-01-01

    The peridotite-H2O-CO2 system is discussed, and it is shown that even traces of H2O and CO2, in minerals or vapor, lower mantle solidus temperatures through hundreds of degrees in comparison with the volatile-free solidus. The solidus for peridotite-H2O-CO2 is a divariant surface traversed by univariant lines that locate the intersections of subsolidus divariant surfaces for carbonation or hydration reactions occurring in the presence of H2O-CO2 mixtures. Vapor phase compositions are normally buffered to these lines, and near the buffered curve for the solidus of partly carbonated peridotite there is a temperature maximum on the peridotite-vapor solidus. Characteristics on the CO2 side of the maximum and on the H2O side of the maximum are described.

  6. The Effect of H2O on Ice Photochemistry

    NASA Astrophysics Data System (ADS)

    Öberg, Karin I.; van Dishoeck, Ewine F.; Linnartz, Harold; Andersson, Stefan

    2010-08-01

    UV irradiation of simple ices is proposed to efficiently produce complex organic species during star formation and planet formation. Through a series of laboratory experiments, we investigate the effects of the H2O concentration, the dominant ice constituent in space, on the photochemistry of more volatile species, especially CH4, in ice mixtures. In the experiments, thin (~40 ML) ice mixtures, kept at 20-60 K, are irradiated under ultra-high vacuum conditions with a broadband UV hydrogen discharge lamp. Photodestruction cross sections of volatile species (CH4 and NH3) and production efficiencies of new species (C2H6, C2H4, CO, H2CO, CH3OH, CH3CHO, and CH3CH2OH) in water-containing ice mixtures are determined using reflection-absorption infrared spectroscopy during irradiation and during a subsequent slow warm-up. The four major effects of increasing the H2O concentration are: (1) an increase of the destruction efficiency of the volatile mixture constituent by up to an order of magnitude due to a reduction of back reactions following photodissociation, (2) a shift to products rich in oxygen, e.g., CH3OH and H2CO, (3) trapping of up to a factor of 5 more of the formed radicals in the ice, and (4) a disproportional increase in the diffusion barrier for the OH radical compared with the CH3 and HCO radicals. The radical diffusion temperature dependencies are consistent with calculated H2O-radical bond strengths. All the listed effects are potentially important for the production of complex organics in H2O-rich icy grain mantles around protostars and should thus be taken into account when modeling ice chemistry.

  7. The H2O2-H2O Hypothesis: Extremophiles Adapted to Conditions on Mars?

    NASA Astrophysics Data System (ADS)

    Houtkooper, Joop M.; Schulze-Makuch, Dirk

    2007-08-01

    The discovery of extremophiles on Earth is a sequence of discoveries of life in environments where it had been deemed impossible a few decades ago. The next frontier may be the Martian surface environment: could life have adapted to this harsh environment? What we learned from terrestrial extremophiles is that life adapts to every available niche where energy, liquid water and organic materials are available so that in principle metabolism and propagation are possible. A feasible adaptation mechanism to the Martian surface environment would be the incorporation of a high concentration of hydrogen peroxide in the intracellular fluid of organisms. The H2O2-H2O hypothesis suggests the existence of Martian organisms that have a mixture of H2O2 and H2O instead of salty water as their intracellular liquid (Houtkooper and Schulze-Makuch, 2007). The advantages are that the freezing point is low (the eutectic freezes at 56.5°C) and that the mixture is hygroscopic. This would enable the organisms to scavenge water from the atmosphere or from the adsorbed layers of water molecules on mineral grains, with H2O2 being also a source of oxygen. Moreover, below its freezing point the H2O2-H2O mixture has the tendency to supercool. Hydrogen peroxide is not unknown to biochemistry on Earth. There are organisms for which H2O2 plays a significant role: the bombardier beetle, Brachinus crepitans, produces a 25% H2O2 solution and, when attacked by a predator, mixes it with a fluid containing hydroquinone and a catalyst, which produces an audible steam explosion and noxious fumes. Another example is Acetobacter peroxidans, which uses H2O2 in its metabolism. H2O2 plays various other roles, such as the mediation of physiological responses such as cell proliferation, differentiation, and migration. Moreover, most eukaryotic cells contain an organelle, the peroxisome, which mediates the reactions involving H2O2. Therefore it is feasible that in the course of evolution, water-based organisms

  8. Transport properties of the H2O@C60-dimer-based junction.

    PubMed

    Zhu, Chengbo; Wang, Xiaolin

    2015-09-23

    Theoretical predictions play an important role in finding potential applications in molecular electronics. Fullerenes have a number of potential applications, and the charge flow from a single C60 molecule to another becomes more versatile and more interesting after doping. Here, we report the conductance of two H2O@C60 molecules in series order and how the number of encapsulated water molecules influences the transport properties of the junction. Encapsulating an H2O molecule into one of the C60 cages increases the conductance of the dimer. Negative differential resistance is found in the dimer systems, and its peak-to-valley current ratio depends on the number of encapsulated H2O molecules. The conductance of the C60 dimer and the H2O@C60 dimer is two orders of magnitude smaller than that of the C60 monomer. Furthermore, we demonstrate that the conductance of the molecular junctions based on the H2O@C60 dimer can be tuned by moving the encapsulated H2O molecules. The conductance is H2O-position dependent. Our findings indicate that H2O@C60 can be used as a building block in C60-based molecular electronic devices and sensors. PMID:26325223

  9. Transport properties of the H2O@C60-dimer-based junction

    NASA Astrophysics Data System (ADS)

    Zhu, Chengbo; Wang, Xiaolin

    2015-09-01

    Theoretical predictions play an important role in finding potential applications in molecular electronics. Fullerenes have a number of potential applications, and the charge flow from a single C60 molecule to another becomes more versatile and more interesting after doping. Here, we report the conductance of two H2O@C60 molecules in series order and how the number of encapsulated water molecules influences the transport properties of the junction. Encapsulating an H2O molecule into one of the C60 cages increases the conductance of the dimer. Negative differential resistance is found in the dimer systems, and its peak-to-valley current ratio depends on the number of encapsulated H2O molecules. The conductance of the C60 dimer and the H2O@C60 dimer is two orders of magnitude smaller than that of the C60 monomer. Furthermore, we demonstrate that the conductance of the molecular junctions based on the H2O@C60 dimer can be tuned by moving the encapsulated H2O molecules. The conductance is H2O-position dependent. Our findings indicate that H2O@C60 can be used as a building block in C60-based molecular electronic devices and sensors.

  10. Stepwise hydration of the cyanide anion: A temperature-controlled photoelectron spectroscopy and ab initio computational study of CN-(H2O)n(n=2-5)

    SciTech Connect

    Wang, Xue B.; Kowalski, Karol; Wang, Lai S.; Xantheas, Sotiris S.

    2010-03-28

    We report the study of microsolvated CN-(H2O)n (n = 1-5) clusters in the gas phase using a combination of experimental and computational approaches. The hydrated cyanide clusters were produced by electrospray and their structural and energetic properties were probed using temperature-controlled photoelectron spectroscopy (PES) and ab initio electronic structure calculations. Comparison between the low temperature (T = 12 K) and the room-temperature (RT) spectra shows a 0.25 eV spectral blue shift in the binding energy of the n = 1 cluster and a significant spectral sharpening and blue shift for n = 2 and 3. The experimental results are complemented with ab initio electronic structure calculations at the MP2 and CCSD(T) levels of theory that identified several isomers on the ground state potential energy function (PEF) arising from the ability of CN- to form hydrogen bonds with water via both the C and N ends. In all cases the N end seems to be the preferred hydration site. The excellent agreement between the low temperature measured PES spectra and the basis set- and correlation-corrected (at the CCSD(T) level of theory) calculated vertical detachment energies, viz. 3.85 vs. 3.84 eV (n = 0), 4.54 vs. 4.54 eV (n = 1), 5.20 vs. 5.32 eV (n = 2), 5.58 vs. 5.50 eV (n = 3) and 5.89 vs. 5.87 eV (n = 4), allow us to firmly establish the global minimum structures for all the hydrated cyanide clusters. The microsolvation pattern was found to be similar to the halide anions (Cl-, Br- and I-), adopting structures in which CN- resides on the surface of a water network. While at T = 12 K the clusters adopt structures that are close to the minimum energy configurations, at room temperature it is expected that other isomers (lying within ~0.6 kcal/mol above the global minima) are also populated, resulting in the broadening of the PES spectra.

  11. The discovery of five new H2O megamasers in active galaxies

    NASA Technical Reports Server (NTRS)

    Braatz, J. A.; Wilson, A. S.; Henkel, C.

    1994-01-01

    H2O megamasers with (isotropic) luminosities between 60 and 200 solar luminosity (H(sub 0) = 75 km/s/Mpc) have been detected in the Seyfert 2 galaxies Mrk 1, Mrk 1210, and NGC 5506 and in the LINERs NGC 1052 and NGC 2639. No megamasers have been found in Seyfert 1's. The galaxies have redshifts between 1500 and 4800 km/s and are the most distant H2O sources reported to date. NGC 1052 is also the first elliptical galaxy known to contain an H2O maser. The intensity distribution of an H2O five-point map obtained toward NGC 5506 shows that the H2O emission is pointlike compared to the 40 sec telescope beam. The lack of CO emission in NGC 1052 implies a conservative lower limit to the H2O brightness temperature of 1000 K, thus ruling out a thermal origin for the H2O emission. The success of this survey relative to other recent searches makes it evident that H2O megamasers are preferentially found in galaxies with active nuclei.

  12. High temperature kinetic study of the reactions H + O2 = OH + O and O + H2 = OH + H in H2/O2 system by shock tube-laser absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Ryu, Si-Ok; Hwang, Soon Muk; Dewitt, Kenneth J.

    1995-01-01

    The reactions: (1) H + O2 = OH + O; and (2) O + H2 = OH + H are the most important elementary reactions in gas phase combustion. They are the main chain-branching reaction in the oxidation of H2 and hydrocarbon fuels. In this study, rate coefficients of the reactions and have been measured over a wide range of composition, pressure, density and temperature behind the reflected shock waves. The experiments were performed using the shock tube - laser absorption spectroscopic technique to monitor OH radicals formed in the shock-heated H2/O2/Ar mixtures. The OH radicals were detected using the P(1)(5) line of (0,0) band of the A(exp 2) Sigma(+) from X(exp 2) Pi transition of OH at 310.023 nm (air). The data were analyzed with the aid of computer modeling. In the experiments great care was exercised to obtain high time resolution, linearity and signal-to-noise. The results are well represented by the Arrhenius expressions. The rate coefficient expression for reaction (1) obtained in this study is k(1) = (7.13 +/- 0.31) x 10(exp 13) exp(-6957+/- 30 K/T) cu cm/mol/s (1050 K less than or equal to T less than or equal to 2500 K) and a consensus expression for k(1) from a critical review of the most recent evaluations of k(1) (including our own) is k(1) = 7.82 x 10(exp 13) exp(-7105 K/T) cu cm/mol/s (960 K less than or equal to T less than or equal to 5300 K). The rate coefficient expression of k(2) is given by k(2) = (1.88 +/- 0.07) x 10(exp 14) exp(-6897 +/- 53 K/T) cu cm/mol/s (1424 K less than or equal to T less than or equal to 2427 K). For k(1), the temperature dependent A-factor and the correlation between the values of k(1) and the inverse reactant densities were not found. In the temperature range of this study, non-Arrhenius expression of k(2) which shows the upward curvature was not supported.

  13. Influence of monolayer amounts of HNO3 on the evaporation rate of H2O over ice in the range 179 to 208 K: a quartz crystal microbalance study.

    PubMed

    Delval, Christophe; Rossi, Michel J

    2005-08-18

    The evaporation flux J(ev) of H2O from thin H2O ice films containing between 0.5 and 7 monolayers of HNO3 has been measured in the range 179 to 208 K under both molecular and stirred flow conditions in isothermal experiments. FTIR absorption of the HNO3/H2O condensate revealed the formation of metastable alpha-NAT (HNO(3).3H2O) converting to stable beta-NAT at 205 K. After deposition of HNO3 for 16-80 s on a 1 mum thick pure ice film at a deposition rate in the range (6-60) x 10(12) molecules s(-1) the initial evaporative flux J(ev)(H2O) was always that of pure ice. J(ev)(H2O) gradually decreased with the evaporation of H2O and the concomitant increase of the average mole fraction of HNO3, chi(HNO3), indicating the presence of an amorphous mixture of H2O/HNO3 that is called complexed or (c)-ice whose vapor pressure is that of pure ice. The final value of J(ev) was smaller by factors varying from 2.7 to 65 relative to pure ice. Depending on the doping conditions and temperature of the ice film the pure ice thickness d(D) of the ice film for which J(ev) < 0.85J(ev)(pure ice) varied between 130 and 700 nm compared to the 1000 nm thick original ice film at 208 and 191 K, respectively, in what seems to be an inverse temperature dependence. There exist three different types of H2O molecules under the present experimental conditions, namely (a) free H2O corresponding to pure ice, (b) complexed H2O or c-ice, and (c) H2O molecules originating from the breakup of NAT or amorphous H2O/HNO3 mixtures. The significant decrease of J(ev)(H2O) with increasing chi(HNO3) leads to an increase of the evaporative lifetime of atmospheric ice particles in the presence of HNO3 and may help explain the occurrence of persistent and/or large contaminated ice particles at certain atmospheric conditions. PMID:16834079

  14. Optical Absorption and Photo-Thermal Conversion Properties of CuO/H2O Nanofluids.

    PubMed

    Wang, Liangang; Wu, Mingyan; Wu, Daxiong; Zhang, Canying; Zhu, Qunzhi; Zhu, Haitao

    2015-04-01

    Stable CuO/H2O nanofluids were synthesized in a wet chemical method. Optical absorption property of CuO/H2O nanofluids was investigated with hemispheric transmission spectrum in the wavelength range from 200 nm to 2500 nm. Photo-thermal conversion property of the CuO/H2O nanofluids was studied with an evaluation system equipped with an AUT-FSL semiconductor/solid state laser. The results indicate that CuO/H2O nanofluids have strong absorption in visible light region where water has little absorption. Under the irradiation of laser beam with a wavelength of 635 nm and a power of 0.015 W, the temperature of CuO/H2O nanofluids with 1.0% mass fraction increased by 5.6 °C within 40 seconds. Furthermore, the temperature elevation of CuO/H2O nanofluids was proved to increase with increasing mass fractions. On the contrast, water showed little temperature elevation under the identical conditions. The present work shows that the CuO/H2O nanofluids have high potential in the application as working fluids for solar utilization purpose. PMID:26353558

  15. Characterization of a real time H2O2 monitor for use in studies on H2O2 production by antibodies and cells.

    PubMed

    Sharma, Harish A; Balcavage, Walter X; Waite, Lee R; Johnson, Mary T; Nindl, Gabi

    2003-01-01

    It was recently shown that antibodies catalyze a reaction between water and ultraviolet light (UV) creating singlet oxygen and ultimately H2O2. Although the in vivo relevance of these antibody reactions is unclear, it is interesting that among a wide variety of non-antibody proteins tested, the T cell receptor is the only protein with similar capabilities. In clinical settings UV is believed to exert therapeutic effects by eliminating inflammatory epidermal T cells and we hypothesized that UV-triggered H2O2 production is involved in this process. To test the hypothesis we developed tools to study production of H2O2 by T cell receptors with the long-term goal of understanding, and improving, UV phototherapy. Here, we report the development of an inexpensive, real time H2O2 monitoring system having broad applicability. The detector is a Clark oxygen electrode (Pt, Ag/AgCl) modified to detect UV-driven H2O2 production. Modifications include painting the electrode black to minimize UV effects on the Ag/AgCl electrode and the use of hydrophilic, large pore Gelnots electrode membranes. Electrode current was converted to voltage and then amplified and recorded using a digital multimeter coupled to a PC. A reaction vessel with a quartz window was developed to maintain constant temperature while permitting UV irradiation of the samples. The sensitivity and specificity of the system and its use in cell-free and cell-based assays will be presented. In a cellfree system, production of H2O2 by CD3 antibodies was confirmed using our real time H2O2 monitoring method. Additionally we report the finding that splenocytes and Jurkat T cells also produce H2O2 when exposed to UV light. PMID:12724951

  16. Heterogeneous degradation of precipitated hexamine from wastewater by catalytic function of silicotungstic acid in the presence of H2O2 and H2O2/Fe2+.

    PubMed

    Taghdiri, Mehdi; Saadatjou, Naghi; Zamani, Navid; Farrokhi, Reyhaneh

    2013-02-15

    The industrial wastewater produced by hexamine plants is considered as a major environmental polluting factor due to resistance to biodegradation. So the treatment of such wastewater is required. In this work, the removal of hexamine from wastewater and its degradation have been studied. Hexamine was precipitated through formation of an insoluble and stable compound with silicotungstic acid. The oxidative heterogeneous degradation of precipitated hexamine was carried out with hydrogen peroxide (H(2)O(2)) aqueous solution and H(2)O(2)/Fe(2+) under the catalysis of silicotungstic acid. The operating conditions including amount of precipitate, hydrogen peroxide and ferrous ion dosage, temperature, time and pH were optimized by evaluating the removal of total organic carbon from system. A total organic carbon conversion higher than 70% was achieved in the presence of H(2)O(2)/Fe(2+). The experimental results showed that hexamine can be effectively degraded with H(2)O(2) and H(2)O(2)/Fe(2+) under the catalysis of silicotungstic acid. It was interesting that the solution of dissolved precipitate with H(2)O(2) can re-react with hexamine after the removal of excess hydrogen peroxide. This observation indicates the catalysis role of silicotungstic acid in the degradation of hexamine. A kinetic analysis based on total organic carbon reduction was carried out. The two steps mechanism was proposed for the degradation of hexamine. PMID:23313893

  17. Advanced H2/O2 space engine parametrics

    NASA Technical Reports Server (NTRS)

    Schneider, J. A.

    1989-01-01

    Engine cycle analyses conducted on a 3000-lbf component testing model of an H2/O2-fueled advanced orbit-transfer vehicle engine employing a dual-expander cycle have yielded pressure and temperature trend predictions. On the basis of the results obtained, the dual-expander cycle is projected to be scalable to thrust levels of as much as 50,000 lbf, with chamber pressures of 2000 psi. The high chamber pressure, in conjunction with the use of a gas-gas injector element, facilitates 10:1-range continuously variable throttling. The preferred thrust level for supporting mission studies would be of the order of 20,000 lbf.

  18. New Optical Constants of Amorphous and Crystalline H2O-ice, 3-20_m

    NASA Technical Reports Server (NTRS)

    Mastrapa, Rachel Michelle Elizab

    2008-01-01

    We will present new optical constants forth amorphous and crystalline H2O-ice in the spectral range 3-20 _m. Our new measurements provide high temperature resolution for crystalline H2O-ice, 10 K intervals from 20-150 K, including temperatures relevant to Solar System ices. We have found that the shape of the 3 _m feature in amorphous H2O-ice is strongly dependant on deposition temperature and the high and low density phases of amorphous H2O-ice are not easily distinguishable. We will present methods of measuring the change in band shape with phase and temperature. We acknowledge financial support from the NASA Origins of the Solar System Program and the NASA Planetary Geology and Geophysics Program.

  19. Competition between H2O and (H2O)2 reactions with CH2OO/CH3CHOO.

    PubMed

    Lin, Liang-Chun; Chang, Hung-Tzu; Chang, Chien-Hsun; Chao, Wen; Smith, Mica C; Chang, Chun-Hung; Jr-Min Lin, Jim; Takahashi, Kaito

    2016-02-14

    In this study, we performed ab initio calculations and obtained the bimolecular rate coefficients for the CH2OO/CH3CHOO reactions with H2O/(H2O)2. The energies were calculated with QCISD(T)/CBS//B3LYP/6-311+G(2d,2p) and the partition functions were estimated with anharmonic vibrational corrections by using the second order perturbation theory. Furthermore, we directly measured the rate of the CH2OO reaction with water vapor at high temperatures (348 and 358 K) to reveal the contribution of the water monomer in the CH2OO decay kinetics. We found that the theoretical rate coefficients reproduce the experimental results of CH2OO for a wide range of temperatures. For anti- (syn-) CH3CHOO, we obtained theoretical rate coefficients of 1.60 × 10(-11) (2.56 × 10(-14)) and 3.40 × 10(-14) (1.98 × 10(-19)) cm(3) s(-1) for water dimer and monomer reactions at room temperature. From the detailed analysis of the quantum chemistry and approximations for the thermochemistry calculations, we conclude that our calculated values would be within a factor of 3 of the correct values. Furthermore, at [H2O] = 1 × 10(17) to 5 × 10(17) cm(-3), we estimate that the effective first-order rate coefficients for CH2OO, anti- and syn-CH3CHOO reactions with water vapor will be ∼10(3), ∼10(4), and ∼10(1) s(-1), respectively. Thereby, for Criegee intermediates with a hydrogen atom on the same side as the terminal oxygen atom, the reaction with water vapor will likely dominate the removal processes of these CIs in the atmosphere. PMID:26797528

  20. Descent without Modification? The Thermal Chemistry of H2O2 on Europa and Other Icy Worlds.

    PubMed

    Loeffler, Mark J; Hudson, Reggie L

    2015-06-01

    The strong oxidant H2O2 is known to exist in solid form on Europa and is suspected to exist on several other Solar System worlds at temperatures below 200 K. However, little is known of the thermal chemistry that H2O2 might induce under these conditions. Here, we report new laboratory results on the reactivity of solid H2O2 with eight different compounds in H2O-rich ices. Using infrared spectroscopy, we monitored compositional changes in ice mixtures during warming. The compounds CH4 (methane), C3H4 (propyne), CH3OH (methanol), and CH3CN (acetonitrile) were unaltered by the presence of H2O2 in ices, showing that exposure to either solid H2O2 or frozen H2O+H2O2 at cryogenic temperatures will not oxidize these organics, much less convert them to CO2. This contrasts strongly with the much greater reactivity of organics with H2O2 at higher temperatures, and particularly in the liquid and gas phases. Of the four inorganic compounds studied, CO, H2S, NH3, and SO2, only the last two reacted in ices containing H2O2, NH3 making NH4+ and SO2 making SO(4)2- by H+ and e- transfer, respectively. An important astrobiological conclusion is that formation of surface H2O2 on Europa and that molecule's downward movement with H2O-ice do not necessarily mean that all organics encountered in icy subsurface regions will be destroyed by H2O2 oxidation. PMID:26060983

  1. Descent Without Modification? The Thermal Chemistry of H2O2 on Europa and Other Icy Worlds

    NASA Technical Reports Server (NTRS)

    Loeffler, Mark Josiah; Hudson, Reggie Lester

    2015-01-01

    The strong oxidant H2O2 is known to exist in solid form on Europa and is suspected to exist on several other Solar System worlds at temperatures below 200 K. However, little is known of the thermal chemistry that H2O2 might induce under these conditions. Here, we report new laboratory results on the reactivity of solid H2O2 with eight different compounds in H2O-rich ices. Using infrared spectroscopy, we monitored compositional changes in ice mixtures during warming. The compounds CH4 (methane), C3H4 (propyne), CH3OH (methanol), and CH3CN (acetonitrile) were unaltered by the presence of H2O2 in ices, showing that exposure to either solid H2O2 or frozen H2O+H2O2 at cryogenic temperatures will not oxidize these organics, much less convert them to CO2. This contrasts strongly with the much greater reactivity of organics with H2O2 at higher temperatures, and particularly in the liquid and gas phases. Of the four inorganic compounds studied, CO, H2S, NH3, and SO2, only the last two reacted in ices containing H2O2, NH3 making NHþ 4 and SO2 making SO2 4 by H+ and e - transfer, respectively. An important astrobiological conclusion is that formation of surface H2O2 on Europa and that molecule's downward movement with H2O-ice do not necessarily mean that all organics encountered in icy subsurface regions will be destroyed by H2O2 oxidation.

  2. Distribution and state of H2O in the high-latitude shallow subsurface of Mars

    NASA Technical Reports Server (NTRS)

    Zent, A. P.; Fanale, F. P.; Salvail, J. R.; Postawko, S. E.

    1986-01-01

    The state and distribution of H2O molecules at high latitudes are evaluated numerically with emphasis on the effects of seasonal temperatures on the kinetics of H2O transport. The investigation is carried out with a thermal model for the regolith regions from the surface through the ice interface and an atmospheric model for the H2O vapor density at the surface as a function of latitude. Few differences are found in the state and distribution of H2O whether the regolith is composed of Montmorillonite or basalt. During an obliquity cycle, the average exchanged H2O mass is determined to be in the range 1-20 gr/sq cm over the planetary surface, with a total maximum exchanged volume of 1500 cu km of H2O. The exchanged mass would arise mainly from ground ice in the case of a basalt regolith and from adsorbed H2O with Montmorillonite. Finally, seasonal ice stabilization is expected to occur at latitudes above 40 deg when obliquities exceed 25 deg.

  3. Electron swarm coefficients for H2O and H2O-N2

    NASA Astrophysics Data System (ADS)

    Juarez, A. M.; Basurto, E.; Hernandez-Avila, J. L.; de Urquijo, J.

    2008-10-01

    We have used a pulsed Townsend technique to measure the electron drift velocity ve, the density normalized longitudinal diffusion coefficient NDL, and effective ionization coefficient (α-η)/N, in water vapour and water vapour-nitrogen mixtures over the density-reduced electric field range E/N, 16-650 x 10-17V cm^2. The ve values are in good agreement with previous ones, while those for NDL agree well with a previous calculation. The limiting value for E/N was found to be E/Nlim=137 x 10-17 V cm^2. For E/N<70x10-17 V cm^2, the ve curves lie below that for pure N2; however, the 10% H2O-N2 curve for ve shows the trend for negative differential conductivity. The (α-η)/N curve for H2O shows a shallow, negative minimum, in disagreement with a recent measurement using the steady-state Townsend technique. The H2O-N2 curves for (α-η)/N show a progressively smaller minima, together with a trend to lower values of (α-η)/N as the N2 content in the mixture increases. This research aims to provide a complete set of self-consistent electron swarm parameters for the simulation of flue-gas discharges.

  4. Phase transitions in natural zeolites and the importance of P H2O

    NASA Astrophysics Data System (ADS)

    Bish, David L.; Wang, Hsiu-Wen

    2010-06-01

    Zeolites are low-density silicates with structures consisting of a negatively charged aluminosilicate framework that creates a system of uniform linked channels and cavities. Variable amounts of extraframework cations and H2O molecules occupy the channel system, and the H2O molecules are very responsive to changes in temperature, pressure and partial pressure of water (i.e. P H2O or relative humidity, RH). As the H2O molecules occupy much of the volume of the extraframework sites, a gain or loss of H2O molecules has a direct effect on the extraframework cations and an indirect effect on the framework. Temperature or RH-induced changes can result in both first- and second-order phase transitions, the latter resulting from continuous, minor changes in hydration state and cation position, and the former resulting from discrete changes in hydration state, which can cause similar shifts in cation position. Second-order transitions are typically reversible with no hysteresis, but first-order transitions exhibit considerable hysteresis. As H2O molecules are crucial in determining zeolite behavior, it is important that any study of thermal behavior involve control of not only temperature but also of relative humidity. Stabilization of a zeolite's hydrated phase to higher temperatures under higher RH conditions can cause some phase transitions to be missed, as is the case with natrolite.

  5. Dissolution of Quartz, Albite and K-feldspar Into H2O-Saturated Haplogranitic Melt at 800oC and 200 MPa: Diffusive Transport Properties of Granitic Melts at Crustal Anatectic Temperatures

    NASA Astrophysics Data System (ADS)

    Acosta, A.; London, D.; Dewers, T.; Morgan, G.

    2002-12-01

    With the aim of investigating the diffusive transport properties of granitic melts at crustal anatectic conditions and obtaining some constraints on speciation and coordination in the melt, we conducted albite, K-feldspar and quartz dissolution experiments in H2O-saturated metaluminous haplogranitic glass (nominal composition of the 200 MPa H2O-saturated haplogranite eutectic of Tuttle and Bowen, 1958) at 800oC and 200 MPa. Mineral and glass cylinders were juxtaposed against flat polished surfaces inside platinum or gold capsules, then run for durations in the range 120-960 h. Based on the time dependence of interface retreat dissolution is interface reaction-controlled up to 700 h, and becomes diffusion-controlled afterwards. Upon dissolution of albite, Al and Na entering the melt decouple and Na diffuses away from the interface to maintain a constant Al/Na molar ratio throughout the entire melt column. Potassium from the bulk melt diffuses uphill towards the albite-melt interface to maintain a constant Aluminum Saturation Index (ASI=molar Al2O3/Na2O+K2O) of 1.00 throughout the entire melt column. Dissolution of K-feldspar results in migration of K away from the interface and uphill diffusion of Na from the bulk melt towards the interface, again maintaining constant Al/Na and ASI ratios in the bulk melt. Dissolution of quartz produces enrichment in SiO2 versus dilution of the rest of components in the interface melt. These results indicate that in the five-component H2O-saturated metaluminous haplogranite system, uncoupled diffusion takes place along the following four directions in composition space: SiO2; Na2O; K2O; and a combination of Al2O3 and alkalis such that the Al/Na molar ratio is equal to that in the bulk melt, and the Al2O3/Na2O+K2O molar ratio is equal to the equilibrium ASI of the melt. These observations are in accord with results obtained from corundum and andalusite dissolution experiments in the same system and P-T-X conditions (Acosta-Vigil et

  6. [Relationships between H2O2 metabolism and Ca2+ transport in dormancy-breaking process of nectarine floral buds].

    PubMed

    Tan, Yue; Gao, Dong-sheng; Li, Ling; Wei, Hai-rong; Wang, Jia-wei; Liu, Qing-zhong

    2015-02-01

    In order to explore regulatory function of H2O2 in bud dormancy release, main effects of three dormancy-breaking treatments (high temperature, hydrogen cyanamide and TDZ) on H2O2 metabolism were determined, and impacts of H2O2 on Ca2+ transport were tested using non-invasive micro-test technique. The results showed that both high temperature and hydrogen cyanamide induced H2O2 accumulation and CAT inhibition were efficient in breaking dormancy during deep dormancy period. However, TDZ showed little impacts on H2O2 metabolism and was much less effective in breaking dormancy. Dormant floral primordium was absorbing state to exogenous Ca2+ due to active calcium channels. The Ca2+ transport could be changed by exogenous H2O2. H2O2 of low concentration reduced the absorption rate of Ca2+, and at high concentration, it changed the Ca2+ transport direction from absorption to release. The results indicated that H2O2 signals were related with Ca2+ signals in dormant buds. Ca2+ signal regulated by H2O2 accumulation might be important in the dormancy-breaking signal transduction process induced by high temperature and hydrogen cyanamide. PMID:26094456

  7. Vibrational and reorientational motions of H2O ligands, phase transition and thermal properties of [Sr(H2O)6]Cl2

    NASA Astrophysics Data System (ADS)

    Hetmańczyk, Joanna; Hetmańczyk, Łukasz; Migdał-Mikuli, Anna; Mikuli, Edward

    2013-11-01

    One phase transition (PT) at TCh = 252.9 K (on heating) and at TCc = 226.5 K (on cooling) was detected by DSC for [Sr(H2O)6]Cl2 in 123-295 K range. Thermal hysteresis of this PT equals to 26.4 K. Entropy change (ΔS) value at this first-order type phase transition equals to ca. 1.5 J mol-1 K-1. The temperature dependences of the full width at half maximum (FWHM) values of the infrared bands associated with ρt(H2O)E and δas(HOH)E modes (at ca. 417 and 1628 cm-1, respectively) suggest that the observed phase transition is associated with a sudden change of a speed of the H2O reorientational motions. The H2O ligands in the high temperature phase reorientate quickly (correlation times 10-11-10-13 s) with the activation energy of ca. 2 kJ mol-1. Below TCc probably a part of the H2O ligands stop their reorientation, while the remainders continue their fast reorientation but with the activation energy of ca. 8 kJ mol-1. Far and middle infrared spectra indicated characteristic changes at the vicinity of PT with decreasing of temperature, which suggested lowering of the crystal structure symmetry. Splitting of the band (at 3601 cm-1) connected with vas(OH) mode near the TCc suggests lowering of the crystal lattice symmetry. All these facts suggest that the discovered PT is connected both with a change of the reorientational dynamics of the H2O ligands and with the change of the crystal structure.

  8. Experimental determination of the H2O-undersaturated peridotite solidus

    NASA Astrophysics Data System (ADS)

    Sarafian, E. K.; Gaetani, G. A.; Hauri, E. H.; Sarafian, A. R.

    2014-12-01

    Knowledge of the H2O-undersaturated lherzolite solidus places important constraints on the process of melt generation and mantle potential temperatures beneath oceanic spreading centers. The small concentration of H2O (~50-200 μg/g) dissolved in the oceanic mantle is thought to exert a strong influence on the peridotite solidus, but this effect has not been directly determined. The utility of existing experimental data is limited by a lack of information on the concentration of H2O dissolved in the peridotite and uncertainties involved with identifying small amounts of partial melt. We have developed an experimental approach for determining the peridotite solidus as a function of H2O content that overcomes these difficulties. Our initial results demonstrate that the solidus temperature for spinel lherzolite containing 150 μg/g H2O is higher than existing estimates for the anhydrous solidus. Our approach to determining the H2O-undersaturated lherzolite solidus is as follows. First, a small proportion (~5 %) of San Carlos olivine spheres, ~300 μm in diameter, are added to a peridotite synthesized from high-purity oxides and carbonates. Melting experiments are then conducted in pre-conditioned Au80Pd20 capsules over a range of temperatures at a single pressure using a piston-cylinder device. Water diffuses rapidly in olivine resulting in thorough equilibration between the olivine spheres and the surrounding fine-grained peridotite, and allowing the spheres to be used as hygrometers. After the experiment, the concentration of H2O dissolved in the olivine spheres is determined by secondary ion mass spectrometry. Melting experiments, spaced 20°C apart, were performed from 1250 to 1430°C at 1.5 GPa. The starting material has the composition of the depleted MORB mantle of Workman and Hart (2005) containing 0.13 wt% Na2O and 150 µg/g H2O. The concentration of H2O in the olivine spheres remains constant up to 1350°C, and then decreases systematically with increasing

  9. Cross Talk between H2O2 and Interacting Signal Molecules under Plant Stress Response.

    PubMed

    Saxena, Ina; Srikanth, Sandhya; Chen, Zhong

    2016-01-01

    It is well established that oxidative stress is an important cause of cellular damage. During stress conditions, plants have evolved regulatory mechanisms to adapt to various environmental stresses. One of the consequences of stress is an increase in the cellular concentration of reactive oxygen species, which is subsequently converted to H2O2. H2O2 is continuously produced as the byproduct of oxidative plant aerobic metabolism. Organelles with a high oxidizing metabolic activity or with an intense rate of electron flow, such as chloroplasts, mitochondria, or peroxisomes are major sources of H2O2 production. H2O2 acts as a versatile molecule because of its dual role in cells. Under normal conditions, H2O2 immerges as an important factor during many biological processes. It has been established that it acts as a secondary messenger in signal transduction networks. In this review, we discuss potential roles of H2O2 and other signaling molecules during various stress responses. PMID:27200043

  10. Cross Talk between H2O2 and Interacting Signal Molecules under Plant Stress Response

    PubMed Central

    Saxena, Ina; Srikanth, Sandhya; Chen, Zhong

    2016-01-01

    It is well established that oxidative stress is an important cause of cellular damage. During stress conditions, plants have evolved regulatory mechanisms to adapt to various environmental stresses. One of the consequences of stress is an increase in the cellular concentration of reactive oxygen species, which is subsequently converted to H2O2. H2O2 is continuously produced as the byproduct of oxidative plant aerobic metabolism. Organelles with a high oxidizing metabolic activity or with an intense rate of electron flow, such as chloroplasts, mitochondria, or peroxisomes are major sources of H2O2 production. H2O2 acts as a versatile molecule because of its dual role in cells. Under normal conditions, H2O2 immerges as an important factor during many biological processes. It has been established that it acts as a secondary messenger in signal transduction networks. In this review, we discuss potential roles of H2O2 and other signaling molecules during various stress responses. PMID:27200043

  11. Tuning the conductance of H2O@C60 by position of the encapsulated H2O.

    PubMed

    Zhu, Chengbo; Wang, Xiaolin

    2015-01-01

    The change of conductance of single-molecule junction in response to various external stimuli is the fundamental mechanism for the single-molecule electronic devices with multiple functionalities. We propose the concept that the conductance of molecular systems can be tuned from inside. The conductance is varied in C60 with encapsulated H2O, H2O@C60. The transport properties of the H2O@C60-based nanostructure sandwiched between electrodes are studied using first-principles calculations combined with the non-equilibrium Green's function formalism. Our results show that the conductance of the H2O@C60 is sensitive to the position of the H2O and its dipole direction inside the cage with changes in conductance up to 20%. Our study paves a way for the H2O@C60 molecule to be a new platform for novel molecule-based electronics and sensors. PMID:26643873

  12. Tuning the conductance of H2O@C60 by position of the encapsulated H2O

    PubMed Central

    Zhu, Chengbo; Wang, Xiaolin

    2015-01-01

    The change of conductance of single-molecule junction in response to various external stimuli is the fundamental mechanism for the single-molecule electronic devices with multiple functionalities. We propose the concept that the conductance of molecular systems can be tuned from inside. The conductance is varied in C60 with encapsulated H2O, H2O@C60. The transport properties of the H2O@C60-based nanostructure sandwiched between electrodes are studied using first-principles calculations combined with the non-equilibrium Green’s function formalism. Our results show that the conductance of the H2O@C60 is sensitive to the position of the H2O and its dipole direction inside the cage with changes in conductance up to 20%. Our study paves a way for the H2O@C60 molecule to be a new platform for novel molecule-based electronics and sensors. PMID:26643873

  13. Tuning the conductance of H2O@C60 by position of the encapsulated H2O

    NASA Astrophysics Data System (ADS)

    Zhu, Chengbo; Wang, Xiaolin

    2015-12-01

    The change of conductance of single-molecule junction in response to various external stimuli is the fundamental mechanism for the single-molecule electronic devices with multiple functionalities. We propose the concept that the conductance of molecular systems can be tuned from inside. The conductance is varied in C60 with encapsulated H2O, H2O@C60. The transport properties of the H2O@C60-based nanostructure sandwiched between electrodes are studied using first-principles calculations combined with the non-equilibrium Green’s function formalism. Our results show that the conductance of the H2O@C60 is sensitive to the position of the H2O and its dipole direction inside the cage with changes in conductance up to 20%. Our study paves a way for the H2O@C60 molecule to be a new platform for novel molecule-based electronics and sensors.

  14. Absolute Infrared Cross Sections of Gas-Phase H2O2 Using Fourier Transform Mid-Infrared Spectroscopy

    SciTech Connect

    Johnson, Timothy J.; Blake, Thomas A.; Sams, Robert L.; Burton, Sarah D.

    2010-01-29

    We report quantitative spectra of pressure-broadened H2O2 vapor. An 83% solution was flowed into a disseminator and diluted with N2 gas; water lines were subtracted. The H2O2 spectrum spans the IR and compares well with HITRAN values for ν6 band.

  15. Drosophila TRPA1 isoforms detect UV light via photochemical production of H2O2

    PubMed Central

    Guntur, Ananya R.; Gu, Pengyu; Takle, Kendra; Chen, Jingyi; Xiang, Yang; Yang, Chung-Hui

    2015-01-01

    The transient receptor potential A1 (TRPA1) channel is an evolutionarily conserved detector of temperature and irritant chemicals. Here, we show that two specific isoforms of TRPA1 in Drosophila are H2O2 sensitive and that they can detect strong UV light via sensing light-induced production of H2O2. We found that ectopic expression of these H2O2-sensitive Drosophila TRPA1 (dTRPA1) isoforms conferred UV sensitivity to light-insensitive HEK293 cells and Drosophila neurons, whereas expressing the H2O2-insensitive isoform did not. Curiously, when expressed in one specific group of motor neurons in adult flies, the H2O2-sensitive dTRPA1 isoforms were as competent as the blue light-gated channelrhodopsin-2 in triggering motor output in response to light. We found that the corpus cardiacum (CC) cells, a group of neuroendocrine cells that produce the adipokinetic hormone (AKH) in the larval ring gland endogenously express these H2O2-sensitive dTRPA1 isoforms and that they are UV sensitive. Sensitivity of CC cells required dTRPA1 and H2O2 production but not conventional phototransduction molecules. Our results suggest that specific isoforms of dTRPA1 can sense UV light via photochemical production of H2O2. We speculate that UV sensitivity conferred by these isoforms in CC cells may allow young larvae to activate stress response—a function of CC cells—when they encounter strong UV, an aversive stimulus for young larvae. PMID:26443856

  16. Effects of Convective Ice Lofting on H2O and HDO in the Tropical Tropopause Layer

    NASA Technical Reports Server (NTRS)

    Dessler, A. E.; Hanisco, T. F.; Fueglistaler, S.

    2007-01-01

    We have added convective ice lofting to a Lagrangian trajectory model of near-tropopause water vapor (H2O) and its isotopologue HDO. The ice lofting simulation is based on a parameterization derived from Aura Microwave Limb Sounder (MLS) icewater content measurements. In previous papers, the Lagrangian model has accurately interannual and seasonal H2O abundances; there was no need for convection to be included in the model. We show here that this model does a poor job of simulating near-tropopause HDO, but that the addition of convective ice lofting greatly improves the HDO simulation. Convective ice lofting has a small effect on lower stratospheric H2O. H2O there is set by the minimum temperature encountered at the cold-point tropopause, so H2O added by convection below this level does not make it through this cold point and into the lower stratosphere. Thus, adding convection to the model does not degrade the model's previously demonstrated accurate simulations of H2O. We conclude that the HDO data suggest an important role for convective mass flux into the so-called tropical tropopause layer.

  17. Optimization of intermolecular potential parameters for the CO2/H2O mixture.

    PubMed

    Orozco, Gustavo A; Economou, Ioannis G; Panagiotopoulos, Athanassios Z

    2014-10-01

    Monte Carlo simulations in the Gibbs ensemble were used to obtain optimized intermolecular potential parameters to describe the phase behavior of the mixture CO2/H2O, over a range of temperatures and pressures relevant for carbon capture and sequestration processes. Commonly used fixed-point-charge force fields that include Lennard-Jones 12-6 (LJ) or exponential-6 (Exp-6) terms were used to describe CO2 and H2O intermolecular interactions. For force fields based on the LJ functional form, changes of the unlike interactions produced higher variations in the H2O-rich phase than in the CO2-rich phase. A major finding of the present study is that for these potentials, no combination of unlike interaction parameters is able to adequately represent properties of both phases. Changes to the partial charges of H2O were found to produce significant variations in both phases and are able to fit experimental data in both phases, at the cost of inaccuracies for the pure H2O properties. By contrast, for the Exp-6 case, optimization of a single parameter, the oxygen-oxygen unlike-pair interaction, was found sufficient to give accurate predictions of the solubilities in both phases while preserving accuracy in the pure component properties. These models are thus recommended for future molecular simulation studies of CO2/H2O mixtures. PMID:25198539

  18. Quantification of the production of hydrogen peroxide H2O2 during accelerated wine oxidation.

    PubMed

    Héritier, Julien; Bach, Benoît; Schönenberger, Patrik; Gaillard, Vanessa; Ducruet, Julien; Segura, Jean-Manuel

    2016-11-15

    Understanding how wines react towards oxidation is of primary importance. Here, a novel approach was developed based on the quantitative determination of the key intermediate H2O2 produced during accelerated oxidation by ambient oxygen. The assay makes use of the conversion of the non-fluorescent Amplex Red substrate into a fluorescent product in presence of H2O2. The total production of H2O2 during 30min was quantified with low within-day and between-day variabilities. Polymerized pigments, but not total polyphenols, played a major role in the determination of H2O2 levels, which were lower in white wines than red wines. H2O2 amounts also increased with temperature and the addition of metal ions, but did not depend on the concentration of many other wine constituents such as SO2. H2O2 levels did not correlate with anti-oxidant properties. We believe that this novel methodology might be generically used to decipher the oxidation mechanisms in wines and food products. PMID:27283717

  19. Heterogeneous distribution of H2O in the Martian interior: Implications for the abundance of H2O in depleted and enriched mantle sources

    NASA Astrophysics Data System (ADS)

    McCubbin, Francis M.; Boyce, Jeremy W.; Srinivasan, Poorna; Santos, Alison R.; Elardo, Stephen M.; Filiberto, Justin; Steele, Andrew; Shearer, Charles K.

    2016-04-01

    We conducted a petrologic study of apatite within 12 Martian meteorites, including 11 shergottites and one basaltic regolith breccia. These data were combined with previously published data to gain a better understanding of the abundance and distribution of volatiles in the Martian interior. Apatites in individual Martian meteorites span a wide range of compositions, indicating they did not form by equilibrium crystallization. In fact, the intrasample variation in apatite is best described by either fractional crystallization or crustal contamination with a Cl-rich crustal component. We determined that most Martian meteorites investigated here have been affected by crustal contamination and hence cannot be used to estimate volatile abundances of the Martian mantle. Using the subset of samples that did not exhibit crustal contamination, we determined that the enriched shergottite source has 36-73 ppm H2O and the depleted source has 14-23 ppm H2O. This result is consistent with other observed geochemical differences between enriched and depleted shergottites and supports the idea that there are at least two geochemically distinct reservoirs in the Martian mantle. We also estimated the H2O, Cl, and F content of the Martian crust using known crust-mantle distributions for incompatible lithophile elements. We determined that the bulk Martian crust has ~1410 ppm H2O, 450 ppm Cl, and 106 ppm F, and Cl and H2O are preferentially distributed toward the Martian surface. The estimate of crustal H2O results in a global equivalent surface layer (GEL) of ~229 m, which can account for at least some of the surface features on Mars attributed to flowing water and may be sufficient to support the past presence of a shallow sea on Mars' surface.

  20. Basalt Reactivity in the Presence of H2O-Saturated Supercritical CO2 Containing Gaseous Sulfur Compounds

    NASA Astrophysics Data System (ADS)

    Schaef, H. T.; McGrail, P.; Owen, A. T.

    2009-12-01

    Future impacts of climate change may be minimized by capture of emissions, primarily CO2 from fossil-fueled electric generating stations and subsequent sequestration in deep geologic formations. Injection of dry liquid CO2 into porous geologic reservoirs for long term storage is expected to eventually form a buoyant water-saturated bubble of supercritical fluid. Depending on purification processes and underground injection control regulations, the injected CO2 also could contain trace compounds associated with flue gas streams (SO2, N2, and O2). Once injected, the scCO2 will absorb water (1500 to 3000 ppmw) until becoming immobilized by reservoir trapping mechanisms. Reactivity of the water-bearing scCO2 with silicate minerals is relatively unknown and could have impacts on long term reservoir seal integrity and trapping by mineralization. To examine the reactivity of H2O-saturated scCO2, basalt experiments were conducted at pressures and temperatures relevant to geologic sequestration. Reaction products differed considerably depending on the gas mixtures used and type of basalt. In the presence of H2O-saturated CO2, the Newark Basin basalt reacted to produce secondary mineralization with needle-like morphologies and chemistries similar to aragonite. Exposing the same basalt to a CO2-H2S mixture (H2O saturated) produced two types of reaction products: carbonates in the form of small discrete nodules or needles and metallic-like circular areas similar in chemistry to pyrite and marcarsite. Tests conducted in the presence of CO2-SO2 produced the most extensive surface reaction products observed during the experiments. Some basalts were completely coated in white precipitate identified as a mixture of gypsum, sulfate bearing minerals (rozenite and melanterite), and a magnesium sulfate compound (MgSO4 ●5H2O). Hawaiian flow top basalts contained extensive reaction products including magnesium sulfate (MgSO4●6H2O), which formed on the large olivine crystals present

  1. Hormetic Effect of H2O2 in Saccharomyces cerevisiae

    PubMed Central

    Valishkevych, Bohdana V.

    2016-01-01

    In this study, we investigated the relationship between target of rapamycin (TOR) and H2O2-induced hormetic response in the budding yeast Saccharomyces cerevisiae grown on glucose or fructose. In general, our data suggest that: (1) hydrogen peroxide (H2O2) induces hormesis in a TOR-dependent manner; (2) the H2O2-induced hormetic dose–response in yeast depends on the type of carbohydrate in growth medium; (3) the concentration-dependent effect of H2O2 on yeast colony growth positively correlates with the activity of glutathione reductase that suggests the enzyme involvement in the H2O2-induced hormetic response; and (4) both TOR1 and TOR2 are involved in the reciprocal regulation of the activity of glucose-6-phosphate dehydrogenase and glyoxalase 1. PMID:27099601

  2. Influence of H2O Rich Fluid Inclusions on Quartz Deformation

    NASA Astrophysics Data System (ADS)

    Thust, Anja; Heilbronner, Renée.; Stünitz, Holger; Tarantola, Alexandre; Behrens, Harald

    2010-05-01

    The effect of H2O on the strength of quartz is well known and has been discussed many times in the literature (e.g. Griggs & Blacic 1965, Kronenberg 1994). In this project we study the H2O interactions between natural dry quartz and H2O rich fluid inclusions during deformation in the solid medium Griggs apparatus. High pressure and temperature experiments were carried out using a quartz single crystal containing a large number of H2O-rich fluid inclusions. Adjacent to the fluid inclusions the crystal is essentially dry (< 100 H/106Si, as determined by FTIR). Two sample orientations where used: (1) ⊥{m} orientation: normal to one of the prism planes, (2) O+ orientation: 45° to and 45° to [c]. Confining pressures were 700 MPa, 1000 MPa and 1500 MPa, with a constant displacement rate of 10-6 s-1 and a constant temperature of 900° C. Additionally, experiments where carried out at lower temperatures (800° C, 700° C) and faster strain rate ( 10-5 s-1). During increasing pressure and temperature we remained close to the fluid inclusion isochore and exceeded the α - β transition as late as possible. The strengths of the majority of the samples are between 150 and 250 MPa (the weakest is 84 MPa, the strongest 414 MPa). Low strength can be explained by dynamic recrystallization and deformation by dislocation creep, higher strength correlates with a lower H2O content and absence of dislocation creep. In the undeformed material, the H2O rich fluid inclusions contain different chlorides like antarticite (CaCl2×6H2O) and hydrohalite (NaCl×2H2O), as measured with micro thermometry. They show a large range in size from 50 μm to 700 μm and their spatial distribution is extremely heterogeneous. After deformation the inclusions are more homogeneously distributed throughout the sample and dramatically reduced in size (< 0.1μm). Regions with a high density of very small fluid inclusions are the regions with the highest concentration of deformation and yield an H2O content

  3. Experimental determination of the solubility constant for magnesium chloride hydroxide hydrate (Mg 3Cl(OH) 5·4H 2O, phase 5) at room temperature, and its importance to nuclear waste isolation in geological repositories in salt formations

    NASA Astrophysics Data System (ADS)

    Xiong, Yongliang; Deng, Haoran; Nemer, Martin; Johnsen, Shelly

    2010-08-01

    In this study, the solubility constant of magnesium chloride hydroxide hydrate, Mg 3Cl(OH) 5·4H 2O, termed as phase 5, is determined from a series of solubility experiments in MgCl 2-NaCl solutions. The solubility constant in logarithmic units at 25 °C for the following reaction, MgCl(OH)·4HO+5H=3Mg+9HO(l)+Cl is calculated as 43.21 ± 0.33 (2 σ) based on the specific interaction theory (SIT) model for extrapolation to infinite dilution. The Gibbs free energy and enthalpy of formation for phase 5 at 25 °C are derived as -3384 ± 2 (2 σ) kJ mol -1 and -3896 ± 6 (2 σ) kJ mol -1, respectively. MgO (bulk, pure MgO corresponding to the mineral periclase) is the only engineered barrier certified by the Environmental Protection Agency (EPA) for emplacement in the Waste Isolation Pilot Plant (WIPP) in the US, and an Mg(OH) 2-based engineered barrier (bulk, pure Mg(OH) 2 corresponding to brucite) is to be employed in the Asse repository in Germany. Phase 5, and its similar phase, phase 3 (Mg 2Cl(OH) 3·4H 2O), could have a significant role in influencing the geochemical conditions in geological repositories for nuclear waste in salt formations where MgO or brucite is employed as engineered barriers. Based on our solubility constant for phase 5 in combination with the literature value for phase 3, we predict that the composition for the invariant point of phase 5 and phase 3 would be mMg = 1.70 and pmH = 8.94 in the Mg-Cl binary system. The recent WIPP Compliance Recertification Application Performance Assessment Baseline Calculations indicate that phase 5, instead of phase 3, is indeed a stable phase when the WIPP Generic Weep Brine (GWB), a Na-Mg-Cl-dominated brine associated with the Salado Formation, equilibrates with actinide-source-term phases, brucite, magnesium carbonates, halite and anhydrite. Therefore, phase 5 is important to the WIPP, and potentially important to other repositories in salt formations.

  4. Direct N2H4/H2O2 Fuel Cells Powered by Nanoporous Gold Leaves

    PubMed Central

    Yan, Xiuling; Meng, Fanhui; Xie, Yun; Liu, Jianguo; Ding, Yi

    2012-01-01

    Dealloyed nanoporous gold leaves (NPGLs) are found to exhibit high electrocatalytic properties toward both hydrazine (N2H4) oxidation and hydrogen peroxide (H2O2) reduction. This observation allows the implementation of a direct hydrazine-hydrogen peroxide fuel cell (DHHPFC) based on these novel porous membrane catalysts. The effects of fuel and oxidizer flow rate, concentration and cell temperature on the performance of DHHPFC are systematically investigated. With a loading of ~0.1 mg cm−2 Au on each side, an open circuit voltage (OCV) of 1.2 V is obtained at 80°C with a maximum power density 195 mW cm−2, which is 22 times higher than that of commercial Pt/C electrocatalyst at the same noble metal loading. NPGLs thus hold great potential as effective and stable electrocatalysts for DHHPFCs. PMID:23230507

  5. Crystal structures of hydrates of simple inorganic salts. III. Water-rich aluminium halide hydrates: AlCl3 · 15H2O, AlBr3 · 15H2O, AlI3 · 15H2O, AlI3 · 17H2O and AlBr3 · 9H2O.

    PubMed

    Schmidt, Horst; Hennings, Erik; Voigt, Wolfgang

    2014-09-01

    Water-rich aluminium halide hydrate structures are not known in the literature. The highest known water content per Al atom is nine for the perchlorate and fluoride. The nonahydrate of aluminium bromide, stable pentadecahydrates of aluminium chloride, bromide and iodide, and a metastable heptadecahydrate of the iodide have now been crystallized from low-temperature solutions. The structures of these hydrates were determined and are discussed in terms of the development of cation hydration spheres. The pentadecahydrate of the chloride and bromide are isostructural. In AlI(3) · 15H2O, half of the Al(3+) cations are surrounded by two complete hydration spheres, with six H2O in the primary and 12 in the secondary. For the heptadecahydrate of aluminium iodide, this hydration was found for every Al(3+). PMID:25186362

  6. Phase Separation Kinetics in Isopycnic Mixtures of H2O/CO2/Ethoxylated Alcohol Surfactants

    NASA Technical Reports Server (NTRS)

    Lesemann, Markus; Paulaitis, Michael E.; Kaler, Eric W.

    1999-01-01

    Ternary mixtures of H2O and CO2 with ethoxylated alcohol (C(sub i)E(sub j)) surfactants form three coexisting liquid phases at conditions where two of the phases have equal densities (isopycnic phases). Isopycnic phase behavior has been observed for mixtures containing C8E5, C10E6, and C12E6 surfactants, but not for those mixtures containing either C4E1 or C8E3 surfactants. Pressure-temperature (PT) projections for this three-phase equilibrium were determined for H2O/CO2/C8E5 and H2O/CO2/C10E6 mixtures at temperatures from approximately 25 to 33 C and pressures between 90 and 350 bar. Measurements of the microstructure in H2O/CO2/C12E6 mixtures as a function of temperature (25-31 C), pressure (63.1-90.7 bar), and CO2 composition (0-3.9 wt%) have also been carried out to show that while micellar structure remains essentially un-changed, critical concentration fluctuations increase as the phase boundary and plait point are approached. In this report, we present our first measurements of the kinetics of isopycnic phase separation for ternary mixtures of H2O/CO2/C8E5.

  7. High pressure experimental study of eclogite with varying H2O contents

    NASA Astrophysics Data System (ADS)

    Rosenthal, A.; Frost, D. J.; Petitgirard, S.; Yaxley, G. M.; Berry, A.; Woodland, A. B.; Pinter, Z.; Vasilyev, P.; Ionov, D. A.; Jacob, D. E.; Pearson, G. D.; Kovacs, I.; Padron-Navarta, A.

    2014-12-01

    Given the strong influence of volatiles on mantle melting processes, it is critical to understand the behaviour of volatiles (such as H2O) in subducted oceanic crustal material (eclogite) during subduction and subsequent recycling and mantle melting processes, and their impacts on volcanism. As natural samples from subduction zones from the deep Earth's interior are largely inaccessible, the only way to determine the H2O content of eclogite is to simulate high pressure (P) and temperature (T) conditions equivalent to conditions of the Earth's interior using high-P experimental facilities. A particular interest is to determine the H2O content of eclogitic nominally anhydrous minerals (NAMs; such as garnet, clinopyroxene) at the conditions where hydrous phases (such as phengite) are breaking down to release H2O that would then leave the slab. As a starting material, we use average oceanic basalt (GA1, representative of recycled oceanic crust [1]) with varying bulk %H2O (≤7 wt.%). We conducted experiments using GA1 at different P's (6-10 GPa), T's (850-1500°C) and bulk %H2O (up to 7 wt.%) using multi anvil apparatuses. The run products at each P, T, and bulk H2O contents show well-equilibrated eclogitic phase assemblages of garnet ± clinopyroxene ± coesite/stishovite ± rutile ± phengite ± melt ± vapour. Runs (>0.5 wt.% H2O) at 6 GPa and up to ~950°C, and at 8-9 GPa and up to ~1050°C are subsolidus, while towards higher T small melt fractions appear. Similar to previous studies [e.g. 2-6], the stability of phengite varies as a function of P, T, buffering mineral paragenesis and bulk H2O concentration. Phengite breaks down >9 GPa. Eclogitic NAMs and phengite also break down at subsolidus conditions in the presence of excess of hydrous fluids. For instance, K2O in phengite and clinopyroxene decrease with increasing bulk H2O content at subsolidus conditions at given P, T, suggesting a leaching role of K2O by a vapour-rich fluid. [1] Yaxley, G. M. & Green, D. H

  8. Observations of H2O in Titan's atmosphere with Herschel

    NASA Astrophysics Data System (ADS)

    Moreno, R.; Lellouch, E.; Lara, L. M.; Courtin, R.; Hartogh, P.; Rengel, M.

    2012-04-01

    Disk averaged observations of several H2O far infrared lines in Titan’s atmosphere were performed with the Herschel Space Observatory, as part of the guaranteed time key program "Water and related chemistry in the Solar System" (HssO, see Hartogh et al 2011). Two instruments were used: (i) HIFI, a heterodyne instrument (R~ 106 ) in the sub-millimeter, which measured the H2O(110-101) rotational transition at 557 GHz on June 10 and Dec. 31, 2010 (ii) PACS, a photoconductor spectrometer (R~103) which measured three water lines at 108.1, 75.4 and 66.4 microns on June 22, 2010. Additional PACS measurements at 66.4 microns on Dec. 15 and 22, 2010 and on July 09, 2011, do not show any significant line intensity variation with time, nor between the leading/trailing sides (i.e. longitude). Spectra were analyzed with a line-by-line radiative transfer code accounting for spherical geometry (Moreno et al. 2011). This model considers the H2O molecular opacity from JPL catalog (Pickett et al. 1998) and also includes collision-induced opacities N2-N2, N2-CH4 and CH4-CH4 (Borysow and Frommhold 1986, 1987, Borysow and Tang 1993). Far infrared aerosol opacities derived by CIRS were included, following Anderson and Samuelson (2011) for their vertical distribution and spectral dependencies. Analysis of the 557 GHz narrow line (FWHM ~ 2 MHz) indicates that it originates at altitudes above 300 km, while lines measured with PACS probe mainly deeper levels (80-150 km). The HIFI and PACS observations are fitted simultaneously, considering a vertical distribution of H2O mixing ratio which follows a power law dependency q=q0(P/P0)n, where q0 is the mixing ratio at some reference pressure level P0, taken near the expected condensation level. Model fits will be presented, and compared with previously proposed H2O vertical distributions. We show in particular that both the steep profile proposed by Lara et al. (1996) (and adopted by Coustenis et al. (1998) to model the first detection of H2O

  9. Measurement and Prediction of H2O Outgassing Kinetics from Silica-Filled Polydimethylsiloxane TR55 and S5370

    SciTech Connect

    Dinh, L N; Burnham, A K; Schildbach, M A; Smith, R A; Maxwell, R S; Balazs, B; McLean II, W

    2006-08-28

    The isoconversional technique was employed for the measurement and prediction of H2O outgassing kinetics from silica-filled polydimethylsiloxane TR55 and S5370 in a vacuum or dry environment. Isoconversional analysis indicates that the energy barrier for H2O release from TR55 and S5370 is an increasing function of the fractional H2O release. This can be interpreted as the release of H2O from physisorbed water and then chemisorbed water with decreasing OH density from the surfaces of the embedded silica particles. Model independent predictions of H2O outgassing based on the measured kinetics follow the trend of actual isothermal outgassing at elevated temperatures, and suggest gradual outgassing in dry storage over many decades at low temperatures for both TR55 and S5370.

  10. Partitioning of H2O in the mantle transition zone and lower mantle

    NASA Astrophysics Data System (ADS)

    Inoue, T.; Katsuda, M.; Yurimoto, H.

    2008-12-01

    Water is the most abundant volatile component in the Earth, and the presence of H2O into the mantle minerals affects the elastic and rheological properties. It is well known that wadsleyite and ringwoodite, which are the most abundant minerals in the mantle transition zone, can accommodate significant amount (~3 wt%) of H2O in the crystal structures (e.g. Inoue et al., 1995; Kohlstedt et al, 1996). On the other hand, majorite garnet is the second abundant mineral in the mantle transition zone, and the H2O content was reported to be ~0.2 wt% (Katayama et al., 2003). It is important to know the maximum H2O storage capacity in the minerals, and also to know the partitioning of H2O in the mantle minerals to evaluate the water content in the Earth with temperature and pressure dependence. We have conducted high pressure experiment to determine the partitioning of H2O between wadsleyite, ringwoodite, perovskite and garnet. High-pressure experiments were conducted by MA-8 type (Kawai-type) high-pressure apparatus in Ehime University. We used pyrolite composition which was approximated with respect to five major components, CaO, MgO, FeO, Al2O3 and SiO2. Three starting H2O contents, 2.9, 8.3 and 15.6 wt% were selected. The experimental P-T conditions were 14-23 GPa and 1200-1700°C. The recovered samples were polished and then the chemical compositions were determined by EPMA in Ehime University and the water contents of minerals were measured by SIMS in Hokkaido University. The H2O contents of wadsleyite and ringwoodite decreased with increasing temperature, which is consistent with Ohtani et al. (2000). However the H2O content of majorite did not change so much with increasing temperature. As the results, the partition coefficients between wadsleyite and majorite, and between ringwoodite and majorite decreased with increasing temperature. Further details will be presented.

  11. Pyruvate Protects Pathogenic Spirochetes from H2O2 Killing

    PubMed Central

    Troxell, Bryan; Zhang, Jun-Jie; Bourret, Travis J.; Zeng, Melody Yue; Blum, Janice; Gherardini, Frank; Hassan, Hosni M.; Yang, X. Frank

    2014-01-01

    Pathogenic spirochetes cause clinically relevant diseases in humans and animals, such as Lyme disease and leptospirosis. The causative agent of Lyme disease, Borrelia burgdorferi, and the causative agent of leptospirosis, Leptospria interrogans, encounter reactive oxygen species (ROS) during their enzootic cycles. This report demonstrated that physiologically relevant concentrations of pyruvate, a potent H2O2 scavenger, and provided passive protection to B. burgdorferi and L. interrogans against H2O2. When extracellular pyruvate was absent, both spirochetes were sensitive to a low dose of H2O2 (≈0.6 µM per h) generated by glucose oxidase (GOX). Despite encoding a functional catalase, L. interrogans was more sensitive than B. burgdorferi to H2O2 generated by GOX, which may be due to the inherent resistance of B. burgdorferi because of the virtual absence of intracellular iron. In B. burgdorferi, the nucleotide excision repair (NER) and the DNA mismatch repair (MMR) pathways were important for survival during H2O2 challenge since deletion of the uvrB or the mutS genes enhanced its sensitivity to H2O2 killing; however, the presence of pyruvate fully protected ΔuvrB and ΔmutS from H2O2 killing further demonstrating the importance of pyruvate in protection. These findings demonstrated that pyruvate, in addition to its classical role in central carbon metabolism, serves as an important H2O2 scavenger for pathogenic spirochetes. Furthermore, pyruvate reduced ROS generated by human neutrophils in response to the Toll-like receptor 2 (TLR2) agonist zymosan. In addition, pyruvate reduced neutrophil-derived ROS in response to B. burgdorferi, which also activates host expression through TLR2 signaling. Thus, pathogenic spirochetes may exploit the metabolite pyruvate, present in blood and tissues, to survive H2O2 generated by the host antibacterial response generated during infection. PMID:24392147

  12. H2O Outgassing from Silicones

    SciTech Connect

    Dinh, L N; Maxwell, R S; Schildbach, M A; Balazs, B; McLean II, W

    2004-11-09

    In this fiscal year, we have tested the H{sub 2}O outgassing model for TR55 against independent core tests performed at different temperatures by our collaborators at Y12. At higher temperature ({approx} 71 C), the model properly predicts moisture outgassing from TR55 over the entire experiment. At lower temperature ({approx} 42.5 C), the model correctly predicts long-term moisture outgassing. However, in short-term limit, a better fit with core tests might be expected when the diffusion effect of H{sub 2}O through the silicone matrix is included into the model in the near future. A lookup table for the moisture content as well as moisture outgassing kinetics for M9787 which have previously been heated to 460K for one day and then exposed to relevant low levels of moisture is also now available as a reference for engineers/technicians in the fields.

  13. Descent with Modification: Thermal Reactions of Subsurface H2O2 of Relevance to Icy Satellites and Other Small Bodies

    NASA Technical Reports Server (NTRS)

    Hudson, Reggie L.; Loefler, Mark J.

    2012-01-01

    Laboratory experiments have demonstrated that magnetospheric radiation in the Jovian system drives reaction chemistry in ices at temperatures relevant to Europa and other icy satellites. Similarly, cosmic radiation (mainly protons) acting on cometary and interstellar ices can promote extensive chemical change. Among the products that have been identified in irradiated H20-ice is hydrogen peroxide (H202), which has been observed on Europa and is suspected on other worlds. Although the infrared spectra and radiation chemistry of H2O2-containing ices are well documented, the thermally-induced solid-phase chemistry of H2O2 is largely unknown. Therefore, in this presentation we report new laboratory results on reactions at 50 - 130 K in ices containing H2O2 and other molecules, both in the presence and absence of H2O. As an example of our results, we find that warming H2O + H2O2 + SO2 ices promotes SO2 oxidation to SO4(2-). We suspect that such redox chemistry may explain some of the observations related to the presence and distribution of H2O2 across Europa's surface as well as the lack of H2O2 on Ganymede and Callisto. If other molecules prove to be just as reactive with frozen H2O2 then it may explain why H2O2 has been absent from surfaces of many of the small icy bodies that are known to be exposed to ionizing radiation. Our results also have implications for the survival of H2O2 as it descends towards a subsurface ocean on Europa.

  14. Electrical conductivity of NaCl-H2O fluid in the crust

    NASA Astrophysics Data System (ADS)

    Sakuma, Hiroshi; Ichiki, Masahiro

    2016-02-01

    Ionic electrical conductivity of NaCl-H2O fluid as a function of pressure (0.2-2.0 GPa), temperature (673-2000 K), and NaCl concentration (0.6-9.6 wt %) was investigated using molecular dynamics (MD) simulations. Conductivity versus NaCl concentration has a nonlinear relationship due to the presence of electrically neutral ion pairs in concentrated solutions. The calculated conductivity at 0.6 wt % NaCl is consistent with the available experimental data, and the calculated conductivity at higher temperatures shows a greater degree of pressure dependence. The major factors controlling the conductivity are the density of the NaCl-H2O fluid and the permittivity of solvent H2O. A purely empirical equation for deriving the conductivity was proposed. Highly conductive zones below a depth of 35 km in the middle portion of the continental crust can be interpreted by the presence of NaCl-H2O fluid with the salinity ranging from 0.2 to 7.0 wt %. A highly conductive zone observed at a depth of 20 to 40 km above the subducting oceanic crust in Cascadia can be explained by the presence of low-salinity (0.5 wt %) NaCl-H2O fluid possibly generated by the dehydration of basalt.

  15. FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT Drought(s)-Elimination FOREVER!!!

    NASA Astrophysics Data System (ADS)

    Ertl, G.; Alefeld, G.; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

    2011-03-01

    "H2O H2O everywhere; ne'er a drop to drink"[Coleridge(1798)]; now: "H2 H2 everywhere; STILL ne'er a drop to drink": ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): {O/H2O}=[16]/[18] 90 % ; O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [{3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9/2007)] crucial geomorph-ology which ONLY maximal-buoyancy H2 can exploit, to again make "Mountains into Fountains", ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': "terraforming"(and ocean-rebasificaton!!!) Siegel proprietary magnetic-hydrogen-valve (MHV) permits H2 flow in already in-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/famine) Hydrogen-economy CATASTROPHIC H2 ozone-layer destruction sobering cavat to dangerous H2-automotion-economy panacea hype!!!

  16. Development of TDLAS sensor for diagnostics of CO, H2O and soot concentrations in reactor core of pilot-scale gasifier

    NASA Astrophysics Data System (ADS)

    Sepman, A.; Ögren, Y.; Gullberg, M.; Wiinikka, H.

    2016-02-01

    This paper reports on the development of the tunable diode laser absorption spectroscopy sensor near 4350 cm-1 (2298 nm) for measurements of CO and H2O mole fractions and soot volume fraction under gasification conditions. Due to careful selection of the molecular transitions [CO ( υ″ = 0 → υ' = 2) R34-R36 and H2O at 4349.337 cm-1], a very weak (negligible) sensitivity of the measured species mole fractions to the temperature distribution inside the high-temperature zone (1000 K < T < 1900 K) of the gasification process is achieved. The selected transitions are covered by the tuning range of single diode laser. The CO and H2O concentrations measured in flat flames generally agree better than 10 % with the results of 1-D flame simulations. Calibration-free absorption measurements of studied species in the reactor core of atmospheric pilot-scale entrained-flow gasifier operated at 0.1 MW power are reported. Soot concentration is determined from the measured broadband transmittance. The estimated uncertainties in the reactor core CO and H2O measurements are 15 and 20 %, respectively. The reactor core average path CO mole fractions are in quantitative agreement with the µGC CO concentrations sampled at the gasifier output.

  17. Atmospheric H2O2 measurement: comparison of cold trap method with impinger bubbling method

    NASA Technical Reports Server (NTRS)

    Sakugawa, H.; Kaplan, I. R.

    1987-01-01

    Collection of atmospheric H2O2 was performed by a cold trap method using dry ice-acetone as the refrigerant. The air was drawn by a pump into a glass gas trap immersed in the dry ice-acetone slush in a dewar flask at a flow rate of 2.5 l min-1 for approximately 2 h. Collection efficiency was > 99% and negligible interferences by O3, SO2 or organic matter with the collected H2O2 in the trap were observed. This method was compared with the air impinger bubbling method which has been previously described (Kok et al., 1978a, b, Envir. Sci. Technol. 12, 1072-1080). The measured total peroxide (H2O2 + organic peroxide) values in a series of aim samples collected by the impinger bubbling method (0.06-3.7 ppb) were always higher than those obtained by the cold trap method (0.02-1.2 ppb). Laboratory experiments suggest that the difference in values between the two methods probably results from the aqueous phase generation of H2O2 and organic peroxide in the impinger solution by a reaction of atmospheric O3 with olefinic and aromatic compounds. If these O3-organic compound reactions which occur in the impinger also occur in aqueous droplets in the atmosphere, the process could be very important for aqueous phase generation of H2O2 in clouds and rainwater.

  18. Active sites and mechanisms for H2O2 decomposition over Pd catalysts.

    PubMed

    Plauck, Anthony; Stangland, Eric E; Dumesic, James A; Mavrikakis, Manos

    2016-04-01

    A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2 We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O-O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O-O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

  19. Atmospheric H 2O 2 measurement: Comparison of cold trap method with impinger bubbling method

    NASA Astrophysics Data System (ADS)

    Sakugawa, Hiroshi; Kaplan, Isaac R.

    Collection of atmospheric H 2O 2 was performed by a cold trap method using dry ice-acetone as the refrigerant. The air was drawn by a pump into a glass gas trap immersed in the dry ice-acetone slush in a dewar flask at a flow rate of 2.5ℓ -1 for ~ 2 h. Collection efficiency was > 99% and negligible interferences by O 3, SO 2 or organic matter with the collected H 2O 2 in the trap were observed. This method was compared with the air impinger bubbling method which has been previously described (Kok et al., 1978a, b, Envir, Sci. Technol.12, 1072-1080). The measured total peroxide (H 2O 2 + organic peroxide) values in a series of air samples collected by the impinger bubbling method (0.06-3.7 ppb) were always higher than those obtained by the cold trap method (0.02-1.2 ppb). Laboratory experiments suggest that the difference in values between the two methods probably results from the aqueous phase generation of H 2O 2 and organic peroxide in the impinger solution by a reaction of atmospheric O 3 with olefinic and aromatic compounds. If these O 3-organic compound reactions which occur in the impinger also occur in aqueous droplets in the atmosphere, the process could be very important for aqueous phase generation of H 2O 2 in clouds and rainwater.

  20. Atmospheric H2O2 measurement: comparison of cold trap method with impinger bubbling method.

    PubMed

    Sakugawa, H; Kaplan, I R

    1987-01-01

    Collection of atmospheric H2O2 was performed by a cold trap method using dry ice-acetone as the refrigerant. The air was drawn by a pump into a glass gas trap immersed in the dry ice-acetone slush in a dewar flask at a flow rate of 2.5 l min-1 for approximately 2 h. Collection efficiency was > 99% and negligible interferences by O3, SO2 or organic matter with the collected H2O2 in the trap were observed. This method was compared with the air impinger bubbling method which has been previously described (Kok et al., 1978a, b, Envir. Sci. Technol. 12, 1072-1080). The measured total peroxide (H2O2 + organic peroxide) values in a series of aim samples collected by the impinger bubbling method (0.06-3.7 ppb) were always higher than those obtained by the cold trap method (0.02-1.2 ppb). Laboratory experiments suggest that the difference in values between the two methods probably results from the aqueous phase generation of H2O2 and organic peroxide in the impinger solution by a reaction of atmospheric O3 with olefinic and aromatic compounds. If these O3-organic compound reactions which occur in the impinger also occur in aqueous droplets in the atmosphere, the process could be very important for aqueous phase generation of H2O2 in clouds and rainwater. PMID:11542111

  1. Upper limits for the rate constant for the reaction Br + H2O2 yields HB2 + HO2

    NASA Technical Reports Server (NTRS)

    Leu, M.-T.

    1980-01-01

    Upper limits for the rate constant for the reaction Br + H2O2 yields HBr + HO2 have been measured over the temperature range 298 to 417 K in a discharge flow system using a mass spectrometer as a detector. Results are k sub 1 less than 1.5 x 10 to the -15th power cu cm/s at 298 K and k sub 1 less than 3.0 x 10 to the -15th power cu cm/s at 417 K, respectively. The implication to stratospheric chemistry is discussed.

  2. H2O2: A precursor for O2 on icy satellites? Laboratory studies

    NASA Astrophysics Data System (ADS)

    Loeffler, M. J.; Baragiola, R. A.

    2005-08-01

    Radiation processes affect the surface chemistry in planetary systems and in the ISM, and thus they need to be studied extensively. Recently, we have studied H2O2 production in water ice by 100 keV H+ irradiation at temperatures relevant to Europa and the ISM. Although hydrogen peroxide has only been detected so far in the infrared reflectance of Europa, this molecule is believed to be an important factor for the radiation-induced chemistry that occurs in water ice in other outer solar system objects. In particular, it has been proposed that this molecule may be a precursor for the production of O2 exospheres around icy satellites and Saturn's rings. Previously, we have irradiated crystalline H2O2 and identified the synthesis of H2O and O3. The saturation water concentration appeared to be high, but quantification of initial radiation yields (G values) was not possible because of the large change in the shape of the infrared absorption bands due to the concurrent amorphization. Further measurements could not be made, because we could only grow H2O2 at high temperatures by distillation, and thus growing amorphous H2O2 was not possible. Recently, we developed a method to grow amorphous H2O2 in the solid phase that allowed us to measure H2O2 destruction quantitatively. We have performed radiolysis with 50 keV H+ at 17 K to ensure that most radiolytic products stay in the ice and have detected H2O, O2 and O3 but not HO2; we have measured initial radiation yields for H2O and O2. Annealing the irradiated samples at 0.2 K/min to 200 K we found that most of the O2 produced stays trapped in the ice until 154 K, where it leaves immediately. Infrared absorption shows the production of dangling H bonds, which grow in importance during annealing and can even be observed at 150 K.

  3. H2O2 Production and Destruction in the Outer Solar System: Laboratory Studies

    NASA Astrophysics Data System (ADS)

    Loeffler, M. J.; Raut, U.; Vidal, R. A.; Baragiola, R. A.; Carlson, R. W.

    2004-11-01

    There has been a recent interest in the possible production mechanisms of H2O2 in water ice, since the Galileo NIMS instrument reported an absorption band (3.5 μm) on the surface of Europa (Carlson 1999). Here we present results from laboratory studies that show H2O2 creation and destruction by ion bombardment. We have found that 100 keV H+ irradiation can produce H2O2 from a water ice film at temperatures as high as 120 K and have measured the production rates at 20 K and 80 K. Furthermore, we have studied the temperature dependence and stability of the 3.5 μm band. To understand the nature of the peroxide produced by ion irradiation, we have grown solid hydrogen peroxide by distillation in an ultra high vacuum chamber and have used infrared spectroscopy to study the band shape and position as a function of temperature in various mixtures of water. Furthermore, we have measured the crystallization and sublimation of H2O2 at temperatures between 155 and 190 K. We have also irradiated a film of crystalline H2O2 with 20 keV H+ at 80 K and have observed what is most likely amorphization of the peroxide. Furthermore, infrared spectroscopy indicated that during irradiation, water and ozone are produced, while HO2 is not detected. The presence of ozone suggests that H2O2 is a likely precursor molecule for oxygen formation at 80 K. Work supported by NSF Astronomy, NASA Planetary Atmospheres and Origin programs.

  4. Interhemispheric differences in polar stratospheric HNO3, H2O, ClO, and O3

    NASA Technical Reports Server (NTRS)

    Santee, M. L.; Read, W. G.; Waters, J. W.; Froidevaux, L.; Manney, G. L.; Flower, D. A.; Jarnot, R. F.; Harwood, R. S.; Peckham, G. E.

    1995-01-01

    Simultaneous global measurements of nitric acid (HNO3), water (H2O), chlorine monoxide (ClO), and ozone (O3) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO3 was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H2O after mid-July. By mid-August, near the time of peak ClO, abundances of gas-phase HNO3 and H2O were extremely low. The concentrations of HNO3 and H2O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO3 or H2O were observed in the 1992-1993 Arctic winter vortex. Although ClO was enhanced over the Arctic as it was over the Antarctic, Arctic O3 depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone 'hole' is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone.

  5. Interhemispheric differences in polar stratospheric HNO3, H2O, ClO, and O3

    SciTech Connect

    Santee, M.L.; Read, W.G.; Waters, J.W.; Froidevaux, L.; Manney, G.L.; Flower, D.A.; Jarnot, R.F.; Harwood, R.S.; Peckham, G.E.

    1995-02-01

    Simultaneous global measurements of nitric acid (HNO3), water (H2O), chlorine monoxide (ClO), and ozone (O3) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO3 was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H2O after mid-July. By mid-August, near the time of peak ClO, abundances of gas-phase HNO3 and H2O were extremely low. The concentrations of HNO3 and H2O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO3 or H2O were observed in the 1992-1993 Arctic winter vortex. Although ClO was enhanced over the Arctic as it was over the Antarctic, Arctic O3 depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone `hole` is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone.

  6. Interhemispheric Differences in Polar Stratospheric HNO3, H2O, CIO, and O3.

    PubMed

    Santee, M L; Read, W G; Waters, J W; Froidevaux, L; Manney, G L; Flower, D A; Jarnot, R F; Harwood, R S; Peckham, G E

    1995-02-10

    Simultaneous global measurements of nitric acid (HNO(3)), water (H(2)O), chlorine monoxide (CIO), and ozone (O(3)) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO(3) was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H(2)O after mid-July. By mid-August, near the time of peak CIO, abundances of gas-phase HNO(3) and H(2)O were extremely low. The concentrations of HNO(3) and H(2)O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO(3) or H(2)O were observed in the 1992-1993 Arctic winter vortex. Although CIO was enhanced over the Arctic as it was over the Antarctic, Arctic O(3) depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone "hole" is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone. PMID:17813911

  7. MUTAGENIC ACTIVITY OF IRRADIATED TOLUENE/NOX/H2O/AIR MIXTURES

    EPA Science Inventory

    Irradiated mixtures of toluene/NOx/H2O/air were brought to a steady-state distribution of reactants and products in a 22.7 cu. m. flow-mode smog chamber, and the effluent was tested for mutagenic activity by exposing Salmonella typhimurum strains TA100 and TA98 to it. Two differe...

  8. The thermodynamic properties of H2O in magnesium and iron cordierite

    NASA Astrophysics Data System (ADS)

    Skippen, G. B.; Gunter, Avril E.

    1996-06-01

    The equilibrium water content of cordierite has been measured for 31 samples synthesized at pressures of 1000 and 2000 bars and temperatures from 600 to 750° C using the cold-seal hydrothermal technique. Ten data points are presented for pure magnesian cordierite, 11 data points for intermediate iron/magnesium ratios from 0.25 to 0.65 and 10 data points for pure iron cordierite. By representing the contribution of H2O to the heat capacity of cordierite as steam at the same temperature and pressure, it is possible to calculate a standard enthalpy and entropy of reaction at 298.18° K and 1 bar for, (Mg,Fe)2Al4Si5O18+H2O ⇄ (Fe,Mg)2Al4Si5O18.H2O Combining the 31 new data points with 89 previously published experimental measurements gives: Δ H ° r = 37141±3520 J and Δ S ° r = 99.2±4 J/degree. This enthalpy of reaction is within experimental uncertainty of calorimetric data. The enthalpy and entropy of hydration derived separately for magnesian cordierite ( 34400±3016 J, 96.5±3.4 J/degree) and iron cordierite ( 39613±2475, 99.5±2.5 J/degree) cannot be distinguished within the present experimental uncertainty. The water content as a function of temperature, T(K), and water fugacity, f(bars), is given by n H2O=1/[1+1/( K ṡ f H2O)] where the equilibrium constant for the hydration reaction as written above is, ln K=4466.4/ T 11.906 with the standard state for H2O as the gas at 1 bar and T, and for cordierite components, the hydrous and anhydrous endmembers at P and T.

  9. Effects of a single water molecule on the OH + H2O2 reaction.

    PubMed

    Buszek, Robert J; Torrent-Sucarrat, Miquel; Anglada, Josep M; Francisco, Joseph S

    2012-06-21

    The effect of a single water molecule on the reaction between H(2)O(2) and HO has been investigated by employing MP2 and CCSD(T) theoretical approaches in connection with the aug-cc-PVDZ, aug-cc-PVTZ, and aug-cc-PVQZ basis sets and extrapolation to an ∞ basis set. The reaction without water has two elementary reaction paths that differ from each other in the orientation of the hydrogen atom of the hydroxyl radical moiety. Our computed rate constant, at 298 K, is 1.56 × 10(-12) cm(3) molecule(-1) s(-1), in excellent agreement with the suggested value by the NASA/JPL evaluation. The influence of water vapor has been investigated by considering either that H(2)O(2) first forms a complex with water that reacts with hydroxyl radical or that H(2)O(2) reacts with a previously formed H(2)O·OH complex. With the addition of water, the reaction mechanism becomes much more complex, yielding four different reaction paths. Two pathways do not undergo the oxidation reaction but an exchange reaction where there is an interchange between H(2)O(2)·H(2)O and H(2)O·OH complexes. The other two pathways oxidize H(2)O(2), with a computed total rate constant of 4.09 × 10(-12) cm(3) molecule(-1) s(-1) at 298 K, 2.6 times the value of the rate constant of the unassisted reaction. However, the true effect of water vapor requires taking into account the concentration of the prereactive bimolecular complex, namely, H(2)O(2)·H(2)O. With this consideration, water can actually slow down the oxidation of H(2)O(2) by OH between 1840 and 20.5 times in the 240-425 K temperature range. This is an example that demonstrates how water could be a catalyst in an atmospheric reaction in the laboratory but is slow under atmospheric conditions. PMID:22455374

  10. Possible sources of H2 to H2O enrichment at evaporation of parent chondritic material

    NASA Technical Reports Server (NTRS)

    Makalkin, A. B.; Dorofeyeva, V. A.; Vityazev, A. V.

    1993-01-01

    One of the results obtained from thermodynamic simulation of recondensation of the source chondritic material is that at 1500-1800 K it's possible to form iron-rich olivine by reaction between enstatite, metallic iron and water vapor in the case of (H2O)/(H2) approximately equal to 0.1. This could be reached if the gas depletion in hydrogen is 200-300 times relative to solar abundance. To get this range of depletion one needs some source material more rich in hydrogen than the carbonaceous CI material which is the richest in volatiles among chondrites. In the case of recondensation at impact heating and evaporation of colliding planetesimals composed of CI material, we obtain insufficiently high value of (H2)/(H2O) ratio. In the present paper we consider some possible source materials and physical conditions necessary to reach gas composition with (H2)/(H2O) approximately 10 at high temperature.

  11. Ortho-para mixing hyperfine interaction in the H2O+ ion and nuclear spin equilibration.

    PubMed

    Tanaka, Keiichi; Harada, Kensuke; Oka, Takeshi

    2013-10-01

    The ortho to para conversion of water ion, H2O(+), due to the interaction between the magnetic moments of the unpaired electron and protons has been theoretically studied to calculate the spontaneous emission lifetime between the ortho- and para-levels. The electron spin-nuclear spin interaction term, Tab(SaΔIb + SbΔIa) mixes ortho (I = 1) and para (I = 0) levels to cause the "forbidden" ortho to para |ΔI| = 1 transition. The mixing term with Tab = 72.0 MHz is 4 orders of magnitude higher for H2O(+) than for its neutral counterpart H2O where the magnetic field interacting with proton spins is by molecular rotation rather than the free electron. The resultant 10(8) increase of ortho to para conversion rate possibly makes the effect of conversion in H2O(+) measurable in laboratories and possibly explains the anomalous ortho to para ratio recently reported by Herschel heterodyne instrument for the far-infrared (HIFI) observation. Results of our calculations show that the ortho ↔ para mixings involving near-degenerate ortho and para levels are high (∼10(-3)), but they tend to occur at high energy levels, ∼300 K. Because of the rapid spontaneous emission, such high levels are not populated in diffuse clouds unless the radiative temperature of the environment is very high. The low-lying 101 (para) and 111 (ortho) levels of H2O(+) are mixed by ∼10(-4) making the spontaneous emission lifetime for the para 101 → ortho 000 transition 520 years and 5200 years depending on the F value of the hyperfine structure. Thus the ortho ↔ para conversion due to the unpaired electron is not likely to seriously affect thermalization of interstellar H2O(+) unless either the radiative temperature is very high or number density of the cloud is very low. PMID:23530629

  12. Synergetic pretreatment of sewage sludge by microwave irradiation in presence of H2O2 for enhanced anaerobic digestion.

    PubMed

    Eskicioglu, Cigdem; Prorot, Audrey; Marin, Juan; Droste, Ronald L; Kennedy, Kevin J

    2008-11-01

    A microwave-enhanced advanced hydrogen peroxide oxidation process (MW/H(2)O(2)-AOP) was studied in order to investigate the synergetic effects of MW irradiation on H(2)O(2) treated waste activated sludges (WAS) in terms of mineralization (permanent stabilization), sludge disintegration/solubilization, and subsequent anaerobic biodegradation as well as dewaterability after digestion. Thickened WAS sample pretreated with 1gH(2)O(2)/g total solids (TS) lost 11-34% of its TS, total chemical oxygen demand (COD) and total biopolymers (humic acids, proteins and sugars) via advanced oxidation. In a temperature range of 60-120 degrees C, elevated MW temperatures (>80 degrees C) further increased the decomposition of H(2)O(2) into OH* radicals and enhanced both oxidation of COD and solubilization of particulate COD (>0.45 micron) of WAS indicating that a synergetic effect was observed when both H(2)O(2) and MW treatments were combined. However, at all temperatures tested, MW/H(2)O(2) treated samples had lower first-order mesophilic (33+/-2 degrees C) biodegradation rate constants and ultimate (after 32 days of digestion) methane yields (mL per gram sample) compared to control and MW irradiated WAS samples, indicating that synergistically (MW/H(2)O(2)-AOP) generated soluble organics were slower to biodegrade or more refractory than those generated during MW irradiation. PMID:18783812

  13. Effect of chirality on domain wall dynamics in molecular ferrimagnet [MnII(HL-pn)(H2O)][MnIII(CN)6]·2H2O

    NASA Astrophysics Data System (ADS)

    Mushenok, F.; Koplak, O.; Morgunov, R.

    2011-11-01

    In this paper we distinguish the contributions of switching, slide, creep and Debye relaxation modes of the domain wall dynamics to the low-frequency magnetic properties of chiral and racemic [MnII(HL-pn)(H2O)][MnIII(CN)6]·2H2O molecular ferrimagnets. We demonstrate that crystal and spin chirality affects the characteristic transition temperatures between different modes. In chiral crystals, transitions to the creep and Debye relaxation modes were observed at T = 7 K and 5 K, whereas in racemic crystals the same transitions occurred at higher temperatures T = 13 K and 9 K, respectively. Difference of the Peierls relief in chiral and racemic crystals is a possible reason of the chirality effect on the domain walls dynamics.

  14. An Accurate Potential Energy Surface for H2O

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Partridge, Harry; Langhoff, Stephen R. (Technical Monitor)

    1997-01-01

    We have carried out extensive high quality ab initio electronic structure calculations of the ground state potential energy surface (PES) and dipole moment function (DMF) for H2O. A small adjustment is made to the PES to improve the agreement of line positions from theory and experiment. The theoretical line positions are obtained from variational ro-vibrational calculations using the exact kinetic energy operator. For the lines being fitted, the root-mean-square error was reduced from 6.9 to 0.08 /cm. We were then able to match 30,092 of the 30,117 lines from the HITRAN 96 data base to theoretical lines, and 80% of the line positions differed less than 0.1 /cm. About 3% of the line positions in the experimental data base appear to be incorrect. Theory predicts the existence of many additional weak lines with intensities above the cutoff used in the data base. To obtain results of similar accuracy for HDO, a mass dependent correction to the PH is introduced and is parameterized by simultaneously fitting line positions for HDO and D2O. The mass dependent PH has good predictive value for T2O and HTO. Nonadiabatic effects are not explicitly included. Line strengths for vibrational bands summed over rotational levels usually agree well between theory and experiment, but individual line strengths can differ greatly. A high temperature line list containing about 380 million lines has been generated using the present PES and DMF

  15. Mixed protein-templated luminescent metal clusters (Au and Pt) for H2O2 sensing

    PubMed Central

    2013-01-01

    A simple and cost-effective method to synthesize the luminescent noble metal clusters (Au and Pt) in chicken egg white aqueous solution at room temperature is reported. The red-emitting Au cluster is used as fluorescent probe for sensitive detection of H2O2. PMID:23601828

  16. Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on TiO2(110)

    SciTech Connect

    Smith, R. Scott; Li, Zhenjun; Chen, Long; Dohnalek, Zdenek; Kay, Bruce D.

    2014-07-17

    The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (BBO), Ti, and oxygen vacancies (VO) sites in order of increasing peak temperature. Analysis of the saturated monolayer peak for both species reveals that the corresponding adsorption energies on all sites are greater for H2O and for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupy the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K. Further analysis shows that a ratio of 4 H2O to 3 CO2 molecules is needed to displace CO2 from the TiO2(110) surface.

  17. Electrochemical, H2O2-Boosted Catalytic Oxidation System

    NASA Technical Reports Server (NTRS)

    Akse, James R.; Thompson, John O.; Schussel, Leonard J.

    2004-01-01

    An improved water-sterilizing aqueous-phase catalytic oxidation system (APCOS) is based partly on the electrochemical generation of hydrogen peroxide (H2O2). This H2O2-boosted system offers significant improvements over prior dissolved-oxygen water-sterilizing systems in the way in which it increases oxidation capabilities, supplies H2O2 when needed, reduces the total organic carbon (TOC) content of treated water to a low level, consumes less energy than prior systems do, reduces the risk of contamination, and costs less to operate. This system was developed as a variant of part of an improved waste-management subsystem of the life-support system of a spacecraft. Going beyond its original intended purpose, it offers the advantage of being able to produce H2O2 on demand for surface sterilization and/or decontamination: this is a major advantage inasmuch as the benign byproducts of this H2O2 system, unlike those of systems that utilize other chemical sterilants, place no additional burden of containment control on other spacecraft air- or water-reclamation systems.

  18. Role of Metabolic H2O2 Generation

    PubMed Central

    Sies, Helmut

    2014-01-01

    Hydrogen peroxide, the nonradical 2-electron reduction product of oxygen, is a normal aerobic metabolite occurring at about 10 nm intracellular concentration. In liver, it is produced at 50 nmol/min/g of tissue, which is about 2% of total oxygen uptake at steady state. Metabolically generated H2O2 emerged from recent research as a central hub in redox signaling and oxidative stress. Upon generation by major sources, the NADPH oxidases or Complex III of the mitochondrial respiratory chain, H2O2 is under sophisticated fine control of peroxiredoxins and glutathione peroxidases with their backup systems as well as by catalase. Of note, H2O2 is a second messenger in insulin signaling and in several growth factor-induced signaling cascades. H2O2 transport across membranes is facilitated by aquaporins, denoted as peroxiporins. Specialized protein cysteines operate as redox switches using H2O2 as thiol oxidant, making this reactive oxygen species essential for poising the set point of the redox proteome. Major processes including proliferation, differentiation, tissue repair, inflammation, circadian rhythm, and aging use this low molecular weight oxygen metabolite as signaling compound. PMID:24515117

  19. Experimental measurements of vapor-liquid equilibria of the H2O + CO2 + CH4 ternary system

    USGS Publications Warehouse

    Qin, J.; Rosenbauer, R.J.; Duan, Zhenhao

    2008-01-01

    Reported are the experimental measurements on vapor-liquid equilibria in the H2O + CO2 + CH4 ternary system at temperatures from (324 to 375) K and pressures from (10 to 50) MPa. The results indicate that the CH4 solubility in the ternary mixture is about 10 % to 40 % more than that calculated by interpolation from the Henry's law constants of the binary system, H2O + CH4, and the solubility of CO2 is 6 % to 20 % more than what is calculated by the interpolation from the Henry's law constants of the binary mixture, H 2O + CO2. ?? 2008 American Chemical Society.

  20. Feasibility of ozone absorption by H2O2 solution in rotating packed beds.

    PubMed

    Lin, Chia-Chang; Chao, Cheng-Yu; Liu, Mei-Yun; Lee, Ya-Ling

    2009-08-15

    This work examined the feasibility of ozone (O(3)) absorption by H(2)O(2) solution in a rotating packed bed (RPB). The O(3) removal efficiency was determined at various operating variables including RPB speed, gas flow rate, and liquid flow rate in three RPBs. For each RPB, the results demonstrated that the RPB speed positively affected the O(3) removal efficiency. Also, the O(3) removal efficiency increased with the liquid flow rate but decreased with the gas flow rate. Moreover, the obtained results indicated that the O(3) removal efficiency increased as the inner radius of the bed was increased and the outer radius of the bed was decreased. Furthermore, the developed method for O(3) absorption using H(2)O(2) solution could provide the removal efficiency of more than 95%. Consequently, the novel method would have a great potential in the removal of O(3) from the exhausted gases. PMID:19261385

  1. High-speed Air Temperature Measurements in a Closed-path Cell and Quality of CO2 and H2O Fluxes from a Short-tube Gas Analyzer.

    NASA Astrophysics Data System (ADS)

    Burba, G. G.; Kathilankal, J. C.; Fratini, G.

    2015-12-01

    Gas analyzers traditionally used for eddy covariance method measure gas density. When fluxes are calculated, corrections are applied to account for the changes in gas density due to changing temperature and pressure (Ideal Gas Law) and changing water vapor density (Dalton's Law). The new generation of gas analyzers with fast air temperature and pressure measurements in the sampling cell enables on-the-fly calculation of fast dry mole fraction. This significantly simplifies the flux processing because the WPL density terms are no longer required, and leads to the reduction in uncertainties associated with latent and sensible heat flux inputs into the density terms. Traditional closed-path instruments with long intake tubes often can effectively dampen the fast temperature fluctuations in the tube before reaching the measurement cell, thus reducing or eliminating the need for temperature correction for density-based fluxes. But in instruments with a short-tube design, most - but not all - of the temperature fluctuations are attenuated, so calculating unbiased fluxes using fast dry mole fraction requires high-speed precise temperature measurements of the air stream inside the cell. Fast pressure and water vapor content of the sampled air should also be measured in the cell and carefully aligned in time with gas density and sample temperature measurements.In this study we examine the impact of fast-response air temperature measurements in the cell on the calculations of carbon dioxide and water vapor fluxes at different time scales from three different ecosystems. The fast cell air temperature data is filtered mathematically to obtain slower response cell temperature time series, which is used in the calculation of fluxes. This exercise is intended to simulate the use of thicker slower response thermocouples instead of fast response fine wire thermocouples for estimating cell temperature. The directly measured block temperature is also utilized to illustrate the

  2. Decomposition reactions of magnesium sulfate hydrates and phase equilibria in the MgSO 4-H 2O and Na +-Mg 2+-Cl --SO 42--H 2O systems with implications for Mars

    NASA Astrophysics Data System (ADS)

    Steiger, Michael; Linnow, Kirsten; Ehrhardt, Dorothee; Rohde, Mandy

    2011-06-01

    We report new measurements of equilibrium relative humidities for stable and metastable hydration-dehydration equilibria involving several magnesium sulfates in the MgSO 4· nH 2O series. We also report a comprehensive thermodynamic treatment of the system including solution properties and experimental data from the published literature, i.e. solubilities, heat capacities and additional decomposition humidities. While for some magnesium sulfate hydrates solubility data in the binary system MgSO 4-H 2O are sparse, there is a reasonable database of solubility measurements of these hydrates in the ternary MgCl 2-MgSO 4-H 2O and the quaternary reciprocal Na +-Mg 2+-Cl --SO 42--H 2O systems. To make these data suitable for the determination of solubility products, we parameterized a Pitzer ion interaction model for the calculation of activity coefficients and water activities in mixed solutions of these systems and report the ion interaction parameters for the Na +-Mg 2+-Cl --SO 42--H 2O system. The model predicted solubilities in the reciprocal system are in very good agreement with experimental data. Using all available experimental data and the solution model an updated phase diagram of the MgSO 4-H 2O system covering the whole temperature range from about 170 to 473 K is established. This treatment includes MgSO 4·H 2O (kieserite), MgSO 4·4H 2O (starkeyite), MgSO 4·5H 2O (pentahydrite), MgSO 4·6H 2O (hexahydrite), MgSO 4·7H 2O (epsomite) and MgSO 4·11H 2O (meridianiite). It is shown that only kieserite, hexahydrite, epsomite and meridianiite show fields of stable existence while starkeyite and pentahydrite are always metastable. Due to sluggish kinetics of kieserite formation, however, there is a rather extended field of metastable existence of starkeyite which makes this solid a major product in dehydration reactions. The model predicted behavior of the magnesium sulfates is in excellent agreement with observations reported in the literature under terrestrial

  3. ALMA Observation of the 658 GHz Vibrationally Excited H2O Maser in Orion KL Source I

    NASA Astrophysics Data System (ADS)

    Hirota, Tomoya; Kim, Mi Kyoung; Honma, Mareki

    2016-02-01

    We present an observational study of the vibrationally excited H2O line at 658 GHz ({ν }2 = 1, {1}{1,0}-1{}{0,1}) toward Orion KL using the Atacama Large Millimeter/Submillimeter Array (ALMA). This line is clearly detected at the position of the massive protostar candidate, Source I. The spatial structure is compact, with a size of about 100 AU, and is elongated along the northeast-southwest low-velocity (18 km -1) bipolar outflow traced by 22 GHz H2O masers, SiO masers, and thermal SiO lines. A velocity gradient can be seen perpendicular to the bipolar outflow. The overall spatial and velocity structure seems to be analogous to that of the 321 GHz H2O maser line previously detected with ALMA and vibrationally excited SiO maser emission. The brightness temperature of the 658 GHz H2O line is estimated to be higher than 2 × 104 K, implying that it is emitted via maser action. Our results suggest that the 658 GHz H2O maser line is emitted from the base of the outflow from a rotating and expanding accretion disk as observed for the SiO masers and the 321 GHz H2O maser. We also search for two other H2O lines at 646 GHz (9{}{7,3}-8{}{8,0} and {9}{7,2}-8{}{8,1}), but they are not detected in Orion KL.

  4. NASA Lewis H2-O2 MHD program

    NASA Technical Reports Server (NTRS)

    Smith, M.; Nichols, L. D.; Seikel, G. R.

    1974-01-01

    Performance and power costs of H2-O2 combustion powered steam-MHD central power systems are estimated. Hydrogen gas is assumed to be transmitted by pipe from a remote coal gasifier into the city and converted to electricity in a steam MHD plant having an integral gaseous oxygen plant. These steam MHD systems appear to offer an attractive alternative to both in-city clean fueled conventional steam power plants and to remote coal fired power plants with underground electric transmission into the city. Status and plans are outlined for an experimental evaluation of H2-O2 combustion-driven MHD power generators at NASA Lewis Research Center.

  5. Maps of [HDO]/[H2O] near Mars’ Aphelion

    NASA Astrophysics Data System (ADS)

    Novak, Robert E.; Mumma, M. J.; Villanueva, G. L.

    2013-10-01

    We report maps of HDO and H2O taken at three seasonal points before and near Mars’ aphelion (Ls = 71°). These observations were taken at Ls = 357° (15 January 2006), Ls = 50° (26 March 2008) and Ls = 72° (2/3 April 2010) using CSHELL at the NASA Infrared Telescope Facility. For these three seasonal dates, the entrance slit of the spectrometer was positioned N-S on Mars centered at the sub-Earth point; on 3 April 2010, the slit was positioned E-W. Data were extracted at 0.6 arc-second intervals from the spectral-spatial images. Individual spectral lines were measured near 3.67 μm (HDO) and 3.29 μm (H2O). The column densities were obtained by comparing the observed lines to those of a multi-layered, radiative transfer model. The model includes solar Fraunhofer lines, two-way transmission through Mars’ atmosphere, thermal emission from Mars’ surface and atmosphere, and a one-way transmission through the Earth’s atmosphere. Latitudinal maps of HDO, H2O, and their ratios were then constructed. The [HDO]/[H2O] ratios have been found to be larger than those on Earth and they vary with both latitude and season. For the Ls = 357° and 50° observations, the ratio peaks near the sub-solar latitude ([HDO]/[H2O] ~ 6.9 VSMOW) and decreases towards both the North and South polar-regions. At Ls = 72°, column densities of both HDO and H2O and their ratios increase from the Southern hemisphere to the North polar-region. Observations from 3 April 2013 show diurnal variations of both the column densities and their ratio. Specific points on Mars’ surface were tracked for four hours. It is believed that this variation is caused by the vaporization of ground frost and water ice clouds that are formed during the night and disappear during daytime. Our results for H2O column densities will be compared to TES results. The results for HDO and the [HDO]/[H2O] ratios will be compared to model results.This work was partially funded by grants from NASA's Planetary Astronomy

  6. Particle-in-Cell Simulations of Atmospheric Pressure He/2%H2O Discharges

    NASA Astrophysics Data System (ADS)

    Kawamura, E.; Lieberman, M. A.; Lichtenberg, A. J.; Graves, D. B.; Gopalakrishnan, R.

    2015-09-01

    Atmospheric pressure micro-discharges in contact with liquid surfaces are of increasing interest, especially in the bio-medical field. We conduct 1D3v particle-in-cell (PIC) simulations of a voltage-driven 1 mm width atmospheric pressure He/2% H2O plasma discharge in series with an 0.5 mm width liquid H2O layer and a 1mm width quartz dielectric layer. A previously developed two-temperature hybrid global model of atmospheric pressure He/H2O discharges was used to determine the most important species and collisional reactions to use in the PIC simulations. We found that H13O6+, H5O3-, and electrons were the most prominent charged species, while most of the metastable helium He* was quenched via Penning ionization. The ion-induced secondary emission coefficient γi was assumed to be 0.15 at all surfaces. A series of simulations were conducted at 27.12 MHz with Jrf ~ 800-2200 A/m2. The H2O rotational and vibrational excitation losses were so high that electrons reached the walls at thermal temperatures. We also simulated a much lower frequency case of 50 kHz with Vrf = 10 kV. In this case, the discharge ran in a pure time-varying γ-mode. This work was supported by the Department of Energy Office of Fusion Energy Science Contract DE-SC0001939.

  7. Photodesorption of H2O, HDO, and D2O ice and its impact on fractionation

    NASA Astrophysics Data System (ADS)

    Arasa, Carina; Koning, Jesper; Kroes, Geert-Jan; Walsh, Catherine; van Dishoeck, Ewine F.

    2015-03-01

    The HDO/H2O ratio measured in interstellar gas is often used to draw conclusions on the formation and evolution of water in star-forming regions and, by comparison with cometary data, on the origin of water on Earth. In cold cores and in the outer regions of protoplanetary disks, an important source of gas-phase water comes from photodesorption of water ice. This research note presents fitting formulae for implementation in astrochemical models using previously computed photodesorption efficiencies for all water ice isotopologues obtained with classical molecular dynamics simulations. The results are used to investigate to what extent the gas-phase HDO/H2O ratio reflects that present in the ice or whether fractionation can occur during the photodesorption process. Probabilities for the top four monolayers are presented for photodesorption of X (X = H, D) atoms, OX radicals, and X2O and HDO molecules following photodissociation of H2O, D2O, and HDO in H2O amorphous ice at ice temperatures from 10-100 K. Significant isotope effects are found for all possible products: (1) H atom photodesorption probabilities from H2O ice are larger than those for D atom photodesorption from D2O ice by a factor of 1.1; the ratio of H and D photodesorbed upon HDO photodissociation is a factor of 2. This process will enrich the ice in deuterium atoms over time; (2) the OD/OH photodesorption ratio upon D2O and H2O photodissociation is on average a factor of 2, but the OD/OH photodesorption ratio upon HDO photodissociation is almost constant at unity for all ice temperatures; (3) D atoms are more effective in kicking out neighbouring water molecules than H atoms. However, the ratio of the photodesorbed HDO and H2O molecules is equal to the HDO/H2O ratio in the ice, therefore, there is no isotope fractionation when HDO and H2O photodesorb from the ice. Nevertheless, the enrichment of the ice in D atoms due to photodesorption can over time lead to an enhanced HDO/H2O ratio in the ice, and

  8. Melting phase relations in the system H2O - NH3 at high pressure

    NASA Astrophysics Data System (ADS)

    Sugimura, E.; Hirose, K.; Komabayashi, T.; Ohishi, Y.; Hirao, N.; Dubrovinsky, L. S.

    2012-12-01

    The density models of Uranus and Neptune constrained by their gravitational moments from Voyager mission suggest that mantles of these planets may be predominantly comprised of water (H2O), methane (CH4), and ammonia (NH3). The impurities in pure water would greatly influence the phase relations in the water-rich system expected in the icy mantle, which must be known to construct a plausible planetary model. One of important effects of the impurity is on the liquidus temperature (Tliq), since it decides the actual presence of solid phase within the icy mantle. In order to determine Tliq in H2O-rich region of the H2O - CH4 - NH3 ternary system, the melting phase relations in the H2O - CH4 and H2O - NH3 systems must be accurately known. However, previous melting experiments on each binary system were limited to several gigapascals, thus need to be explored to higher P-T conditions for application in interiors of Uranus and Neptune. We have investigated high-pressure (P) and -temperature (T) melting phase relations in the H2O - NH3 system based on a combination of visual observation and angle-dispersive x-ray diffraction (XRD) measurements at BL10XU, SPring-8. High-P-T conditions were generated in an externally-resistive heated diamond anvil cell (DAC). Starting material was 20wt% NH3 aqueous solution whose composition was checked via Tliq of the solution measured in a DAC at near atmospheric pressure. The aqueous solution was loaded into a gold-lined hole in a preindented rhenium gasket in order to insulate the sample from rhenium. Pressure was determined from the unit-cell volume of gold liner. Melting and freezing of the sample were detected by monitoring disappearance/appearance of diffraction peaks of solid and diffuse scattering of liquids, as well as observing melting/crystallization of crystal grains under microscope. Up to 20 GPa at room temperature, in addition to ice VII, diffraction peaks of bcc-like phase, which is most likely to be the reported phase VI

  9. Bacterial Ice Nucleation in Monodisperse D2O and H2O-in-Oil Emulsions.

    PubMed

    Weng, Lindong; Tessier, Shannon N; Smith, Kyle; Edd, Jon F; Stott, Shannon L; Toner, Mehmet

    2016-09-13

    Ice nucleation is of fundamental significance in many areas, including atmospheric science, food technology, and cryobiology. In this study, we investigated the ice-nucleation characteristics of picoliter-sized drops consisting of different D2O and H2O mixtures with and without the ice-nucleating bacteria Pseudomonas syringae. We also studied the effects of commonly used cryoprotectants such as ethylene glycol, propylene glycol, and trehalose on the nucleation characteristics of D2O and H2O mixtures. The results show that the median freezing temperature of the suspension containing 1 mg/mL of a lyophilized preparation of P. syringae is as high as -4.6 °C for 100% D2O, compared to -8.9 °C for 100% H2O. As the D2O concentration increases every 25% (v/v), the profile of the ice-nucleation kinetics of D2O + H2O mixtures containing 1 mg/mL Snomax shifts by about 1 °C, suggesting an ideal mixing behavior of D2O and H2O. Furthermore, all of the cryoprotectants investigated in this study are found to depress the freezing phenomenon. Both the homogeneous and heterogeneous freezing temperatures of these aqueous solutions depend on the water activity and are independent of the nature of the solute. These findings enrich our fundamental knowledge of D2O-related ice nucleation and suggest that the combination of D2O and ice-nucleating agents could be a potential self-ice-nucleating formulation. The implications of self-nucleation include a higher, precisely controlled ice seeding temperature for slow freezing that would significantly improve the viability of many ice-assisted cryopreservation protocols. PMID:27495973

  10. H2-O2 auxiliary power unit for Space Shuttle vehicles - A progress report.

    NASA Technical Reports Server (NTRS)

    Joyce, J. P.; Beremand, D. G.; Cameron, H. M.; Jefferies, K. S.

    1973-01-01

    Description of a program to establish technology readiness of hydrogen-oxygen (H2-O2) auxiliary power units for use on board the Space Shuttle orbiter vehicle. Fundamental objectives include experimentally establishing an acceptable propellant flow control method, verification of combustor stability, and adequate thermal management. An initial auxiliary power unit (APU) configuration with recycled hydrogen flow has been studied and revised toward greater simplicity and scaling ease. The selected APU is a recuperated open-cycle, turbine-driven unit. Series flow of cryogenic hydrogen removes internally-generated heat and heat from the hydraulic system. The revised configuration schematic and its calculated performance are reviewed. A weight comparison is made between the shuttle baseline hydrazine and H2-O2 APU systems, showing that hydrogen-oxygen APUs have the potential of increasing the payload of the Space Shuttle.

  11. New Optical Constants for Amorphous and Crystalline H2O-ice and H2O-mixtures.

    NASA Technical Reports Server (NTRS)

    Mastrapa, Rachel; Bernstein, Max; Sandford, Scott

    2006-01-01

    We will present the products of new laboratory measurements of ices relevant to Trans-Neptunian Objects. We have calculated the real and imaginary indices of refraction for amorphous and crystalline H2O-ice and also H2O-rich ices containing other molecular species. We create ice samples by condensing gases onto a cold substrate. We measure the thickness of the sample by reflecting a He-Ne laser off of the sample and counting interference fringes as it grows. We then collect transmission spectra of the samples in the wavelength range from 0.7-22 micrometers. Using the thickness and the transmission spectra of the ice we calculate the imaginary part of the index of refraction. We then use a Kramers-Kronig calculation to calculate the real part of the index of refraction (Berland et al. 1994; Hudgins et al. 1993). These optical constants can then be used to create model spectra for comparison to spectra from Solar System objects, including TNOs. We will summarize the difference between the amorphous and crystalline H2O-ice spectra. These changes include weakening of features and shifting of features to shorter wavelength. One important result is that the 2 pm feature is stronger in amorphous H2O ice than it is in crystalline H2O-ice. We will also discuss the changes seen when H2O is mixed with other components, including CO2, CH4, HCN, and NH3 (Bernstein et al. 2005; Bernstein et al. 2006).

  12. CO 2-H 2O mixtures in the geological sequestration of CO 2. I. Assessment and calculation of mutual solubilities from 12 to 100°C and up to 600 bar

    NASA Astrophysics Data System (ADS)

    Spycher, Nicolas; Pruess, Karsten; Ennis-King, Jonathan

    2003-08-01

    Evaluating the feasibility of CO 2 geologic sequestration requires the use of pressure-temperature-composition ( P- T- X) data for mixtures of CO 2 and H 2O at moderate pressures and temperatures (typically below 500 bar and below 100°C). For this purpose, published experimental P- T- X data in this temperature and pressure range are reviewed. These data cover the two-phase region where a CO 2-rich phase (generally gas) and an H 2O-rich liquid coexist and are reported as the mutual solubilities of H 2O and CO 2 in the two coexisting phases. For the most part, mutual solubilities reported from various sources are in good agreement. In this paper, a noniterative procedure is presented to calculate the composition of the compressed CO 2 and liquid H 2O phases at equilibrium, based on equating chemical potentials and using the Redlich-Kwong equation of state to express departure from ideal behavior. The procedure is an extension of that used by King et al. (1992), covering a broader range of temperatures and experimental data than those authors, and is readily expandable to a nonideal liquid phase. The calculation method and formulation are kept as simple as possible to avoid degrading the performance of numerical models of water-CO 2 flows for which they are intended. The method is implemented in a computer routine, and inverse modeling is used to determine, simultaneously, (1) new Redlich-Kwong parameters for the CO 2-H 2O mixture, and (2) aqueous solubility constants for gaseous and liquid CO 2 as a function of temperature. In doing so, mutual solubilities of H 2O from 15 to 100°C and CO 2 from 12 to 110°C and up to 600 bar are generally reproduced within a few percent of experimental values. Fugacity coefficients of pure CO 2 are reproduced mostly within one percent of published reference data.

  13. Experimental studies of the formation of cluster ions formed by corona discharge in an atmosphere containing SO2, NH3, and H2O

    NASA Astrophysics Data System (ADS)

    Pedersen, J. O.; Hvelplund, P.; Støchkel, K.; Enghoff, M. B.; Kurten, T.

    2013-12-01

    We report on studies of ion induced nucleation in a corona discharge taking place in an atmosphere containing SO2, NH3, and H2O at standard temperature and pressure. Positive ions such as H3O+(H2O)n, NH4+(H2O)n, and H+(H2SO4)(H2O)n and negative ions such as HSO5-(H2O)n, SO4-(H2O)n, HSO4-(H2O)n and NO3-(H2O)n have been recorded. Large values of n (> 100) were observed and the experiment indicates the existence of even larger water clusters. In contrast, only clusters with a maximum of 2 sulfuric acid molecules were observed. Fragmentation studies also revealed that the negative ion HSO5-, which has been observed in many studies, in our experiments is contaminated by O2-(HNO3)(H2O) ions, and this may also have been the case in other experiments. Finally an ion with m/z = 232 (where m is the cluster mass in amu and z the charge state), capable of attaching H2O-molecules was observed and studied by fragmentation. Positive ion m/z (mass/charge) spectrum

  14. Multidimentional Normal Mode Calculations for the OH Vibrational Spectra of (H_2O)_3^+, (H_2O)_3^+Ar, H^+(H_2O)_3, and H^+(H_2O)_3Ar

    NASA Astrophysics Data System (ADS)

    Li, Ying-Cheng; Chuang, Hsiao-Han; Tan, Jake Acedera; Takahashi, Kaito; Kuo, Jer-Lai

    2014-06-01

    Recent experimental observations of (H_2O)_3^+, (H_2O)_3^+Ar, H^+(H_2O)_3, and H^+(H_2O)_3Ar clusters in the region 1400-3800 wn show that the OH stretching vibration has distinct characteristics. Multidimensional normal mode calculations were carried out for OH stretching vibrations in the 1200-4000 wn photon energy range. The potential energy and dipole surfaces were evaluated by using first-principles methods. By comparing the calculated frequencies and intensities of OH stretching vibration with experimental spectra, we found that the assignment of OH strecthing of H_3O^+ moiety and free OH strectching vibration have resonable agreement with experimental data. Jeffrey M. Headrick, Eric G. Diken, Richard S. Walters, Nathan I. Hammer, Richard A. Christie, Jun Cui, Evgeniy M. Myshakin, Michael A. Duncan, Mark A. Johnson, Kenneth D. Jordan, Science, 2005, 17, 1765. Kenta Mizuse, Jer-Lai Kuo and Asuka Fujii, Chem. Sci., 2011, 2, 868 Kenta Mizuse and Asuka Fujii, J. Phys. Chem. A, 2013, 117, 929.

  15. Water in planetary and cometary atmospheres: H2O/HDO transmittance and fluorescence models

    NASA Astrophysics Data System (ADS)

    Villanueva, G. L.; Mumma, M. J.; Bonev, B. P.; Novak, R. E.; Barber, R. J.; Disanti, M. A.

    2012-02-01

    We developed a modern methodology to retrieve water (H2O) and deuterated water (HDO) in planetary and cometary atmospheres, and constructed an accurate spectral database that combines theoretical and empirical results. On the basis of a greatly expanded set of spectroscopic parameters, we built a full non-resonance cascade fluorescence model and computed fluorescence efficiencies for H2O (500 million lines) and HDO (700 million lines). The new line list was also integrated into an advanced terrestrial radiative transfer code (LBLRTM) and adapted to the CO2 rich atmosphere of Mars, for which we adopted the complex Robert-Bonamy formalism for line shapes. We retrieved water and D/H in the atmospheres of Mars, comet C/2007 W1 (Boattini), and Earth by applying the new formalism to spectra obtained with the high-resolution spectrograph NIRSPEC/Keck II atop Mauna Kea (Hawaii). The new model accurately describes the complex morphology of the water bands and greatly increases the accuracy of the retrieved abundances (and the D/H ratio in water) with respect to previously available models. The new model provides improved agreement of predicted and measured intensities for many H2O lines already identified in comets, and it identifies several unassigned cometary emission lines as new emission lines of H2O. The improved spectral accuracy permits retrieval of more accurate rotational temperatures and production rates for cometary water.

  16. Water Planetary and Cometary Atmospheres: H2O/HDO Transmittance and Fluorescence Models

    NASA Technical Reports Server (NTRS)

    Villanueva, G. L.; Mumma, M. J.; Bonev, B. P.; Novak, R. E.; Barber, R. J.; DiSanti, M. A.

    2012-01-01

    We developed a modern methodology to retrieve water (H2O) and deuterated water (HDO) in planetary and cometary atmospheres, and constructed an accurate spectral database that combines theoretical and empirical results. Based on a greatly expanded set of spectroscopic parameters, we built a full non-resonance cascade fluorescence model and computed fluorescence efficiencies for H2O (500 million lines) and HDO (700 million lines). The new line list was also integrated into an advanced terrestrial radiative transfer code (LBLRTM) and adapted to the CO2 rich atmosphere of Mars, for which we adopted the complex Robert-Bonamy formalism for line shapes. We then retrieved water and D/H in the atmospheres of Mars, comet C/2007 WI, and Earth by applying the new formalism to spectra obtained with the high-resolution spectrograph NIRSPEC/Keck II atop Mauna Kea (Hawaii). The new model accurately describes the complex morphology of the water bands and greatly increases the accuracy of the retrieved abundances (and the D/H ratio in water) with respect to previously available models. The new model provides improved agreement of predicted and measured intensities for many H2O lines already identified in comets, and it identifies several unassigned cometary emission lines as new emission lines of H2O. The improved spectral accuracy permits retrieval of more accurate rotational temperatures and production rates for cometary water.

  17. Quantitative evaluation of the effect of H2O degassing on the oxidation state of magmas

    NASA Astrophysics Data System (ADS)

    Lange, R. A.; Waters, L.

    2014-12-01

    The extent to which degassing of the H2O component affects the oxidation state of hydrous magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of various magmas, whereas our focus is on the H2O component. There are two ways that degassing of H2O by itself may cause oxidation: (1) the reaction: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt), and/or (2) if dissolved water preferentially enhances the activity of ferrous vs. ferric iron in magmatic liquids. In this study, a comparison is made between the pre-eruptive oxidation states of 14 crystal-poor, jet-black obsidian samples (obtained from two Fe-Ti oxides) and their post-eruptive values (analyzed with the Wilson 1960 titration method tested against USGS standards). The obsidians are from Medicine Lake (CA), Long Valley (CA), and the western Mexican arc; all have low FeOT (1.1-2.1 wt%), rendering their Fe2+/Fe3+ ratios highly sensitive to the possible effects of substantial H2O degassing. The Fe-Ti oxide thermometer/oxybarometer of Ghiorso and Evans, (2008) gave temperatures for the 14 samples that range for 720 to 940°C and ∆NNO values of -0.9 to +1.4. With temperature known, the plagioclase-liquid hygrometer was applied and show that ≤ 6.5 wt% H2O was dissolved in the melts prior to eruption. In addition, pre-eruptive Cl and S concentrations were constrained on the basis of apatite analyses (Webster et al., 2009) and sulfur concentrations needed for saturation with pyrrhotite (Clemente et al., 2004), respectively. Maximum pre-eruptive chlorine and sulfur contents are 6000 and 200 ppm, respectively. After eruption, the rhyolites lost nearly all of their volatiles. Our results indicate no detectable change between pre- and post-eruptive Fe2+ concentrations, with an average deviation of ± 0.1 wt % FeO. Although degassing of large concentrations of S and/or Cl may affect the oxidation state of magmas, at the pre-eruptive levels

  18. Promotion of CO oxidation on PdO(101) by adsorbed H2O

    NASA Astrophysics Data System (ADS)

    Choi, Juhee; Pan, Li; Mehar, Vikram; Zhang, Feng; Asthagiri, Aravind; Weaver, Jason F.

    2016-08-01

    We investigated the influence of adsorbed H2O on the oxidation of CO on PdO(101) using temperature programmed reaction spectroscopy (TPRS), reflection absorption infrared spectroscopy (RAIRS) and density functional theory (DFT) calculations. We find that water inhibits CO adsorption on PdO(101) by site blocking, but also provides a more facile pathway for CO oxidation compared with the bare oxide surface. In the presence of adsorbed H2O, the oxidation of CO on PdO(101) produces a CO2 TPRS peak that is centered at a temperature ~ 50 K lower than the main CO2 TPRS peak arising from CO oxidation on clean PdO(101) (~ 330 vs. 380 K). RAIRS shows that CO continues to adsorb on atop-Pd sites of PdO(101) when H2O is co-adsorbed, and provides no evidence of other reactive intermediates. DFT calculations predict that the CO oxidation mechanism follows the same steps for CO adsorbed on PdO(101) with and without co-adsorbed H2O, wherein an atop-CO species recombines with an oxygen atom from the oxide surface lattice. According to DFT, hydrogen bonding interactions with adsorbed H2O species stabilize the carboxyl-like transition structure and intermediate that result from the initial recombination of CO and O on the PdO(101) surface. This stabilization lowers the energy barrier for CO oxidation on PdO(101) by ~ 10 kJ/mol, in good agreement with our experimental estimate.

  19. Electronic and chemical structure of the H2O/GaN(0001) interface under ambient conditions

    NASA Astrophysics Data System (ADS)

    Zhang, Xueqiang; Ptasinska, Sylwia

    2016-04-01

    We employed ambient pressure X-ray photoelectron spectroscopy to investigate the electronic and chemical properties of the H2O/GaN(0001) interface under elevated pressures and/or temperatures. A pristine GaN(0001) surface exhibited upward band bending, which was partially flattened when exposed to H2O at room temperature. However, the GaN surface work function was slightly reduced due to the adsorption of molecular H2O and its dissociation products. At elevated temperatures, a negative charge generated on the surface by a vigorous H2O/GaN interfacial chemistry induced an increase in both the surface work function and upward band bending. We tracked the dissociative adsorption of H2O onto the GaN(0001) surface by recording the core-level photoemission spectra and obtained the electronic and chemical properties at the H2O/GaN interface under operando conditions. Our results suggest a strong correlation between the electronic and chemical properties of the material surface, and we expect that their evolutions lead to significantly different properties at the electrolyte/electrode interface in a photoelectrochemical solar cell.

  20. Electronic and chemical structure of the H2O/GaN(0001) interface under ambient conditions.

    PubMed

    Zhang, Xueqiang; Ptasinska, Sylwia

    2016-01-01

    We employed ambient pressure X-ray photoelectron spectroscopy to investigate the electronic and chemical properties of the H2O/GaN(0001) interface under elevated pressures and/or temperatures. A pristine GaN(0001) surface exhibited upward band bending, which was partially flattened when exposed to H2O at room temperature. However, the GaN surface work function was slightly reduced due to the adsorption of molecular H2O and its dissociation products. At elevated temperatures, a negative charge generated on the surface by a vigorous H2O/GaN interfacial chemistry induced an increase in both the surface work function and upward band bending. We tracked the dissociative adsorption of H2O onto the GaN(0001) surface by recording the core-level photoemission spectra and obtained the electronic and chemical properties at the H2O/GaN interface under operando conditions. Our results suggest a strong correlation between the electronic and chemical properties of the material surface, and we expect that their evolutions lead to significantly different properties at the electrolyte/electrode interface in a photoelectrochemical solar cell. PMID:27108711

  1. Electronic and chemical structure of the H2O/GaN(0001) interface under ambient conditions

    PubMed Central

    Zhang, Xueqiang; Ptasinska, Sylwia

    2016-01-01

    We employed ambient pressure X-ray photoelectron spectroscopy to investigate the electronic and chemical properties of the H2O/GaN(0001) interface under elevated pressures and/or temperatures. A pristine GaN(0001) surface exhibited upward band bending, which was partially flattened when exposed to H2O at room temperature. However, the GaN surface work function was slightly reduced due to the adsorption of molecular H2O and its dissociation products. At elevated temperatures, a negative charge generated on the surface by a vigorous H2O/GaN interfacial chemistry induced an increase in both the surface work function and upward band bending. We tracked the dissociative adsorption of H2O onto the GaN(0001) surface by recording the core-level photoemission spectra and obtained the electronic and chemical properties at the H2O/GaN interface under operando conditions. Our results suggest a strong correlation between the electronic and chemical properties of the material surface, and we expect that their evolutions lead to significantly different properties at the electrolyte/electrode interface in a photoelectrochemical solar cell. PMID:27108711

  2. Electronic and chemical structure of the H2O/GaN(0001) interface under ambient conditions

    DOE PAGESBeta

    Zhang, Xueqiang; Ptasinska, Sylwia

    2016-04-25

    We employed ambient pressure X-ray photoelectron spectroscopy to investigate the electronic and chemical properties of the H2O/GaN(0001) interface under elevated pressures and/or temperatures. A pristine GaN(0001) surface exhibited upward band bending, which was partially flattened when exposed to H2O at room temperature. However, the GaN surface work function was slightly reduced due to the adsorption of molecular H2O and its dissociation products. At elevated temperatures, a negative charge generated on the surface by a vigorous H2O/GaN interfacial chemistry induced an increase in both the surface work function and upward band bending. We tracked the dissociative adsorption of H2O onto themore » GaN(0001) surface by recording the core-level photoemission spectra and obtained the electronic and chemical properties at the H2O/GaN interface under operando conditions. In conclusion, our results suggest a strong correlation between the electronic and chemical properties of the material surface, and we expect that their evolutions lead to significantly different properties at the electrolyte/ electrode interface in a photoelectrochemical solar cell.« less

  3. Degassing of H2O in a phonolitic melt: A closer look at decompression experiments

    NASA Astrophysics Data System (ADS)

    Marxer, Holger; Bellucci, Philipp; Nowak, Marcus

    2015-05-01

    Melt degassing during magma ascent is controlled by the decompression rate and can be simulated in decompression experiments. H2O-bearing phonolitic melts were decompressed at a super-liquidus T of 1323 K in an internally heated argon pressure vessel, applying continuous decompression (CD) as well as to date commonly used step-wise decompression (SD) techniques to investigate the effect of decompression method on melt degassing. The hydrous melts were decompressed from 200 MPa at nominal decompression rates of 0.0028-1.7 MPa·s- 1. At final pressure (Pfinal), the samples were quenched rapidly at isobaric conditions with ~ 150 K·s- 1. The bubbles in the quenched samples are often deformed and dented. Flow textures in the glass indicate melt transport at high viscosity. We suggest that this observation is due to bubble shrinkage during quench. This general problem was mostly overlooked in the interpretation of experimentally degassed samples to date. Bubble shrinkage due to decreasing molar volume (Vm) of the exsolved H2O in the bubbles occurs during isobaric rapid quench until the melt is too viscous too relax. The decrease of Vm(H2O) during cooling at Pfinal of the experiments results in a decrease of the bubble volume by a shrinking factor Bs: At nominal decompression rates > 0.17 MPa·s- 1 and a Pfinal of 75 MPa, the decompression method has only minor influence on melt degassing. SD and CD result in high bubble number densities of 104-105 mm- 3. Fast P drop leads to immediate supersaturation with H2O in the melt. At such high nominal decompression rates, the diffusional transport of H2O is limited and therefore bubble nucleation is the predominant degassing process. The residual H2O contents in the melts decompressed to 75 MPa increase with nominal decompression rate. After homogeneous nucleation is triggered, CD rates ≤ 0.024 MPa·s- 1 facilitate continuous reduction of the supersaturation by H2O diffusion into previously nucleated bubbles. Bubble number

  4. Boiling Temperature and Reversed Deliquescence Relative Humidity Measurements for Mineral Assemblages in the NaCl + NaNO3 + KNO3 + Ca(NO3)2 + H2O System

    SciTech Connect

    Rard, J A; Staggs, K J; Day, S D; Carroll, S A

    2005-12-01

    Boiling temperature measurements have been made at ambient pressure for saturated ternary solutions of NaCl + KNO{sub 3} + H{sub 2}O, NaNO{sub 3} + KNO{sub 3} + H{sub 2}O, and NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O over the full composition range, along with those of the single salt systems. Boiling temperatures were also measured for the four component NaCl + NaNO{sub 3} + KNO{sub 3} + H{sub 2}O and five component NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O mixtures, where the solute mole fraction of Ca(NO{sub 3}){sub 2}, x(Ca(NO{sub 3}){sub 2}), was varied between 0 and 0.25. The maximum boiling temperature found for the NaCl + KNO{sub 3} + H{sub 2}O system is {approx} 134.9 C; for the NaNO{sub 3} + KNO{sub 3} + H{sub 2}O system is {approx} 165.1 C at x(NaNO{sub 3}) {approx} 0.46 and x(KNO{sub 3}) {approx} 0.54; and for the NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O system is 164.7 {+-} 0.6 C at x(NaCl) {approx} 0.25 and x(Ca(NO{sub 3}){sub 2}) {approx} 0.75. The NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O system forms molten salts below their maximum boiling temperatures, and the temperatures corresponding to the cessation of boiling (dry out temperatures) of these liquid mixtures were determined. These dry out temperatures range from {approx} 300 C when x(Ca(NO{sub 3}){sub 2}) = 0 to {ge} 400 C when x(Ca(NO{sub 3}){sub 2}) = 0.20 and 0.25. Mutual deliquescence/efflorescence relative humidity (MDRH/MERH) measurements were also made for the NaNO{sub 3} + KNO{sub 3} and NaCl + NaNO{sub 3} + KNO{sub 3} salt mixture from 120 to 180 C at ambient pressure. The NaNO{sub 3} and NaCl + NaNO{sub 3} + KNO{sub 3} salt mixture has a MDRH of 26.4% at 120 C and 20.0% at 150 C. This salt mixture also absorbs water at 180 C, which is higher than expected from the boiling temperature experiments. The NaCl + NaNO{sub 3} + KNO{sub 3} salt mixture was found to have a MDRH of 25.9% at 120 C and 10.5% at 180 C. The investigated mixture

  5. Thermodynamic modelling of a double-effect LiBr-H2O absorption refrigeration cycle

    NASA Astrophysics Data System (ADS)

    Iranmanesh, A.; Mehrabian, M. A.

    2012-12-01

    The goal of this paper is to estimate the conductance of components required to achieve the approach temperatures, and gain insights into a double-effect absorption chiller using LiBr-H2O solution as the working fluid. An in-house computer program is developed to simulate the cycle. Conductance of all components is evaluated based on the approach temperatures assumed as input parameters. The effect of input data on the cycle performance and the exergetic efficiency are investigated.

  6. Detection of H2O2 at the nanomolar level by electrode modified with ultrathin AuCu nanowires.

    PubMed

    Wang, Ning; Han, Yu; Xu, Ying; Gao, Caizhen; Cao, Xia

    2015-01-01

    Bimetallic AuCu nanowires (AuCuNWs) are synthesized via a facile water solution method at room temperature. Enhanced electrocatalytic activity is observed toward the oxidation of H2O2, which makes the AuCu nanowire, along with its unique catalytic properties, intriguing bifunctional mechanism, and surface atomic construction, a promising platform for the amplification of interfacing signal. A highly sensitive H2O2 biosensor is thus developed on the base of the as-prepared AuCuNW catalyst. A very low real determination limit (2.0 nM) was reached, and a linear range as wide as 5 orders of magnitude was demonstrated. In addition, a trace amount of H2O2, which was released from Raw 264.7 cells, was selectively detected, hinting at the possible applications for real-time quantitative detection of H2O2 in a biological environment. PMID:25418032

  7. Mapping of [HDO]/[H2O] in the Martian Atmosphere

    NASA Astrophysics Data System (ADS)

    Novak, R. E.; Mumma, M. J.; Villanueva, G.; Bonev, B.; Disanti, M.

    Observations of the Martian atmosphere were taken for several seasonal dates at NASA's IRTF using CSHELL. Column densities of HDO and H2O were extracted from individual spectral lines near 3.67 ìm and 3.29 ìm. The slit was positioned N-S on Mars centered at the sub-earth point producing spectral/spatial images. Spectra were extracted at 0.6 arc-sec. intervals and analyzed with models created from GENLN2 atmospheric software; the models include solar Fraunhofer lines, a two-way transmission through Mars' atmosphere, thermal emission from Mars' surface and atmosphere, and a one way transmission through the Earth's atmosphere. From these, latitudinal maps of HDO/H2O were constructed across the observable planet. The HDO/H2O ratios have been found to be larger than those on Earth and they vary with both latitude and season. The higher global HDO/H2O value on Mars compared to that of the Earth is attributed to differential Jeans escape of D and H over geologic time. The ratio in the southern Martian hemisphere is found to be larger than that in the north. This difference could be the signature of Rayleigh distillation, a process in which the different mean temperatures of the polar caps causes a different degree of HDO sequestration resulting in different degrees of enrichment in the polar caps. Detailed results for Ls= 357o in 2006 will be presented when both the HDO and the H2O column densities were obtain from CSHELL data. These will be compared to results from other seasons.Observations of the Martian atmosphere were taken for several seasonal dates at NASA's IRTF using CSHELL. Column densities of HDO and H2O were extracted from individual spectral lines near 3.67 ìm and 3.29 ìm. The slit was positioned N-S on Mars centered at the sub-earth point producing spectral/spatial images. Spectra were extracted at 0.6 arc-sec. intervals and analyzed with models created from GENLN2 atmospheric software; the models include solar Fraunhofer lines, a two-way transmission

  8. Oxidative degradation of endotoxin by advanced oxidation process (O3/H2O2 & UV/H2O2).

    PubMed

    Oh, Byung-Taek; Seo, Young-Suk; Sudhakar, Dega; Choe, Ji-Hyun; Lee, Sang-Myeong; Park, Youn-Jong; Cho, Min

    2014-08-30

    The presence of endotoxin in water environments may pose a serious public health hazard. We investigated the effectiveness of advanced oxidative processes (AOP: O3/H2O2 and UV/H2O2) in the oxidative degradation of endotoxin. In addition, we measured the release of endotoxin from Escherichia coli following typical disinfection methods, such as chlorine, ozone alone and UV, and compared it with the use of AOPs. Finally, we tested the AOP-treated samples in their ability to induce tumor necrosis factor alpha (TNF-α) in mouse peritoneal macrophages. The production of hydroxyl radical in AOPs showed superior ability to degrade endotoxin in buffered solution, as well as water samples from Korean water treatment facilities, with the ozone/H2O2 being more efficient compared to UV/H2O2. In addition, the AOPs proved effective not only in eliminating E. coli in the samples, but also in endotoxin degradation, while the standard disinfection methods lead to the release of endotoxin following the bacteria destruction. Furthermore, in the experiments with macrophages, the AOPs-deactivated endotoxin lead to the smallest induction of TNF-α, which shows the loss of inflammation activity, compared to ozone treatment alone. In conclusion, these results suggest that AOPs offer an effective and mild method for endotoxin degradation in the water systems. PMID:25038578

  9. Vibrational investigations of CO2-H2O, CO2-(H2O)2, and (CO2)2-H2O complexes isolated in solid neon.

    PubMed

    Soulard, P; Tremblay, B

    2015-12-14

    The van der Waals complex of H2O with CO2 has attracted considerable theoretical interest as a typical example of a weak binding complex with a dissociation energy less than 3 kcal/mol. Up to now, experimental vibrational data are sparse. We have studied by FTIR the complexes involving CO2 and water molecules in solid neon. Many new absorption bands close to the well known monomers fundamentals give evidence for at least three (CO2)n-(H2O)m complexes, noted n:m. Concentration effects combined with a detailed vibrational analysis allow for the identification of sixteen, twelve, and five transitions for the 1:1, 1:2, and 2:1 complexes, respectively. Careful examination of the far infrared spectral region allows the assignment of several 1:1 and 1:2 intermolecular modes, confirmed by the observation of combinations of intra + intermolecular transitions, and anharmonic coupling constants have been derived. Our results demonstrate the high sensibility of the solid neon isolation to investigate the hydrogen-bonded complexes in contrast with the gas phase experiments for which two quanta transitions cannot be easily observed. PMID:26671379

  10. Vibrational investigations of CO2-H2O, CO2-(H2O)2, and (CO2)2-H2O complexes isolated in solid neon

    NASA Astrophysics Data System (ADS)

    Soulard, P.; Tremblay, B.

    2015-12-01

    The van der Waals complex of H2O with CO2 has attracted considerable theoretical interest as a typical example of a weak binding complex with a dissociation energy less than 3 kcal/mol. Up to now, experimental vibrational data are sparse. We have studied by FTIR the complexes involving CO2 and water molecules in solid neon. Many new absorption bands close to the well known monomers fundamentals give evidence for at least three (CO2)n-(H2O)m complexes, noted n:m. Concentration effects combined with a detailed vibrational analysis allow for the identification of sixteen, twelve, and five transitions for the 1:1, 1:2, and 2:1 complexes, respectively. Careful examination of the far infrared spectral region allows the assignment of several 1:1 and 1:2 intermolecular modes, confirmed by the observation of combinations of intra + intermolecular transitions, and anharmonic coupling constants have been derived. Our results demonstrate the high sensibility of the solid neon isolation to investigate the hydrogen-bonded complexes in contrast with the gas phase experiments for which two quanta transitions cannot be easily observed.

  11. CO2 and H2O diluted oxy-fuel combustion for zero-emission power

    SciTech Connect

    G A Richards; K H Casleton; B T Chorpening

    2005-01-01

    Concerns about climate change have encouraged significant interest in concepts for zero-emission power generation systems. These systems are intended to produce power without releasing CO2 into the atmosphere. One method to achieve this goal is to produce hydrogen from the gasification of fossil or biomass fuels. Using various membrane and reforming technologies, the carbon in the parent fuel can be shifted to CO2 and removed from the fuel stream, followed by direct CO2 sequestration. The hydrogen fuel can be used directly in gas turbines fitted with low-NOx combustors. A second approach to producing zero-emission power is to replace the nitrogen diluent that accompanies conventional combustion in air with either CO2 or H2O. In this concept, CO2 or H2O is added to oxygen to control combustion temperatures in oxygen–fuel reactions. In the absence of nitrogen, the primary combustion products for any hydrocarbon under lean conditions are then simply CO2 and H2O. Thus, merely cooling the exhaust stream condenses the water and produces an exhaust of pure CO2, ready for sequestration. The dilute oxy-fuel combustion strategy can be incorporated in power cycles that are similar to Brayton or Rankine configurations, using CO2 or H2O as the primary diluent respectively. While the relativemerits of the various strategies to zero-emission power are the subject of various technical and economic studies, very little work has focused on defining the combustion issues associated with the dilute oxy-fuel option. In this paper, the expected combustion performance of CO2 and H2O diluted systems are compared. Experimental results from a high-pressure oxy-fuel combustor are also presented.

  12. Chemistry in glow discharges of H2 / O2 mixtures. Diagnostics and modelling

    PubMed Central

    Jiménez-Redondo, M; Carrasco, E; Herrero, V J; Tanarro, I

    2015-01-01

    The chemistry of low pressure H2 + O2 discharges with different mixture ratios has been studied in a hollow cathode DC reactor. Neutral and positive ion distributions have been measured by mass spectrometry, and Langmuir probes have been used to provide charge densities and electron temperatures. A simple zero order kinetic model including neutral species and positive and negative ions, which takes into account gas-phase and heterogeneous chemistry, has been used to reproduce the global composition of the plasmas over the whole range of mixtures experimentally studied, and allows for the identification of the main physicochemical mechanisms that may explain the experimental results. To our knowledge, no combined experimental and modelling studies of the heavy species kinetics of low pressure H2 + O2 plasmas including ions has been reported before. As expected, apart from the precursors, H2O is detected in considerable amounts. The model also predicts appreciable concentrations of H and O atoms and the OH radical. The relevance of the metastable species O(1D) and O2(a1Δg) is analysed. Concerning the charged species, positive ion distributions are dominated by H3O+ for a wide range of intermediate mixtures, while H3+ and O2+ are the major ions for the higher and lower H2/O2 ratios, respectively. The mixed ions OH+, H2O+ and HO2+ are also observed in small amounts. Negative ions are shown to have a limited relevance in the global chemistry; their main contribution is the reduction of the electron density available for electron impact processes. PMID:26702195

  13. Distillation of H2O from hard-frozen Martian permafrost

    NASA Technical Reports Server (NTRS)

    Zent, A. P.; Gwynne, O.

    1991-01-01

    The authors present a method for distillation of hard-frozen Martian permafrost. A cable-tool is drilled into hard frozem permafrost to a depth of 10 to 20 m. They calculate that a 10 m hole could be drilled in a few days. A 10 m shaft with a diameter equal to the bore is inserted into the hole, and a air tight tent-like structure is erected over the borehole. Photovoltaic cells mounted on the tent supply electrical energy that is dissipated in the shaft. Drilling power can be supplied by other sources. With 1000 watts, the shaft can be heated to near 350 K, producing relatively high temperatures in the vicinity of the borehole. Surrounding H2O is vaporized and diffuses up through the regolith. The authors calculate that a tent of a radius of no more than a few meters would intercept most of the H2O as it diffused to the surface. Calculations suggest that it would require perhaps 30 days to extract H2O from most of the volume drained by this technique. Assuming that the hard frozen regolith is no more than 10 percent ice, the author's calculate that that about 2890 kg of H2O could be extracted in 30 days. Since the nominal requirement for each crew member is about 5 kg/day, one such borehole might be expected to supply enough H2O to maintain a crew of 5 for perhaps 100 days. Additional engineering studies will be done to attempt to improve the capacity or efficiency of this method.

  14. Distillation of H2O from hard-frozen Martian permafrost

    NASA Astrophysics Data System (ADS)

    Zent, A. P.; Gwynne, O.

    The authors present a method for distillation of hard-frozen Martian permafrost. A cable-tool is drilled into hard frozem permafrost to a depth of 10 to 20 m. They calculate that a 10 m hole could be drilled in a few days. A 10 m shaft with a diameter equal to the bore is inserted into the hole, and a air tight tent-like structure is erected over the borehole. Photovoltaic cells mounted on the tent supply electrical energy that is dissipated in the shaft. Drilling power can be supplied by other sources. With 1000 watts, the shaft can be heated to near 350 K, producing relatively high temperatures in the vicinity of the borehole. Surrounding H2O is vaporized and diffuses up through the regolith. The authors calculate that a tent of a radius of no more than a few meters would intercept most of the H2O as it diffused to the surface. Calculations suggest that it would require perhaps 30 days to extract H2O from most of the volume drained by this technique. Assuming that the hard frozen regolith is no more than 10 percent ice, the author's calculate that that about 2890 kg of H2O could be extracted in 30 days. Since the nominal requirement for each crew member is about 5 kg/day, one such borehole might be expected to supply enough H2O to maintain a crew of 5 for perhaps 100 days. Additional engineering studies will be done to attempt to improve the capacity or efficiency of this method.

  15. Preliminary results in the NASA Lewis H2-O2 combustion MHD experiment

    NASA Technical Reports Server (NTRS)

    Smith, J. M.

    1979-01-01

    MHD (magnetohydrodynamic) power generation experiments were carried out in the NASA Lewis Research Center cesium-seeded H2-O2 combustion facility. This facility uses a neon-cooled cryomagnet capable of producing magnetic fields in excess of 5 tesla. The effects of power takeoff location, generator loading, B-field strength, and electrode breakdown on generator performance are discussed. The experimental data is compared to a theory based on one-dimensional flow with heat transfer, friction, and voltage drops.

  16. FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT ETERNAL Drought(s)-Elimination FOREVER!!!

    NASA Astrophysics Data System (ADS)

    Wignall, J.; Lyons, Marv; Ertl, G.; Alefeld, Georg; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

    2013-03-01

    ''H2O H2O everywhere; ne'er a drop to drink''[Coleridge(1798)] now: ''H2 H2 everywhere; STILL ne'er a drop to drink'': ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): { ∖{}O/H2O{ ∖}} =[16]/[18] ∖sim 90{ ∖%} O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [ ∖underline {3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9 /2007)] crucial geomorphology which ONLY maximal-buoyancy H2 can exploit, to again make ''Mountains into Fountains'', ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': ''terraforming''(and ocean-rebasificaton!!!) ONLY VIA Siegel[APS March MTGS.:1960s-2000ss) DIFFUSIVE-MAGNETORESISTANCE (DMR) proprietary MAGNETIC-HYDROGEN-VALVE(MHV) ALL-IMPORTANT PRECLUDED RADIAL-diffusion, permitting ONLY AXIAL-H2-BALLISTIC-flow (``G.A''.''/DoE''/''Terrapower''/''Intellectual-Ventures''/ ''Gileland''/ ''Myhrvold''/''Gates'' ``ARCHIMEDES'') in ALREADY IN-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/ famine)

  17. The target: H2O on the Moon

    NASA Astrophysics Data System (ADS)

    Green, J.; Wys, J. Negusde; Zuppero, A.

    1992-09-01

    The importance of H2O on the lunar surface has long been identified as a high priority for the existence of a human colony for mining activities and, more recently, for space fuel. Using the Earth as an analog, volcanic activity would suggest the generation of water during lunar history. Evidence of volcanism is found not only in present lunar morphology, but in over 400 locations of lunar transient events cataloged by Middlehurst and Kuiper in the 1960's. These events consisted of sightings since early history of vapor emissions and bright spots or flares. Later infrared scanning by Saari and Shorthill showed 'hot spots', many of which coincided with transient event sites. Many of the locations of Middlehurst and Kuiper were the sites of repeat events, leading to the conclusion that these were possibly volcanic in nature. The detection and use of H2O from the lunar surface is discussed.

  18. Antiferromagnetism of UO2⋅2H2O

    USGS Publications Warehouse

    Pankey, T.; Senftle, F.E.; Cuttitta, F.

    1963-01-01

    Magnetic susceptibility measurements have been made on UO2⋅xH2O for x=1.78 to x=2.13, and from 77° to 375°K. As the value of x decreased the susceptibility increased. Both these data and structural arguments imply that the formula of this compound is U(OH)4 rather than the dihydrate form. Based on this concept the data have been corrected for diamagnetism and also small amounts of UO2 and H2O which were present. The molar susceptibility of U4+ in U(OH)4 is nearly an order of magnitude less than in other uranium compounds, and it is suggested that this is probably due to superexchange between adjacent uranium atoms through intervening oxygen atoms.

  19. The Target: H2O on the Moon

    NASA Technical Reports Server (NTRS)

    Green, J.; Wys, J. Negusde; Zuppero, A.

    1992-01-01

    The importance of H2O on the lunar surface has long been identified as a high priority for the existence of a human colony for mining activities and, more recently, for space fuel. Using the Earth as an analog, volcanic activity would suggest the generation of water during lunar history. Evidence of volcanism is found not only in present lunar morphology, but in over 400 locations of lunar transient events cataloged by Middlehurst and Kuiper in the 1960's. These events consisted of sightings since early history of vapor emissions and bright spots or flares. Later infrared scanning by Saari and Shorthill showed 'hot spots', many of which coincided with transient event sites. Many of the locations of Middlehurst and Kuiper were the sites of repeat events, leading to the conclusion that these were possibly volcanic in nature. The detection and use of H2O from the lunar surface is discussed.

  20. Detection Of OH+ And H2O+ Towards Orion KL

    NASA Astrophysics Data System (ADS)

    Gupta, Harshal; Rimmer, P.; Pearson, J. C.; Herbst, E.; Yu, S.; Bergin, E. A.; Key Program, HEXOS

    2011-01-01

    The reactive molecular ions, OH+, H2O+, and H3O+, key probes of the oxygen chemistry of the interstellar gas, have been observed toward Orion KL with the Heterodyne Instrument for Far Infrared on board the Herschel Space Observatory. All three N = 1 - 0 fine-structure transitions of OH+ at 909, 971, and 1033 GHz and both fine-structure components of the doublet ortho-H2O+ 111 - 000 transition at 1115 and 1139 GHz were detected, and an upper limit was obtained for H3O+. OH+ and H2O+ are observed purely in absorption, showing a narrow component at the source velocity of 9 km s-1, and a broad blue shifted absorption similar to that reported recently for HF and para-H218O, and attributed to the low velocity outflow of Orion KL. We estimate column densities of OH+ and H2O+ for the 9 km s-1 component of 9 ± 3 x 1012 cm-2 and 7 ± 2 x 1012 cm-2, and those in the outflow of 1.9 ± 0.7 x 1013 cm-2 and 1.0 ± 0.3 x 1013 cm-2. Upper limits of 2.4 x 1012 cm-2 and 8.7 ± 1012 cm-2 were derived for the column densities of ortho and para-H3O+ from transitions near 985 and 1657 GHz. The column densities of the three ions are up to an order of magnitude lower than those obtained from recent observations of W31C and W49N. A higher gas density, despite the assumption of a large ionization rate, may explain the comparatively low column densities of the ions. A part of this work was performed at the Jet Propulsion Laboratory, California Institute of Technology under contract with the National Aeronautics and Space Administration. Copyright 2010© California Institute of Technology. All rights reserved.

  1. Bactericidal Effect of Photolysis of H2O2 in Combination with Sonolysis of Water via Hydroxyl Radical Generation

    PubMed Central

    Sheng, Hong; Nakamura, Keisuke; Kanno, Taro; Sasaki, Keiichi; Niwano, Yoshimi

    2015-01-01

    The bactericidal effect of hydroxyl radical (·OH) generated by combination of photolysis of hydrogen peroxide (H2O2) and sonolysis of water was examined under the condition in which the yield of ·OH increased additively when H2O2 aqueous solution was concomitantly irradiated with laser and ultrasound. The suspension of Staphylococcus aureus mixed with the different concentrations of H2O2 was irradiated simultaneously with a laser light (wavelength: 405 nm, irradiance: 46 and 91 mW/cm2) and ultrasound (power: 30 w, frequency: 1.65 MHz) at 20 ± 1°C of the water bulk temperature for 2 min. The combination of laser and ultrasound irradiation significantly reduced the viable bacterial count in comparison with the laser irradiation of H2O2 alone. By contrast, the ultrasound irradiation alone exerted almost no bactericidal effect. These results suggested that the combination effect of photolysis of H2O2 and sonolysis of water on bactericidal activity was synergistic. A multi-way analysis of variance also revealed that the interaction of H2O2 concentration, laser power and ultrasound irradiation significantly affected the bactericidal activity. Since the result of oxidative DNA damage evaluation demonstrated that the combination of laser and ultrasound irradiation significantly induced oxidative damage of bacterial DNA in comparison with the laser irradiation of H2O2 alone, it was suggested that the combination effect of photolysis of H2O2 and sonolysis of water on bactericidal activity would be exerted via oxidative damage of cellular components such as DNA. PMID:26148024

  2. Kinetics of the reaction OH + H2O2 yields HO2 + H2O

    NASA Technical Reports Server (NTRS)

    Sridharan, U. C.; Reimann, B.; Kaufman, F.

    1980-01-01

    The paper describes an experimental study of the title reaction that uses the discharge-flow technique, laser-induced-fluorescence detection of OH and simultaneous monitoring of O and H atoms in the 250-459 K range. The reaction is normal and free from surface effect interference in Teflon or halocarbon wax-coated tube, but not in clean Pyrex. OH radicals are generated in three ways and at low concentrations to eliminate side reactions. The rate constants were determined at 298 K and over the 250-459 K range, with a factor of two higher at 298 K and factors of 3 to 5 higher at 10 to 30 km altitude in the terrestrial atmosphere than previous studies have indicated. The effect of the higher rate constant on atmospheric processes and on recent laboratory measurements of other reactions is also discussed.

  3. Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

    USGS Publications Warehouse

    Circone, S.; Kirby, S.H.; Stern, L.A.

    2006-01-01

    Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.

  4. 3-µm spectroscopy of Near-Earth Asteroids: Searching for OH/H2O on small planetary bodies

    NASA Astrophysics Data System (ADS)

    Wigton, Nathanael; Emery, Joshua; Thomas, Cristina; Rivkin, Andy

    2015-11-01

    Near-Earth asteroids (NEAs) are not expected to have OH and/or H2O ice on their surfaces because; a) most accreted dry in the inner Solar System and therefore never contained hydrated materials, and b) their relatively high surface temperatures should quickly drive OH/H2O off their surface. However, OH/H2O has been detected on other anhydrous inner solar system objects, including the Moon and Vesta. Possible mechanisms to explain OH/H2O on surfaces in the inner Solar System include production via solar wind interactions, carbonaceous chondrite or cometary impact delivery, or native OH/H2O molecules bound to phyllosilicates. As these processes are active in near-Earth space, we hypothesize that detectable levels of OH/H2O are present on NEAs.The OH/H2O feature can be comprised of an OH absorption feature centered near 2.7 μm and H2O features near 2.9 and 3.1 μm, or a blend of both, producing a relatively wide feature spanning 2.7 - 3.1 μm. Analysis of the shape of the 3-µm feature, coupled with the observed NEA orbital parameters and albedos, can help distinguish between the possible sources of OH/H2O.Here we present results of an ongoing observational program to measure spectra of NEAs in the 3-μm region. We are using the SpeX instrument on NASA’s IRTF to measure spectra from ~2 to 4.2 μm. So far, we have 12 observations of 8 NEAs. Of these objects, three exhibit a 3-μm feature: both of our observations of (443) Eros, three observations of (1036) Ganymed, and (3122) Florence exhibit. The NEAs (54789) 2001 MZ7, (96590) 1998 XB, (285944) 2001 RZ11, (214088) 2004 JN13, (357439) 2004 BL86 do not exhibit a feature. Rivkin et al. (2013; LPSC) has also reported detections of the 3-μm feature on Ganymed and Eros with data taken in the same year as ours (2012). Band shape, albedo, and orbital analysis of the NEAs exhibiting the 3-µm feature indicate that the primary production mechanism of OH/H2O on Eros and Ganymed is solar wind interactions. For Florence, on

  5. Reaction Pathways and Excited States in H2O2+OH → HO2+H2O : A New ab initio Investigation

    SciTech Connect

    Ginovska, Bojana; Camaioni, Donald M.; Dupuis, Michel

    2007-08-28

    The mechanism of the hydrogen abstraction reaction H2O2+OH→ HO2+H2O in gas phase was studied, using DFT (MPW1K) level of theory. We located 2 pathways for the reaction, both going through the same intermediate complex OH-H2O2, but via two distinct transition state structures that differ by the orientation of the hydroxyl hydrogen relative to the incipient hydroperoxy hydrogen. In one case, these hydrogens are on same side of the plane made by the 3 oxygen atoms and in the other these hydrogens are on opposite sides of the plane. The first two excited states were calculated for selected points of both pathways using time-dependent DFT, multiconfigurational quasi-degenerate-perturbation theory (MCQDPT2/ CASSCF) and equation of motion coupled cluster singles, doubles model (EOM-CCSD) EOMCCSD energies and completely renormalized EOM-CCSD(T)(IA) correction. An avoided crossing between the two excited states was found on both reaction pathways, on the product side of the barrier to H-transfer on the ground state surface, near the transition states. Further more, we report on the calculation of the rate of the reaction in the gas phase for temperatures in the range of 250-500 K, and suggest that the strong temperature dependence of the rate at high temperatures is due to reaction on the low-lying excited state surface over a barrier that is much larger than on the ground state surface. This work was supported in part by the Office of Basic Energy Sciences of the Department of Energy (DOE), Chemical Sciences program (BG and MD) and in part by the U.S. Department of Energy’s Office of Biological and Environmental Research, Environmental Management Science Program (BG and DMC). The Pacific Northwest National Laboratory is operated for DOE by Battelle Memorial Institute.

  6. Absorption by H2O and H2O-N2 mixtures at 153 GHz

    NASA Technical Reports Server (NTRS)

    Bauer, A.; Godon, M.; Carlier, J.; Ma, Q.; Tippings, R. H.

    1993-01-01

    New experimental data on and a theoretical analysis of the absorption coefficient at 153 GHz are presented for pure water vapor and water vapor-nitrogen mixtures. This frequency is 30 GHz lower than the resonant frequency of the nearest strong water line (183 GHz) and complements our previous measurements at 213 GHz. The pressure dependence is observed to be quadratic in the case of pure water vapor, while in the case of mixtures there are both linear and quadratic density components. By fitting our experimental data taken at several temperatures we have obtained the temperature dependence of the absorption. Our experimental data are compared to several theoretical models with and without a continuum contribution, and we find that none of the models is in very good agreement with the data; in the case of pure water vapor, the continuum contribution calculated using the recent theoretical absorption gives the best results. In general, the agreement between the data and the various models is less satisfactory than found previously in the high-frequency wing. The anisotropy in the observed absorption differs from that currently used in atmospheric models.

  7. Mechanism for the Direct Synthesis of H2O2 on Pd Clusters: Heterolytic Reaction Pathways at the Liquid-Solid Interface.

    PubMed

    Wilson, Neil M; Flaherty, David W

    2016-01-20

    Direct synthesis (H2 + O2 → H2O2) is a promising reaction for producing H2O2, which can replace chlorinated oxidants in industrial processes. The mechanism of this reaction and the reasons for the importance of seemingly unrelated factors (e.g., Pd cluster size and solvent pH) remain unclear despite significant research. We propose a mechanism for H2O2 formation on Pd clusters consistent with steady-state H2O2 and H2O formation rates measured as functions of reactant pressures and temperature and the interpretations of proton concentration effects. H2O2 forms by sequential proton-electron transfer to O2 and OOH surface intermediates, whereas H2O forms by O-O bond rupture within OOH surface species. Direct synthesis, therefore, does not proceed by the Langmuir-Hinshelwood mechanism often invoked. Rather, H2O2 forms by heterolytic reaction pathways resembling the two-electron oxygen reduction reaction (ORR); however, the chemical potential of H2 replaces an external electrical potential as the thermodynamic driving force. Activation enthalpies (ΔH(⧧)) for H2O formation increase by 14 kJ mol(-1) when Pd cluster diameters increase from 0.7 to 7 nm because changes in the electronic structure of Pd surface atoms decrease their propensity to cleave O-O bonds. ΔH(⧧) values for H2O2 remain nearly constant because barriers for proton-electron transfer depend weakly on the coordinative saturation of Pd surface atoms. Collectively, these results provide a self-consistent mechanism, which clarifies many studies in which H2O2 rates and selectivities were shown to depend on the concentration of acid/halide additives and Pd cluster size. These findings will guide the rational design of selective catalysts for direct synthesis. PMID:26597848

  8. The effects of small amounts of H2O on partial melting of model spinel lherzolite in the system CMAS

    NASA Astrophysics Data System (ADS)

    Liu, X.; St. C. Oneill, H.

    2003-04-01

    Water (H_2O) is so effective at lowering the solidus temperatures of silicate systems that even small amounts of H_2O are suspected to be important in the genesis of basaltic magmas. The realization that petrologically significant amounts of H_2O can be stored in nominally anhydrous mantle minerals (olivine and pyroxenes) has fundamental implications for the understanding of partial melting in the mantle, for it implies that the role that H_2O plays in mantle melting may not be appropriately described by models in which the melting is controlled by hydrous phases such as amphibole. Although the effect of water in suppressing the liquidus during crystallization is quite well understood, such observations do not provide direct quantitative information on the solidus. This is because liquidus crystallization occurs at constant major-element composition of the system, but at unbuffered component activities (high thermodynamic variance). By contrast, for partial melting at the solidus the major-element component activities are buffered by the coexisting crystalline phases (low variance), but the major-element composition of the melt can change as a function of added H_2O. Accordingly we have determined both the solidus temperature and the melt composition in the system CMAS with small additions of H_2O, to 4 wt%, in equilibrium with the four-phase lherzolite assemblage of fo+opx+cpx+sp. Experiments were conducted at 1.1 GPa and temperatures from 1473 K to the dry solidus at 1593 K in a piston-cylinder apparatus. Starting materials were pre-synthesised assemblage of fo+opx+cpx+sp, plus an oxide/hydroxide mix of approximately the anticipated melt composition. H_2O was added as either Mg(OH)_2 or Al(OH)_3. The crystalline assemblage and melt starting mix were added as separate layers inside sealed Pt capsules, to ensure large volumes of crystal-free melt. After the run doubly polished sections were prepared in order to analyse the quenched melt by FTIR spectroscopy, to

  9. Isopycnic Phases and Structures in H2O/CO2/Ethoxylated Alcohol Surfactant Mixtures

    NASA Technical Reports Server (NTRS)

    Paulaitis, Michael E.; Zielinski, Richard G.; Kaler, Eric W.

    1996-01-01

    Ternary mixtures of H2O and CO2 with ethoxylated alcohol (C(i)E(j)) surfactants can form three coexisting liquid phases at conditions where two of the phases have the same density (isopycnic phases). Isopycnic phase behavior has been observed for mixtures containing the surfactants C8E5, C10E6, and C12E6, but not for those mixtures containing either C4E1 or CgE3. Pressure-temperature (PT) projections for this isopycnic three-phase equilibrium were determined for H2O/CO2/C8E5 and H2O/CO2/C10E6 mixtures at temperatures from approximately 25 to 33 C and pressures between 90 and 350 bar. As a preliminary to measuring the microstructure in isopycnic three component mixtures, phase behavior and small angle neutron scattering (SANS) experiments were performed on mixtures of D2O/CO2/ n-hexaethyleneglycol monododecyl ether (C12E6) as a function of temperature (25-31 C), pressure (63.1-90.7 bar), and CO2 composition (0-3.9 wt%). Parameters extracted from model fits of the SANS spectra indicate that, while micellar structure remains essentially unchanged, critical concentration fluctuations increase as the phase boundary and plait point are approached.

  10. H2-O2 auxiliary power unit for space shuttle vehicles

    NASA Technical Reports Server (NTRS)

    Joyce, J. P.; Beremand, D. G.; Cameron, H. M.; Jefferies, K. S.

    1973-01-01

    A program to establish technology readiness of hydrogen-oxygen (H2-O2) auxiliary power units for use on board the space shuttle orbiter vehicle is discussed. Fundamental objectives include experimentally establishing an acceptable propellant flow control method, verification of combustor stability, and adequate thermal management. An initial APU configuration with recycled hydrogen flow has been studied and revised towards greater simplicity and scaling ease. The selected APU is a recuperated open-cycle, turbine-driven unit. Series flow of cryogenic hydrogen removes internally-generated heat and from the hydraulic system. Steady-state test of the combustor has been successful.

  11. Mesospheric H2O and H2O2 densities inferred from in situ positive ion composition measurement

    NASA Technical Reports Server (NTRS)

    Kopp, E.

    1984-01-01

    A model for production and loss of oxonium ions in the high-latitude D-region is developed, based on the observed excess of 34(+) which has been interpreted as H2O2(+). The loss mechanism suggested in the study is the attachment of N2 and/or CO2 in three-body reactions. Furthermore, mesospheric water vapor and H2O2 densities are inferred from measurements of four high-latitude ion compositions, based on the oxonium model. Mixing ratios of hydrogen peroxide of up to two orders of magnitude higher than previous values were obtained. A number of reactions, reaction constants, and a block diagram of the oxonium ion chemistry in the D-region are given.

  12. Sensitization of H2O2-induced TRPM2 activation and subsequent interleukin-8 (CXCL8) production by intracellular Fe(2+) in human monocytic U937 cells.

    PubMed

    Shimizu, Shunichi; Yonezawa, Ryo; Negoro, Takaharu; Yamamoto, Shinichiro; Numata, Tomohiro; Ishii, Masakazu; Mori, Yasuo; Toda, Takahiro

    2015-11-01

    Transient receptor potential melastatin 2 (TRPM2) is an oxidative stress-sensitive Ca(2+)-permeable channel. In monocytes/macrophages, H2O2-induced TRPM2 activation causes cell death and/or production of chemokines that aggravate inflammatory diseases. However, relatively high concentrations of H2O2 are required for activation of TRPM2 channels in vitro. Thus, in the present study, factors that sensitize TRPM2 channels to H2O2 were identified and subsequent physiological responses were examined in U937 human monocytes. Temperature increase from 30°C to 37°C enhanced H2O2-induced TRPM2-mediated increase in intracellular free Ca(2+) ([Ca(2+)]i) in TRPM2-expressing HEK 293 cells (TRPM2/HEK cells). The H2O2-induced TRPM2 activation enhanced by the higher temperature was dramatically sensitized by intracellular Fe(2+)-accumulation following pretreatment with FeSO4. Thus intracellular Fe(2+)-accumulation sensitizes H2O2-induced TRPM2 activation at around body temperature. Moreover, intracellular Fe(2+)-accumulation increased poly(ADP-ribose) levels in nuclei by H2O2 treatment, and the sensitization of H2O2-induced TRPM2 activation were almost completely blocked by poly(ADP-ribose) polymerase inhibitors, suggesting that intracellular Fe(2+)-accumulation enhances H2O2-induced TRPM2 activation by increase of ADP-ribose production through poly(ADP-ribose) polymerase pathway. Similarly, pretreatment with FeSO4 stimulated H2O2-induced TRPM2 activation at 37°C in U937 cells and enhanced H2O2-induced ERK phosphorylation and interleukin-8 (CXCL8) production. Although the addition of H2O2 to cells under conditions of intracellular Fe(2+)-accumulation caused cell death, concentration of H2O2 required for CXCL8 production was lower than that resulting in cell death. These results indicate that intracellular Fe(2+)-accumulation sensitizes TRPM2 channels to H2O2 and subsequently produces CXCL8 at around body temperature. It is possible that sensitization of H2O2-induced TRPM2

  13. 20th Century Trends in the H2O2 Ice Core Record From West Antarctica: Contributions From Accumulation Variability and Stratospheric Ozone Depletion

    NASA Astrophysics Data System (ADS)

    Frey, M. M.; Stewart, R. W.; McConnell, J. R.; Bales, R. C.

    2005-12-01

    An array of centennial-scale ice core records of hydrogen peroxide (H2O2) was recently developed using shallow cores drilled at 24 different locations across the West Antarctic Ice Sheet (WAIS). H2O2 is a major atmospheric oxidant that is closely linked to chemical feedback mechanisms controlling the composition of the atmosphere. Ice core records of H2O2 offer the potential to reconstruct past changes in the oxidation capacity of the atmosphere if the processes controlling deposition and long-term preservation are quantitatively understood. Comparison of the 1900-50 with the 1950-2000 time period shows in all cores increases of >40% in mean H2O2 during the latter half of the 20th century. Atmospheric concentration, seasonal timing and rate of snow accumulation, as well as the site temperature largely determine the amount of H2O2 preserved in an ice core. Sensitivities of the long-term H2O2 record to changes in annual accumulation and temperature quantified with a semi-empirical deposition model suggest that interannual variability in H2O2 is dominated by the accumulation signal under the current WAIS temperature regime. However, observed trends can only be explained in part by changes in accumulation rate and timing. Recent field and model experiments in West Antarctica showed a negative correlation between stratospheric ozone and summer levels of atmospheric H2O2. Using the NASA-Goddard Flight Center (GSFC) point photochemical model the magnitude of atmospheric H2O2 enhancement due to changes in surface UV radiation over the past decades was estimated and compared to the H2O2 residual not accounted for by the deposition model. We suggest that part of the observed H2O2 increase in the core record is due to the occurrence of the spring time ozone hole since the 1970s.

  14. Kinetic Studies of Iron Deposition in Horse Spleen Ferritin Using H2O2 and O2 as Oxidants

    NASA Technical Reports Server (NTRS)

    Lowery, Thomas J., Jr.; Bunker, Jared; Zhang, Bo; Costen, Robert; Watt, Gerald D.

    2004-01-01

    The reaction of horse spleen ferritin (HoSF) with Fe(2+) at pH 6.5 and 7.5 using O2, H2O2 and 1:1 a mixture of both showed that the iron deposition reaction using H2O2 is approx. 20- to 50-fold faster than the reaction with O2 alone. When H2O2 was added during the iron deposition reaction initiated with O2 as oxidant, Fe(2+) was preferentially oxidized by H2O2, consistent with the above kinetic measurements. Both the O2 and H202 reactions were well defined from 15 to 40 C from which activation parameters were determined. The iron deposition reaction was also studied using O2 as oxidant in the presence and absence of catalase using both stopped-flow and pumped-flow measurements. The presence of catalase decreased the rate of iron deposition by approx. 1.5-fold, and gave slightly smaller absorbance changes than in its absence. From the rate constants for the O2 (0.044 per second) and H2O2 (0.67 per second) iron-deposition reactions at pH 7.5, simulations of steady-state H2O2 concentrations were computed to be 0.45 micromolar. This low value and reported Fe2(+)/O2 values of 2.0-2.5 are consistent with H2O2 rapidly reacting by an alternate but unidentified pathway involving a system component such as the protein shell or the mineral core as previously postulated.

  15. Increasing extracellular H2O2 produces a bi-phasic response in intracellular H2O2, with peroxiredoxin hyperoxidation only triggered once the cellular H2O2-buffering capacity is overwhelmed.

    PubMed

    Tomalin, Lewis Elwood; Day, Alison Michelle; Underwood, Zoe Elizabeth; Smith, Graham Robert; Dalle Pezze, Piero; Rallis, Charalampos; Patel, Waseema; Dickinson, Bryan Craig; Bähler, Jürg; Brewer, Thomas Francis; Chang, Christopher Joh-Leung; Shanley, Daryl Pierson; Veal, Elizabeth Ann

    2016-06-01

    Reactive oxygen species, such as H2O2, can damage cells but also promote fundamental processes, including growth, differentiation and migration. The mechanisms allowing cells to differentially respond to toxic or signaling H2O2 levels are poorly defined. Here we reveal that increasing external H2O2 produces a bi-phasic response in intracellular H2O2. Peroxiredoxins (Prx) are abundant peroxidases which protect against genome instability, ageing and cancer. We have developed a dynamic model simulating in vivo changes in Prx oxidation. Remarkably, we show that the thioredoxin peroxidase activity of Prx does not provide any significant protection against external rises in H2O2. Instead, our model and experimental data are consistent with low levels of extracellular H2O2 being efficiently buffered by other thioredoxin-dependent activities, including H2O2-reactive cysteines in the thiol-proteome. We show that when extracellular H2O2 levels overwhelm this buffering capacity, the consequent rise in intracellular H2O2 triggers hyperoxidation of Prx to thioredoxin-resistant, peroxidase-inactive form/s. Accordingly, Prx hyperoxidation signals that H2O2 defenses are breached, diverting thioredoxin to repair damage. PMID:26944189

  16. H2O masers from low and intermediate luminosity young stellar objects: H2O masers and YSOs

    NASA Astrophysics Data System (ADS)

    Persi, P.; Palagi, F.; Felli, M.

    1994-11-01

    We have used the Medicina 32-m radiotelescope to search for H2O 22.2 GHz maser emission from a sample of 68 red peculiar nebulosities associated with low luminosity (LIR less than 103 solar luminosity)) and intermediate luminosity (LIR approximately 104 solar luminosity) Young Stellar Objects (YSOs). H2O maser emission was detected in 9 sources, with a new detection in IRAS 18265+0028. Comparison with other samples indicates that YSOs have a higher probability of hosting an H2O maser, when they are associated with red peculiar nebulosities. Seven of the detected sources are associated with molecular outflows, which confirms that these two phenomena are strictly correlated. The maser sources associated with the Class I YSOs (IRAS 03225+3034, and IRAS 03245+3002, in the dark clouds L1448 and L1455 respectively) appear overluminous with respect to their IR luminosity. The maser emission shows a remarkable variability on time scales of months and years, which tends to be larger for lower luminosity sources. This is indicative of unsaturated emission in low luminosity sources.

  17. First spectrally-resolved H2 observations towards HH 54 . Low H2O abundance in shocks

    NASA Astrophysics Data System (ADS)

    Santangelo, G.; Antoniucci, S.; Nisini, B.; Codella, C.; Bjerkeli, P.; Giannini, T.; Lorenzani, A.; Lundin, L. K.; Cabrit, S.; Calzoletti, L.; Liseau, R.; Neufeld, D.; Tafalla, M.; van Dishoeck, E. F.

    2014-09-01

    Context. Herschel observations suggest that the H2O distribution in outflows from low-mass stars resembles the H2 emission. It is still unclear which of the different excitation components that characterise the mid- and near-IR H2 distribution is associated with H2O. Aims: The aim is to spectrally resolve the different excitation components observed in the H2 emission. This will allow us to identify the H2 counterpart associated with H2O and finally derive directly an H2O abundance estimate with respect to H2. Methods: We present new high spectral resolution observations of H2 0-0 S(4), 0-0 S(9), and 1-0 S(1) towards HH 54, a bright nearby shock region in the southern sky. In addition, new Herschel/HIFI H2O (212 - 101) observations at 1670 GHz are presented. Results: Our observations show for the first time a clear separation in velocity of the different H2 lines: the 0-0 S(4) line at the lowest excitation peaks at -7 km s-1, while the more excited 0-0 S(9) and 1-0 S(1) lines peak at -15 km s-1. H2O and high-J CO appear to be associated with the H2 0-0 S(4) emission, which traces a gas component with a temperature of 700-1000 K. The H2O abundance with respect to H2 0-0 S(4) is estimated to be X(H2O) < 1.4 × 10-5 in the shocked gas over an area of 13''. Conclusions: We resolve two distinct gas components associated with the HH 54 shock region at different velocities and excitations. This allows us to constrain the temperature of the H2O emitting gas (≤1000 K) and to derive correct estimates of H2O abundance in the shocked gas, which is lower than what is expected from shock model predictions. Based on observations made with ESO telescopes at the La Silla Paranal Observatory under programme IDs: 089.C-0772, 292.C-5025.

  18. Measurements of H2O broadening coefficients of infrared methane lines

    NASA Astrophysics Data System (ADS)

    Delahaye, T.; Landsheere, X.; Pangui, E.; Huet, F.; Hartmann, J.-M.; Tran, H.

    2016-04-01

    H2O-broadening and shifting coefficients of 76 ro-vibrational transitions of methane in the mid-and near-infrared regions were measured for the first time. For this, eight spectra of methane diluted in water vapor were recorded with a high resolution Fourier Transform spectrometer for pressures ranging from 20 to 80 Torr and at 323 and 367 K. Line broadening and shifting coefficients were retrieved from the measured spectra through fits using Voigt profiles. Values at room temperature (296 K) were then deduced and compared with those of dry air. The results show that H2O-broadenings of methane lines are, on average, 34% larger than those for dry air.

  19. In situ electrical conductivity measurements of H2O under static pressure up to 28 GPa

    NASA Astrophysics Data System (ADS)

    Liu, Bao; Gao, Yang; Han, Yonghao; Ma, Yanzhang; Gao, Chunxiao

    2016-08-01

    The in situ electrical conductivity measurements on water in both solid state and liquid state were performed under pressure up to 28 GPa and temperature from 77 K to 300 K using a microcircuit fabricated on a diamond anvil cell (DAC). Water chemically ionization mainly contributes to electrical conduction in liquid state, which is in accord with the results obtained under dynamic pressure. Energy band theory of liquid water was used to understand effect of static pressure on electrical conduction of water. The electric conductivity of H2O decreased discontinuously by four orders of magnitude at 0.7-0.96 GPa, indicating water frozen at this P-T condition. Correspondingly, the conduction of H2O in solid state is determined by arrangement and bending of H-bond in ice VI and ice VII. Based on Jaccard theory, we have concluded that the charge carriers of ice are already existing ions and Bjerrum defects.

  20. Broadening parameters of the H2O-He collisional system for astrophysical applications

    NASA Astrophysics Data System (ADS)

    Petrova, T. M.; Solodov, A. M.; Solodov, A. A.; Starikov, V. I.

    2016-03-01

    The water vapor line broadening γ and shift δ coefficients in the ν1 + ν2, ν2 + ν3, ν1 + ν3, 2ν3, 2ν1, 2ν2 + ν3, and ν1 + 2ν2 vibrational bands were obtained from the analysis of the H2O-He absorption spectra, recorded in the region from 5000 to 7500 cm-1 with the spectral resolution of 0.01 cm-1 using a Bruker IFS 125HR FTIR spectrometer. The vibrational bands 2ν3 and ν1 + 2ν2 were investigated for the first time. The calculations of γ and δ were performed in the framework of the semi-classical method. The rotational contributions as well as the contributions connected with the accidental resonances were taken into account in the used H2O-He interaction potential. The analytical representation of the broadening coefficients γ at planetary temperatures was introduced and discussed.

  1. The physical conditions in IRDC clumps from Herschel/HIFI observations of H2O

    NASA Astrophysics Data System (ADS)

    Shipman, R. F.; van der Tak, F. F. S.; Wyrowski, F.; Herpin, F.; Frieswijk, W.

    2014-10-01

    Context. The earliest phases of high-mass star formation are poorly understood. Aims: Our goal is to determine the physical conditions and kinematic structure of massive starforming cloud clumps. Methods: We analyse H2O 557 GHz line profiles observed with HIFI toward four positions in two infrared-dark cloud clumps. By comparison with ground-based C17O, N2H+, CH3OH, and NH3 line observations, we constrain the volume density and kinetic temperature of the gas and estimate the column density and abundance of H2O and N2H+. Results: The observed water lines are complex with emission and absorption components. The absorption is redshifted and consistent with a cold envelope, while the emission is interpreted as resulting from proto-stellar outflows. The gas density in the clumps is ~107 cm-3. The o-H2O outflow column density is 0.3-3.0 × 1014 cm-2. The o-H2O absorption column density is between 1.5 × 1014 and 2.6 × 1015 cm-2 with cold o-H2O abundances between 1.5 × 10-9 and 3.1 × 10-8. Conclusions: All clumps have high gas densities (~107 cm-3) and display infalling gas. Three of the four clumps have outflows. The clumps form an evolutionary sequence as probed by H2O N2H+, NH3, and CH3OH. We find that G28-MM is the most evolved, followed by G11-MM and then G28-NH3. The least evolved clump is G11-NH3 which shows no signposts of starformation; G11-NH3 is a high-mass pre-stellar core. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia with important participation of NASA.Tables 4, 6, 8, 10, 11, and Appendix A are available in electronic form at http://www.aanda.orgFinal Herschel and APEX data used in the paper (FITS files) are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/570/A51

  2. Production and characterization of thin a-C:(H) films for gas permeation barrier functionality against He, CO(2), N(2), O(2) and H(2)O.

    PubMed

    Laidani, N; Bartali, R; Gottardi, G; Anderle, M; Chuste, G; Bellachioma, C

    2006-07-01

    This work reports on (i) the gas barrier properties of a-C:H films rf-sputtered in Ar-H(2) plasmas from a graphite target on polyethylene terephthalate (PET) and (ii) the influence of the film chemical structure and defect properties on the gas permeability. The intrinsic permeabilities of the films to He, CO(2), O(2), N(2) gases and H(2)O vapour were determined and found to be orders of magnitude lower than that of the bare PET. Indirect evidence was given to a solubility-diffusion process as the more probable permeation mechanism, over a gas flow through microdefects or gas transport through nanodefects by a Knudsen diffusion mechanism. The barrier capability of the films was found to scale as the gas molecular diameter within the He, CO(2), O(2) and N(2) series, and inversely with the gas critical temperature for the CO(2), O(2), N(2) and H(2)O series. A correlation between the film Urbach energy, E(u), and the gas permeability was established, except for H(2)O. Such findings further favour a bulk diffusion contributing mechanism to permeation over the gas state transport. Conversely, this E(u)-permeability relation shed more light on the origin of the valence band tailing of the amorphous carbon electron structure. PMID:21690810

  3. Production and characterization of thin a-C:(H) films for gas permeation barrier functionality against He, CO2, N2, O2 and H2O

    NASA Astrophysics Data System (ADS)

    Laidani, N.; Bartali, R.; Gottardi, G.; Anderle, M.; Chuste, G.; Bellachioma, C.

    2006-07-01

    This work reports on (i) the gas barrier properties of a-C:H films rf-sputtered in Ar-H2 plasmas from a graphite target on polyethylene terephthalate (PET) and (ii) the influence of the film chemical structure and defect properties on the gas permeability. The intrinsic permeabilities of the films to He, CO2, O2, N2 gases and H2O vapour were determined and found to be orders of magnitude lower than that of the bare PET. Indirect evidence was given to a solubility-diffusion process as the more probable permeation mechanism, over a gas flow through microdefects or gas transport through nanodefects by a Knudsen diffusion mechanism. The barrier capability of the films was found to scale as the gas molecular diameter within the He, CO2, O2 and N2 series, and inversely with the gas critical temperature for the CO2, O2, N2 and H2O series. A correlation between the film Urbach energy, Eu, and the gas permeability was established, except for H2O. Such findings further favour a bulk diffusion contributing mechanism to permeation over the gas state transport. Conversely, this Eu-permeability relation shed more light on the origin of the valence band tailing of the amorphous carbon electron structure.

  4. Synthetic fluid inclusions XX. Critical PTx properties of H2O-FeCl2 fluids

    NASA Astrophysics Data System (ADS)

    Steele-MacInnis, Matthew; Lecumberri-Sanchez, Pilar; Bodnar, Robert J.

    2015-01-01

    Iron chloride is a common and abundant component in hydrothermal fluids in many geologic environments, yet the thermodynamic and PTx properties of FeCl2-bearing aqueous fluids are poorly known. In this study we have used the synthetic fluid inclusion technique to characterize the PTx conditions along the critical curve of the system H2O-FeCl2. For a given temperature or salinity, the critical pressure in the H2O-FeCl2 system is lower than that in the H2O-NaCl system. In contrast, the critical curves of aqueous solutions of other divalent-cation chlorides, such as MgCl2 and CaCl2, are at higher pressure than that of NaCl solutions of equivalent temperature or salinity. The results of this study provide the first quantitative constraints on the PTx extent of liquid-vapor immiscibility for FeCl2-rich fluids. Owing to the low pressure along the critical curve compared to other common aqueous chloride systems, immiscibility of FeCl2-rich fluids appears to be limited to relatively low pressures, or relatively shallow levels in the crust, compared to other saline hydrothermal fluids.

  5. Ni/YSZ pattern anodes fabrication and their microstructure and electrochemical behavior changes in H2-H2O environments

    NASA Astrophysics Data System (ADS)

    Yao, W.; Croiset, E.

    2013-03-01

    An effective photolithographic process was investigated to fabricate Ni/YSZ pattern anodes using a bi-layer lift-off resist method. Suitable undercut size was found critical for successful pattern fabrication. Effects of Ni thickness, temperature and H2O content on Ni pattern microstructure were evaluated. Ni/YSZ pattern anodes with 0.5 μm thick Ni was tested in dry H2 at 550 °C without significantly changing the TPB line. Ni/YSZ pattern anodes with Ni thickness of 0.8 μm were tested at 550 °C under dry and humidified H2 (3-50% H2O) conditions without TPB line change. At 700 °C, and for 0.8 μm thick patterns, the TPB length showed pronounced change in H2 with 10-50% H2O. Significant increase in TPB length due to holes formation was observed at 800 °C with 3% and 10% H2O. Ni/YSZ pattern anodes with 1.0 μm thick Ni was stable in H2 with 3% H2O in the range 550-800 °C, with TPB line only slightly modified. However, distinct change of TPB line and Ni microstructure was observed with 10-70% H2O above 700 °C. Stabilization of the polarization resistance depends on temperature. To accelerate stabilization of the cell, pre-treatment of the cell in H2 with 3% H2O at 750 °C or 800 °C could be performed.

  6. VUV photoionization cross sections of HO2, H2O2, and H2CO.

    PubMed

    Dodson, Leah G; Shen, Linhan; Savee, John D; Eddingsaas, Nathan C; Welz, Oliver; Taatjes, Craig A; Osborn, David L; Sander, Stanley P; Okumura, Mitchio

    2015-02-26

    The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO2), hydrogen peroxide (H2O2), and formaldehyde (H2CO) have been measured from their first ionization thresholds to 12.008 eV. HO2, H2O2, and H2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO2, H2O2, and H2CO on an absolute scale, resulting in absolute photoionization spectra. PMID:25621533

  7. H2O2-responsive antioxidant polymeric nanoparticles as therapeutic agents for peripheral arterial disease.

    PubMed

    Kwon, Byeongsu; Kang, Changsun; Kim, Jinsub; Yoo, Donghyuck; Cho, Byung-Ryul; Kang, Peter M; Lee, Dongwon

    2016-09-25

    Peripheral artery disease (PAD) is a common circulatory disorder in which narrowed arteries limit blood flow to the lower extremity and affect millions of people worldwide. Therapeutic angiogenesis has emerged as a promising strategy to treat PAD patients because surgical intervention has been showing limited success. Leg muscles of PAD patients have significantly high level of ROS (reactive oxygen species) and the increased production of ROS is a key mechanism of initiation and progression of PAD. We have recently developed H2O2-responsive polymer PVAX, which is designed to rapidly scavenge H2O2 and release vanillyl alcohol with antioxidant and anti-inflammatory activity. In this study, we investigated the therapeutic efficacy of PVAX nanoparticles for PAD using a cell culture model and a mouse model of hindlimb ischemia. PVAX nanoparticles significantly enhanced the expression of angiogenic inducers such as vascular endothelial growth factor (VEGF) and platelet endothelial cell adhesion molecule (PECAM)-1 in human umbilical vein endothelial cells (HUVEC). PVAX nanoparticles promoted revascularization and restoration of blood perfusion into ischemic tissues by upregulating angiogenic VEGF and PECAM-1. This work demonstrates that H2O2-responsive PVAX nanoparticles facilitate therapeutic angiogenesis and hold tremendous translational potential as therapeutic systems for ischemic diseases such as PAD. PMID:27521705

  8. Crystal structures, UV spectra of solid iodide anionic water clusters I(-)(H2O)(1-4), and electrochemical reaction of I(-)(H2O)(1-4) → I· + e(-)(H2O)(1-4).

    PubMed

    Qiu, Yanxuan; Yang, Meng; Chen, Wenbin; Su, Yuzhi; Ouyang, Zhenjie; Yan, Hua; Gao, Feixian; Dong, Wen

    2013-05-16

    Four iodide anionic water clusters of I(-)(H2O)1-4 in two supramolecular complexes of [Fe(phen)3][I2(H2O)3] (1) and [Zn(phen)3][I2(H2O)4.5] (2) have been determined by single-crystal X-ray diffraction analysis. The diffuse reflectance spectra for the solid iodide anionic water clusters of I(-)(H2O)1-4 were investigated, and their absorption bands were demonstrated by denisty functional theory calculation. The electrochemical reaction of I(-)(H2O)1-4 → I· + e(-)(H2O)1-4 with the oxidation potential of Ep = 0.61 eV was first found and reported in two aqueous solutions (1 mmol·dm(-3)) of 1 and 2. PMID:23614806

  9. H2O heating in molecular clouds - Line transfer and thermal balance in a warm dusty medium

    NASA Technical Reports Server (NTRS)

    Takahashi, T.; Silk, J.; Hollenbach, D. J.

    1983-01-01

    An investigation is undertaken into the possibility of the heating of molecular gas through collisions with radiatively pumped H2O, in the context of the overall thermal balance of optically thick molecular clouds with embedded sources. In order to solve the line transfer equation, which includes warm dust grains, an extended method of escape probability approximation is developed in which the equilibrium gas temperature arises from the balance of heating by cosmic ray ionization of H2, and by collisions with warm dust grains and radiatively pumped H2O molecules against cooling by collisions with CO and C I. The equilibrium gas temperature for a given dust temperature strongly depends on the efficiency of the cooling species, and is therefore most sensitive to the cloud optical depth. It is less dependent, in decreasing order, on H2O abundance, gas density, and velocity dispersion.

  10. H2O Isotopologues in Extreme OH/IR Stars

    NASA Astrophysics Data System (ADS)

    Justtanont, K.; Barlow, M. J.; Blommaert, J. A. D. L.; Decin, L.; Kerschbaum, F.; Matsuura, M.; Olofsson, H.; Swinyard, B.; Teyssier, D.; Waters, L. B. F. M.; Yates, J.

    2015-08-01

    Using Herschel Space Observatory, we observed isotopologues of H2O in extreme OH/IR stars. We detected strong H216O and H217O while the H218O lines are missing, contrary to the overall galactic oxygen abundance in the interstellar medium and the Sun, where 18O is more abundant than 17O. Theoretical stellar evolution suggests that 18O is being destroyed during the hot-bottom burning. This implies that these OH/IR stars come from a population of intermediate-mass stars which have an initial mass ≥ 5 M⊙.

  11. Timescales of magma ascent recorded by H2O zonation in clinopyroxene

    NASA Astrophysics Data System (ADS)

    Lloyd, A. S.; Plank, T. A.; Ruprecht, P.; Hauri, E. H.; Rose, W. I.

    2013-12-01

    Magma ascent prior to explosive eruptions occurs on timescales of minutes to hours, and so requires exceptionally fast chronometers to quantify. One promising approach involves the diffusion of water in clinopyroxene (cpx), given laboratory measurements of diffusivities on the order of 10-9.5 to 10-11.5 at temperatures appropriate for mafic magmas [1]. Previous studies have observed H2O zonation in cpx grains but this was accompanied by major element zonation, leaving open the possibility for crystal growth zonation instead of diffusive loss of water [2]. We report SIMS and EMP analyses for three cpx phenocrysts from ash samples collected in situ during the Oct 17, 1974 sub-plinian eruption of Volcán de Fuego. Concentration profiles were assessed by 5-6 measurements along ~350-450 μm transects measured perpendicular to glassy rims. The maximum H2O measured in the cores of the cpx ranges from 230-320 ppm; whereas, the measurements closest to the rim range from 80-170 ppm. Importantly, we chose grains with limited major element zonation (i.e., Mg# and Al2O3 remain relatively constant or do not co-vary with H2O concentrations). Based on a temperature-dependent parameterization for the partition coefficient of H2O between cpx and melt that accounts for tetrahedrally coordinated Al3+ [3], cores and rims of these cpx are in equilibrium with a melt containing 2.0-2.7 wt% (core) and 0.7-1.6 wt% (rim). The maximum H2O concentration measured in olivine-hosted melt inclusions (~4.2 wt% H2O) erupted on the same day as the cpx phenocrysts [4] suggests that the cpx are not in equilibrium with the melt inclusions. The Mg# of the cpxs (73-77) fall within the range of that for the olivines (72-78) indicating that cpx and olivine were co-crystalizing and that H+ loss by diffusion has potentially occurred. Utilizing the same melt inclusion data to constrain the degassing path for the ascending magma under Fuego, we used forward models to estimate the decompression rate needed to

  12. Thermodynamics of Silicon-Hydroxide Formation in H2O Containing Atmospheres

    NASA Technical Reports Server (NTRS)

    Copland, Evan; Myers, Dwight; Opila, Elizabeth J.; Jacobson, Nathan S.

    2001-01-01

    The formation of volatile silicon-hydroxide species from SiO2 in water containing atmospheres has been identified as a potentially important mode of degradation of Si-based ceramics. Availability of thermodynamic data for these species is a major problem. This study is part of an ongoing effort to obtain reliable, experimentally determined thermodynamic data for these species. The transpiration method was used to measure the pressure of Si-containing vapor in equilibrium with SiO2 (cristobalite) and Ar + H2O(g) with various mole fractions of water vapor, X(sub H2O), at temperatures ranging from 1000 to 1780 K. Enthalpies and entropies for the reaction, SiO2(s) + 2H2O(g) = Si(OH)4(g), were obtained, at X(sub H2O) = 0.15 and 0.37, from the variation of lnK with 1/T according to the 'second law method'. The following data were obtained: delta(H)deg = 52.9 +/- 3.7 kJ/mole and delta(S)deg = -68.6 +/- 2.5 J/mole K at an average temperature of 1550 K, and delta(H)deg = 52.5+/-2.0 kJ/mole and delta(S)deg= -69.7 +/- 1.5 J/moleK at an average temperature of 1384 K, for X(sub H2O)= 0.15 and 0.37, respectively. These data agree with results from the literature obtained at an average temperature of 1600 K, and strongly suggest Si(OH)4(g) is the dominant vapor species. Contradictory results were obtained with the determination of the dependence of Si-containing vapor pressure on the partial pressure of water vapor at 1187 and 1722 K. These results suggested the Si-containing vapor could be a mixture of Si(OH)4 + SiO(OH)2. Further pressure dependent studies are in progress to resolve these issues.

  13. Solvothermal syntheses, high- and low-temperature crystal structures, and thermochromic behavior of [1,2-diethyl-3,4,5-trimethyl-pyrazolium] 4[Bi 4I 16] and [1,10-phenanthrolinium][BiI 4]·(H 2O)

    NASA Astrophysics Data System (ADS)

    Tershansy, M. A.; Goforth, A. M.; Gardinier, J. R.; Smith, M. D.; Peterson, L.; zur Loye, H.-C.

    2007-05-01

    A new iron(II) scorpionate complex, {Fe[HC(3,4,5-Me 3pz) 3] 2}(I) 2 (pz = pyrazolyl) ( 1), and two novel compounds containing low-dimensional poly(iodobismuthate) anions [1,2-Et 2-3,4,5-Me 3pz] 4[Bi 4I 16] ([1,2-Et 2-3,4,5-Me 3pz] + = [1,2-diethyl-3,4,5-trimethyl-pyrazolium] +) ( 2), and [H(1,10-phen)][BiI 4]·(H 2O) ([H(1,10-phen)] + = [1,10-phenanthrolinium] +) ( 3), have been synthesized and characterized by single crystal X-ray diffraction. Crystals of 2 resulted from the solvothermal reaction of BiI 3 and {Fe[HC(3,4,5-Me 3pz) 3] 2}(I) 2 in an ethanol/water solvent mixture. The anion of this compound is discrete (0-D) and consists of four slightly distorted BiI 6 octahedra joined in an edge-sharing arrangement, and the cation is a decomposition/solvent attack product of the iron scorpionate complex. Crystals of 3 resulted from the solvothermal reaction of BiI 3, 1,10-phenanthroline, and CuI in an ethanol/water solvent mixture. [H(1,10-phen)][BiI 4]·(H 2O) contains 1-D chains of BiI 6 octahedra and a protonated phenanthroline/water molecule complex. Both 2 and 3 are thermochromic compounds as their colors change, respectively, from orange at 296 K to yellow upon cooling to 100 K and from red-orange at 296 K to orange at 100 K. Crystallographic data at both temperatures were recorded for each sample and are reported here. The crystallographic data indicate that interatomic distances (Bi-I and Bi⋯Bi) within the inorganic anions change as a function of temperature, and it is believed that these changes are associated with the observation of thermochromism. {Fe[HC(3,4,5-Me 3pz) 3] 2}(I) 2 ( 1) crystallizes in the monoclinic space group P2 1/ n with the following lattice parameters at 150(1) K: a = 10.8489(5) Å, b = 17.6642(9) Å, c = 15.4131(8) Å, β = 102.4860(10)°. [Et 2Me 3pz] 4[Bi 4I 16] ( 2) and [H(1,10-phen)][BiI 4]·(H 2O) ( 3) both crystallize in the triclinic space group P1¯ with the following lattice parameters for 2 at 296(1) K and 100(1) K

  14. OH radicals distribution in an Ar-H2O atmospheric plasma jet

    NASA Astrophysics Data System (ADS)

    Li, L.; Nikiforov, A.; Xiong, Q.; Britun, N.; Snyders, R.; Lu, X.; Leys, C.

    2013-09-01

    Recently, plasma jet systems found numerous applications in the field of biomedicine and treatment of temperature-sensitive materials. OH radicals are one of the main active species produced by these plasmas. Present study deals with the investigation of RF atmospheric pressure plasma jet in terms of OH radicals production by admixture of H2O into argon used as a feed gas. Generation of OH radicals is studied by laser-induced fluorescence spectroscopy. The excitation dynamics of OH radicals induced by the laser photons is studied by time-resolved spectroscopy. It is shown that vibrational and rotational energy transfer processes, which are sensitive to the surrounding species, can lead to the complication in the OH radicals diagnostics at high pressure and have to be considered during experiments. The axial and radial 2D maps of absolute densities of hydroxyl radicals at different water contents are obtained. The highest density of 1.15 × 1020 m-3 is measured in the plasma core for the case of 0.3% H2O. In the x-y-plane, the OH density steeply decreases within a range of ±2 mm from its maximum value down to 1018 m-3. The effect of H2O addition on the generation of OH radicals is investigated and discussed.

  15. Liquid water on Mars - An energy balance climate model for CO2/H2O atmospheres

    NASA Technical Reports Server (NTRS)

    Hoffert, M. I.; Callegari, A. J.; Hsieh, C. T.; Ziegler, W.

    1981-01-01

    A simple climatic model is developed for a Mars atmosphere containing CO2 and sufficient liquid water to account for the observed hydrologic surface features by the existence of a CO2/H2O greenhouse effect. A latitude-resolved climate model originally devised for terrestrial climate studies is applied to Martian conditions, with the difference between absorbed solar flux and emitted long-wave flux to space per unit area attributed to the divergence of the meridional heat flux and the poleward heat flux assumed to equal the atmospheric eddy heat flux. The global mean energy balance is calculated as a function of atmospheric pressure to assess the CO2/H2O greenhouse liquid water hypothesis, and some latitude-resolved cases are examined in detail in order to clarify the role of atmospheric transport and temperature-albedo feedback. It is shown that the combined CO2/H2O greenhouse at plausible early surface pressures may account for climates hot enough to support a hydrological cycle and running water at present-day insolation and visible albedo levels.

  16. Verification of the H2O Linelists with Theoretically Developed Tools

    NASA Technical Reports Server (NTRS)

    Ma, Qiancheng; Tipping, R.; Lavrentieva, N. N.; Dudaryonok, A. S.

    2013-01-01

    Two basic rules (i.e., the pair identity and the smooth variation rules) resulting from the properties of the energy levels and wave functions of H2O states govern how the spectroscopic parameters vary with the H2O lines within the individually defined groups of lines. With these rules, for those lines involving high j states in the same groups, variations of all their spectroscopic parameters (i.e., the transition frequency, intensity, pressure broadened half-width, pressure-induced shift, and temperature exponent) can be well monitored. Thus, the rules can serve as simple and effective tools to screen the H2O spectroscopic data listed in the HITRAN database and verify the latter's accuracies. By checking violations of the rules occurring among the data within the individual groups, possible errors can be picked up and also possible missing lines in the linelist whose intensities are above the threshold can be identified. We have used these rules to check the accuracies of the spectroscopic parameters and the completeness of the linelists for several important H2O vibrational bands. Based on our results, the accuracy of the line frequencies in HITRAN 2008 is consistent. For the line intensity, we have found that there are a substantial number of lines whose intensity values are questionable. With respect to other parameters, many mistakes have been found. The above claims are consistent with a well known fact that values of these parameters in HITRAN contain larger uncertainties. Furthermore, supplements of the missing line list consisting of line assignments and positions can be developed from the screening results.

  17. Thorium terephthalates coordination polymers synthesized in solvothermal DMF/H2O system.

    PubMed

    Falaise, Clément; Charles, Jean-Sébastien; Volkringer, Christophe; Loiseau, Thierry

    2015-03-01

    A series of thorium-based terephthalates have been solvothermaly synthesized in N,N-dimethylformamide (DMF) with different amounts of water and various temperatures (100-150 °C). Without the addition of water, the Th-H2bdc-DMF system gives rise to the formation of two phases, Th(bdc)2(DMF)2 (1) and Th6O4(OH)4(H2O)6(bdc)6·6DMF·12H2O (3) (bdc = 1,4-benzenedicarboxylate or terephthalate). Their structures are built up of isolated thorium centers ThO8(DMF)2 for (1) and the hexanuclear core Th6O4(OH)4(H2O)6 for (3). The latter adopts the UiO-66 metal-organic framework topology and exhibits a very high porosity for an actinides-based porous material (BET surface up to 730(6) m(2)·g(-1)). The synthesis of (3) is also favored upon adding water. However, for pure aqueous solutions or for a very low amount of water, a third solid Th(bdc)2 (2) crystallizes and contains thorium monomers ThO8. The main similitude with the parent system dedicated to tetravalent uranium concerns the possibility to stabilize the An6O8(H2O)6 core by terephthalate linkers and to reproduce An(bdc)2(DMF)2 for both actinides U(4+) and Th(4+). The thermal treatment of the latter shows a structural transition into the crystalline Th(bdc)2 (2) solid. PMID:25668215

  18. Dissolved Carbonate Species in Mixed-Volatile Rhyolitic melts: Carbon Speciation Correlates with Dissolved H2O Content

    NASA Astrophysics Data System (ADS)

    Moore, G.; Roggensack, K.; Holloway, J.

    2006-12-01

    The solubility and speciation of volatiles (H2O, CO2) in silicate melts play an important role in determining magma behavior and properties (e.g. volcanic degassing, viscosity, density, glass transition temperature). Carbon dioxide is an important volatile component to consider because of its abundance in volcanic systems, its potential effect on melt behavior, and its low solubility (relative to H2O) that makes it the primary bubble former at high pressures. In previous volatile solubility and spectroscopic work, carbon dioxide has been observed to dissolve as a molecular CO2 unit in silicic melts (e.g. Blank and Holloway, 1994; Tamic et al, 2001), as a carbonate ion in mafic melts (Fine and Stolper, 1986), while intermediate magma compositions such as andesites contain both species (King et al, 2002). FTIR spectroscopic results from low pressure (400- 600 MPa) piston-cylinder experiments show that a calc-alkaline rhyolite melt saturated with a mixed (H2O + CO2) fluid of known composition, has both molecular CO2 and carbonate species present. Dissolved carbonate is not observed in glasses with less than ~2.5 wt% H2O, but its abundance increases linearly with increasing water content thereafter to ~80% carbonate (relative to total dissolved CO2) at ~6 wt% H2O. These results are consistent with H2O depolymerizing the rhyolite (i.e. making it more basalt-like), thereby favoring the formation of the carbonate species. We speculate that the reasons previous mixed volatile studies on rhyolites (e.g. Tamic et al, 2001; Liu et al, 2004) have not observed dissolved carbonate may include bulk compositional differences (i.e. more or less network modifiers present), different P-T conditions, and/or differing quench rates for the experimental apparatus used. These observations have significant implications for understanding the processes occuring during volatile degassing of explosive rhyolitic volcanic systems that contain both H2O and CO2.

  19. Enhanced Removal of Hexavalent Chromium in the Presence of H2O2 in Frozen Aqueous Solutions.

    PubMed

    Kim, Kitae; Kim, Jaesung; Bokare, Alok D; Choi, Wonyong; Yoon, Ho-Il; Kim, Jungwon

    2015-09-15

    The reductive transformation of Cr(VI) to Cr(III) by H2O2 in ice was compared with that in water. The reduction of Cr(VI) was significant at -20 °C (ice), whereas the reduction efficiency was very low at 25 °C (water). This enhanced reduction of Cr(VI) in ice was observed over a wide range of H2O2 concentration (20-1000 μM), pH (3-11), and freezing temperature (-10 to -30 °C). The observed molar ratio of consumed [H2O2] to reduced [Cr(VI)] in ice was in close agreement with the theoretical (stoichiometric) molar ratio (1.5) for H2O2-mediated Cr(VI) reduction through proton-coupled electron transfer (PCET). The synergistic increase in Cr(VI) reduction in water by increasing the H2O2 and proton concentrations confirms that the freeze concentration of both H2O2 and protons in the liquid brine is primarily responsible for the enhanced Cr(VI) reduction in ice. In comparison, the one-electron reduction of Cr(VI) to Cr(V) and subsequent reoxidation of Cr(V) to Cr(VI) is the major reaction mechanism in aqueous solution. The reduction efficiency of Cr(VI) by H2O2 in the frozen aqueous electroplating wastewater was similar to that in the frozen aqueous deionized water, which verifies the enhanced reduction of Cr(VI) by freezing in real Cr(VI)-contaminated aquatic systems. PMID:26317508

  20. H2O and O(3PJ) photodesorption from amorphous solid water deposited on a lunar mare basalt

    NASA Astrophysics Data System (ADS)

    DeSimone, Alice J.; Orlando, Thomas M.

    2015-07-01

    H2O (ν = 0) and O(3PJ=2,1,0) desorbates were measured with resonance-enhanced multiphoton ionization following 157-nm irradiation of amorphous solid water (ASW) deposited on a lunar mare basalt. Both H2O photodesorption and O(3PJ) photodissociation products of ASW were studied in the attempt to better understand the competition between photodesorption and photodissociation of water in the condensed phase on a lunar surface. The oxygen atom time-of-flight (TOF) spectrum was measured as a function of spin-orbit state, H2O exposure, and 157-nm irradiation time. Maxwell-Boltzmann distributions with translational temperatures of 10,000 K, 1800 K, 400 K, and 89 K fit the four TOF components. For high H2O exposures, diffusion out of pores in the lunar substrate made a large portion of the O(3PJ) signal appear to be sub-thermal. Water depletion cross sections were measured at exposures between 0.1 and 10 Langmuir (1 L = 10-6 Torr s). These cross sections decreased with increasing coverage and matched previously measured cross sections from a lunar impact melt breccia. Additionally, non-resonant ionization was employed to detect vibrationally excited water indirectly through its fragments. The OH+ fragment of H2O (ν*) and the O(3PJ) photodissociation product increased in intensity during prolonged irradiation as hydroxyl groups accumulated on the surface and then recombined. For an initial exposure of 5 L H2O, after reaching maximum signal, the cross sections for H2O (ν*) and O(3P2) depletion were measured to be 1.2 × 10-19 cm2 and 6.7 × 10-20 cm2, respectively.

  1. Radiative Lifetime for Nuclear Spin Conversion of Water-Ion H_2O^+

    NASA Astrophysics Data System (ADS)

    Tanaka, Keiichi; Harada, Kensuke; Oka, Takeshi

    2013-06-01

    Nuclear spin conversion interaction of the water ion, H_2O^+, has been studied to derive the spontaneous emission lifetime between the ortho- and para-levels. The H_2O^+ ion is a radical with ^2 B _1 electronic ground state and the off-diagonal electron spin-nuclear spin interaction term, T_{ab} (S_aΔ I_b + S_bΔ I_a), connects para and ortho levels, because Δ {I} = {I}_1 - {I}_2 has nonvanishing matrix elements between I = 0 and 1. The T_{ab} coupling constant, derived by an ab initio calculation in MRD-CI/Bk level to be 72 MHz, is larger than that of H_2O by 4 orders of magnitude, makes the ortho to para conversion of H_2O^+ faster than that of H_2O by 8 orders of magnitude and possibly competitive with other astrophysical processes. Last year we reported ortho and para coupling channels below 900 cm^{-1} caused by accidental near degeneracy of rotational levels. For example, hyperfine components of the 4_{2,2}(o) and 3_{3,0}(p) levels mix each other by 1.2 x 10^{-3} due to the near degeneracy (Δ E = 0.417 cm^{-1}), but the lower lying 1_{0,1}(p) and 1_{1,1}(o) levels mix only by 8.9 x 10^{-5} because of their large separation (Δ E = 16.27 cm^{-1}). In the present study, we solved the radiative rate equations including all the rotational levels below 900 cm^{-1} to give the o-p conversion lifetime to be 0.451, 3.27, 398 and 910 years for the equilibrium o/p ratio of 3.00, 3.00, 4.52, and 406 when the radiation temperature T_r is 100, 60, 20 and 5 K. These results qualitatively help to understand the observed high o/p ratio of 4.8 ± 0.5 (corresponding to the nuclear spin temperature of 21 K) toward Sgr B2, but they are too slow to compete with the reaction by collision unless the number of density of H_2 in the region is very low (n˜1 cm^{-3}) or the radiative temperature is very high (T_r > 50K). K. Tanaka, K. Harada, and T. Oka, the 67th OSU Symposium MG06, 2012. P. Schilke, et al., A&A 521, L11 (2010). K. Tanaka, K. Harada, and T. Oka, J. Phys. Chem. A

  2. VOLATILECALC: A silicate melt-H2O-CO2 solution model written in Visual Basic for excel

    USGS Publications Warehouse

    Newman, S.; Lowenstern, J. B.

    2002-01-01

    We present solution models for the rhyolite-H2O-CO2 and basalt-H2O-CO2 systems at magmatic temperatures and pressures below ~ 5000 bar. The models are coded as macros written in Visual Basic for Applications, for use within MicrosoftR Excel (Office'98 and 2000). The series of macros, entitled VOLATILECALC, can calculate the following: (1) Saturation pressures for silicate melt of known dissolved H2O and CO2 concentrations and the corresponding equilibrium vapor composition; (2) open- and closed-system degassing paths (melt and vapor composition) for depressurizing rhyolitic and basaltic melts; (3) isobaric solubility curves for rhyolitic and basaltic melts; (4) isoplethic solubility curves (constant vapor composition) for rhyolitic and basaltic melts; (5) polybaric solubility curves for the two end members and (6) end member fugacities of H2O and CO2 vapors at magmatic temperatures. The basalt-H2O-CO2 macros in VOLATILECALC are capable of calculating melt-vapor solubility over a range of silicate-melt compositions by using the relationships provided by Dixon (American Mineralogist 82 (1997) 368). The output agrees well with the published solution models and experimental data for silicate melt-vapor systems for pressures below 5000 bar. ?? 2002 Elsevier Science Ltd. All rights reserved.

  3. Molecular complex morpholine-CO 2-H 2O

    NASA Astrophysics Data System (ADS)

    Jiang, Huiming; Zhang, Shufen; Xu, Yingmei

    2009-02-01

    Morpholine absorbs CO 2 and H 2O in air to form a molecular complex: morpholinium-1-morpholinecarboxylate-H 2O. The structure of the complex was characterized by X-ray single crystal diffraction, 1H NMR and FT-IR. The crystal structure was determined to be triclinic, space group P1¯ with a = 6.494(2) Å, b = 8.098(4) Å, c = 13.533(4) Å, α = 96.99(3)°, β = 102.57(2)°, γ = 104.15(3)°, Z = 2. The complex is stabilized via three hydrogen bonds between the three components, N…O electrostatic attraction and O…O interaction (electron transfer). Due to electron transfer of the carbamate ion, the oxygen atom in water molecule is strongly negatively charged and the O sbnd H bond is considerably shorter than that of free water molecules. The formation of the molecular complex is a reversible process and will decompose upon heating. The mechanism of formation and stabilization is further investigated herein.

  4. Putative role of the malate valve enzyme NADP-malate dehydrogenase in H2O2 signalling in Arabidopsis.

    PubMed

    Heyno, Eiri; Innocenti, Gilles; Lemaire, Stéphane D; Issakidis-Bourguet, Emmanuelle; Krieger-Liszkay, Anja

    2014-04-19

    In photosynthetic organisms, sudden changes in light intensity perturb the photosynthetic electron flow and lead to an increased production of reactive oxygen species. At the same time, thioredoxins can sense the redox state of the chloroplast. According to our hypothesis, thioredoxins and related thiol reactive molecules downregulate the activity of H2O2-detoxifying enzymes, and thereby allow a transient oxidative burst that triggers the expression of H2O2 responsive genes. It has been shown recently that upon light stress, catalase activity was reversibly inhibited in Chlamydomonas reinhardtii in correlation with a transient increase in the level of H2O2. Here, it is shown that Arabidopsis thaliana mutants lacking the NADP-malate dehydrogenase have lost the reversible inactivation of catalase activity and the increase in H2O2 levels when exposed to high light. The mutants were slightly affected in growth and accumulated higher levels of NADPH in the chloroplast than the wild-type. We propose that the malate valve plays an essential role in the regulation of catalase activity and the accumulation of a H2O2 signal by transmitting the redox state of the chloroplast to other cell compartments. PMID:24591715

  5. One-pot synthesis of fluorescent DHLA-stabilized Cu nanoclusters for the determination of H2O2.

    PubMed

    Zhou, Tingyao; Yao, Qiuhong; Zhao, Tingting; Chen, Xi

    2015-08-15

    A facile one-pot approach has been developed to prepare orange-emitting Cu nanoclusters (NCs) using tetrakis(hydroxymethyl)phosphonium chloride as a reducing agent and lipoic acid as a capping agent under an alkaline medium at room temperature. The as-prepared Cu NCs exhibited excellent water solubility, large Stokes shift, long lifetime and good dispersion. After the addition of polyvinyl pyrrolidone, the fluorescence intensity of dihydrolipoic acid-stabilized Cu NCs (DHLA-Cu NCs) was greatly enhanced, and their fluorescence signal remained stable for 5 weeks storage in the dark at room temperature. Based on H2O2-induced fluorescence quenching, DHLA-Cu NCs showed high sensitivity and selectivity for the detection of H2O2 in aqueous solution with a detection limit of 0.3μM, and were applied successfully to the detection of H2O2 in human urine samples. PMID:25966384

  6. Thermodynamic and transport properties of frozen and reacting pH2-oH2 mixtures

    NASA Technical Reports Server (NTRS)

    Carter, H. G.; Bullock, R. E.

    1972-01-01

    Application of experimental state data and spectroscopic term values shows that the thermodynamic and transport properties of reacting pH2-oH2 mixtures are considerably different than those of chemically frozen pH2 at temperatures below 300 R. Calculated H-S data also show that radiation-induced pH2-oH2 equilibration at constant enthalpy produces a temperature drop of at least 28 R, corresponding to an ideal shaft work loss of 15% or more for a turbine operating downstream from the point of conversion. Aside from differences in thermodynamic and transport properties, frozen pH2-oH2 mixtures may differ from pure pH2 on a purely hydrodynamical basis.

  7. Volatile products in the corrosion of Cr, Mo, Ti and four superalloys exposed to O2 containing H2O and gaseous NaCl

    NASA Technical Reports Server (NTRS)

    Fryburg, G. C.; Miller, R. A.; Kohl, F. J.; Stearns, C. A.

    1977-01-01

    Cooled target collection techniques were used to study the formation of volatile products when samples of Cr, Ti, IN-738, 713C, NASA-TRW VIA and B-1900 were exposed, at elevated temperatures, to oxidizing environments containing H2O(g) and NaCl(g). Samples were heated to 1050 C in one atmosphere of slowly flowing oxygen, saturated with water at 21 C, and containing about 50 ppm NaCl(g). Volatile products were detected for all materials except B-1900 and Ti. High pressure mass spectrometric sampling was used to directly identify volatile products emanating from samples of Cr and IN-738 subject to the above environments.

  8. Crystal structures of Ca(ClO4)2·4H2O and Ca(ClO4)2·6H2O.

    PubMed

    Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

    2014-12-01

    The title compounds, calcium perchlorate tetra-hydrate and calcium perchlorate hexa-hydrate, were crystallized at low temperatures according to the solid-liquid phase diagram. The structure of the tetra-hydrate consists of one Ca(2+) cation eightfold coordinated in a square-anti-prismatic fashion by four water mol-ecules and four O atoms of four perchlorate tetra-hedra, forming chains parallel to [01-1] by sharing corners of the ClO4 tetra-hedra. The structure of the hexa-hydrate contains two different Ca(2+) cations, each coordinated by six water mol-ecules and two O atoms of two perchlorate tetra-hedra, forming [Ca(H2O)6(ClO4)]2 dimers by sharing two ClO4 tetra-hedra. The dimers are arranged in sheets parallel (001) and alternate with layers of non-coordinating ClO4 tetra-hedra. O-H⋯O hydrogen bonds between the water mol-ecules as donor and ClO4 tetra-hedra and water mol-ecules as acceptor groups lead to the formation of a three-dimensional network in the two structures. Ca(ClO4)2·6H2O was refined as a two-component inversion twin, with an approximate twin component ratio of 1:1 in each of the two structures. PMID:25552974

  9. Slow spin relaxation induced by magnetic field in [NdCo(bpdo)(H2O)4(CN)6]⋅3H2O.

    PubMed

    Vrábel, P; Orendáč, M; Orendáčová, A; Čižmár, E; Tarasenko, R; Zvyagin, S; Wosnitza, J; Prokleška, J; Sechovský, V; Pavlík, V; Gao, S

    2013-05-01

    We report on a comprehensive investigation of the magnetic properties of [NdCo(bpdo)(H2O)4(CN)6]⋅3H2O (bpdo=4, 4'-bipyridine-N,N'-dioxide) by use of electron paramagnetic resonance, magnetization, specific heat and susceptibility measurements. The studied material was identified as a magnet with an effective spin S = 1/2 and a weak exchange interaction J/kB = 25 mK. The ac susceptibility studies conducted at audio frequencies and at temperatures from 1.8 to 9 K revealed that the application of a static magnetic field induces a slow spin relaxation. It is suggested that the relaxation in the magnetic field appears due to an Orbach-like process between the two lowest doublet energy states of the magnetic Nd(3+) ion. The appearance of the slow relaxation in a magnetic field cannot be associated with a resonant phonon trapping. The obtained results suggest that the relaxation is influenced by nuclear spin driven quantum tunnelling which is suppressed by external magnetic field. PMID:23587762

  10. The Frequency Detuning Correction and the Asymmetry of Line Shapes: The Far Wings of H2O-H2O

    NASA Technical Reports Server (NTRS)

    Ma, Q.; Tipping, R. H.; Hansen, James E. (Technical Monitor)

    2002-01-01

    A far-wing line shape theory which satisfies the detailed balance principle is applied to the H2O-H2O system. Within this formalism, two line shapes are introduced, corresponding to band-averages over the positive and negative resonance lines, respectively. Using the coordinate representation, the two line shapes can be obtained by evaluating 11-dimensional integrations whose integrands are a product of two factors. One depends on the interaction between the two molecules and is easy to evaluate. The other contains the density matrix of the system and is expressed as a product of two 3-dimensional distributions associated with the density matrices of the absorber and the perturber molecule, respectively. If most of the populated states are included in the averaging process, to obtain these distributions requires extensive computer CPU time, but only have to be computed once for a given temperature. The 11-dimensional integrations are evaluated using the Monte Carlo method, and in order to reduce the variance, the integration variables are chosen such that the sensitivity of the integrands on them is clearly distinguished.

  11. A model-based understanding of solid-oxide electrolysis cells (SOECs) for syngas production by H2O/CO2 co-electrolysis

    NASA Astrophysics Data System (ADS)

    Menon, Vikram; Fu, Qingxi; Janardhanan, Vinod M.; Deutschmann, Olaf

    2015-01-01

    High temperature co-electrolysis of H2O and CO2 offers a promising route for syngas (H2, CO) production via efficient use of heat and electricity. The performance of a SOEC during co-electrolysis is investigated by focusing on the interactions between transport processes and electrochemical parameters. Electrochemistry at the three-phase boundary is modeled by a modified Butler-Volmer approach that considers H2O electrolysis and CO2 electrolysis, individually, as electrochemically active charge transfer pathways. The model is independent of the geometrical structure. A 42-step elementary heterogeneous reaction mechanism for the thermo-catalytic chemistry in the fuel electrode, the dusty gas model (DGM) to account for multi-component diffusion through porous media, and a plug flow model for flow through the channels are used in the model. Two sets of experimental data are reproduced by the simulations, in order to deduce parameters of the electrochemical model. The influence of micro-structural properties, inlet cathode gas velocity, and temperature are discussed. Reaction flow analysis is performed, at OCV, to study methane production characteristics and kinetics during co-electrolysis. Simulations are carried out for configurations ranging from simple one-dimensional electrochemical button cells to quasi-two-dimensional co-flow planar cells, to demonstrate the effectiveness of the computational tool for performance and design optimization.

  12. A new oxovanadium(IV) complex containing an O,N-bidentate Schiff base ligand: Synthesis at ambient temperature, characterization, crystal structure and catalytic performance in selective oxidation of sulfides to sulfones using H2O2 under solvent-free conditions

    NASA Astrophysics Data System (ADS)

    Menati, Saeid; Rudbari, Hadi Amiri; Khorshidifard, Mahsa; Jalilian, Fariba

    2016-01-01

    A new bidentate ON Schiff base ligand, HL, was synthesized by simple condensation reaction of isopropylamine and salicylaldehyde. Then by reaction of HL and VO(acac)2 in the ratio of 2:1 at ambient temperature, a new oxovanadium(IV) Schiff base complex, VOL2, was synthesized. The Schiff base ligand and its oxovanadium(IV) complex were characterized by elemental analyses, FT-IR, 1H NMR, 13C NMR and UV-visible spectroscopies. The crystal structure of oxovanadium(IV) complex, VOL2, was also determined by single crystal X-ray analysis. The vanadium center in this structure is coordinated to two bidentate Schiff base ligands with the two nitrogen and two phenolate oxygen atoms in equatorial positions and one oxo oxygen in the axial position to complete the distorted trigonal bipyramidal N2O3 coordination sphere. Catalytic performance of the VOL2 complex was studied in the selective oxidation of thioanisole with the green oxidant 35% aqueous H2O2 under solvent-free conditions and under organic solvents (EtOH, CHCl3, CH2Cl2, DMF, CH3CN, EtOAc) as a model. Due to better catalytic performance of the VOL2 complex under solvent-free conditions, this complex used for the oxidation of the different sulfides to the corresponding sulfones under solvent-free conditions. The use of hydrogen peroxide as oxidant and the absence of solvent makes these reactions interesting from environmental and economic points of view.

  13. Effects of architectures and H2O2 additions on the photocatalytic performance of hierarchical Cu2O nanostructures

    NASA Astrophysics Data System (ADS)

    Deng, Xiaolong; Zhang, Qiang; Zhao, Qinqin; Ma, Lisha; Ding, Meng; Xu, Xijin

    2015-01-01

    Cu2O hierarchical nanostructures with different morphologies were successfully synthesized by a solvothermal method using copper (II) nitrate trihydrate (Cu(NO3)2ṡ3H2O) and ethylene glycol (EG) as initial reagents. The obtained nanostructures were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) specific surface area test, and UV-vis spectroscopy. The synthesis conditions (copper source, temperature, and reaction time) dominated the compositions and the formation of crystals with different morphologies. The visible light photocatalytic properties of as-prepared Cu2O nanostructures were investigated with and without hydrogen peroxide (H2O2), and the effect of H2O2 were evaluated by monitoring the degradation of methyl orange (MO) with various amounts of H2O2. It was revealed that the degree of the photodegradation of MO depends on the amount of H2O2 and the morphology of Cu2O.

  14. Calcite solubility in supercritical CO 2H 2O fluids

    NASA Astrophysics Data System (ADS)

    Fein, Jeremy B.; Walther, John V.

    1987-06-01

    An extraction-quench apparatus was used to measure calcite solubilities in supercritical CO 2H 2O mixtures. Experiments were conducted at 1 kbar and 2 kbar, between 240°C and 620°C and from XCO 2 = .02 toXCO 2 = .15 in order to determine the solubility behavior as a function of pressure, temperature and CO 2 content. The results indicate that calcite solubilities under these conditions behave similarly to previously investigated calcite solubilities at lower pressures and temperatures (SHARP and Kennedy, 1965). At constant XCO 2, the solubility increases with increasing pressure, but it decreases with increasing temperature. When the temperature and pressure are constant, the calcite solubility rises with increasing XCO 2 to a maximum value at XCO 2 between 0.02 and 0.05. For higher CO 2 contents, up to XCO 2 = .15, the calcite solubility decreases, probably due to the decrease of H 2O activities to values significantly below unity. The solubility behavior can be successfully modeled by making the assumption that Ca ++ is the dominant calcium species and that the carbon-bearing species are CO 2(aq) and HCO -3. Since for these dilute H 2OCO 2 fluids, all activity coefficients can be assumed to not differ significantly from unity, ionization constants for the reaction H 2O + CO 2(aq) H + + HCO -3 can be calculated at 1 and 2 kbar between 250°C and 550°C. These calculated values are in good agreement with the low temperature determinations of the ionization constants for this reaction determined by Read (1975). Values of the molal Gibbs free energy of CO 2(aq) obtained in our study exhibit a much greater positive departure from ideality than those calculated with the modified Redlich-Kwong equations of either Flowers (1979) or Kerrick and Jacobs (1981) for dilute CO 2 aqueous solutions.

  15. Seasonal Mapping of [HDO]/[H2O] in the Martian Atmosphere

    NASA Astrophysics Data System (ADS)

    Novak, Robert E.; Mumma, M. J.; Villanueva, G.; DiSanti, M. A.; Bonev, B.; Rahon, C. L.; Sanstead, C. C.

    2007-10-01

    We report seasonal changes in isotopic water on Mars, based on observations taken at NASA's IRTF using CSHELL. Column densities of HDO and H2O were extracted from individual spectral lines near 3.67 μm and 3.29 μm. The slit was positioned N-S on Mars' central meridian. Data were acquired in an ABBA sequence and their difference constitutes a spectral/spatial image from which each species was quantified. The frames were rectified by re-sampling in wavelength and spatial dimension, and spectra were then extracted at 0.6 arc-second intervals along the slit. We created atmospheric models for Earth and Mars using GENLN2 atmospheric software. The models include solar continuum (and Fraunhofer lines) with two-way transmission through Mars’ atmosphere, thermal emission from Mars’ surface and atmosphere with one-way transmission through Mars atmosphere, and one-way transmission through Earth's atmosphere for both. Latitudinal maps of [HDO]/[H2O] were constructed. The [HDO]/[H2O] ratios are always higher than terrestrial and they vary with both latitude and season. The ratio in the southern Martian hemisphere is found to be larger than that in the northern. This difference could be the signature of Rayleigh distillation, a process in which the different mean temperatures of the polar caps cause a different degree of HDO sequestration, resulting in different degrees of enrichment in the polar caps. For Ls =155o in 2003 and Ls =357o in 2006, HDO and H2O column densities were both obtained from CSHELL data. They will be compared with results from other seasons (Ls =67o in 1997, Ls =223o in 2005, and Ls =333o in 2004) when HDO was measured with CSHELL and H2O was measured by MGS-TES. This work was partially funded by grants from NASA's Planetary Astronomy Program (RTOP 344-32-51-96) and NSF RUI Program (AST-0505765). We acknowledge the NASA-IRTF for observing time and M. Smith for providing TES results.

  16. Excited OH+, H2O+, and H3O+ in NGC 4418 and Arp 220

    NASA Astrophysics Data System (ADS)

    González-Alfonso, E.; Fischer, J.; Bruderer, S.; Müller, H. S. P.; Graciá-Carpio, J.; Sturm, E.; Lutz, D.; Poglitsch, A.; Feuchtgruber, H.; Veilleux, S.; Contursi, A.; Sternberg, A.; Hailey-Dunsheath, S.; Verma, A.; Christopher, N.; Davies, R.; Genzel, R.; Tacconi, L.

    2013-02-01

    We report on Herschel/PACS observations of absorption lines of OH+, H2O+ and H3O+ in NGC 4418 and Arp 220. Excited lines of OH+ and H2O+ with Elower of at least 285 and ~200 K, respectively, are detected in both sources, indicating radiative pumping and location in the high radiation density environment of the nuclear regions. Abundance ratios OH+/H2O+ of 1-2.5 are estimated in the nuclei of both sources. The inferred OH+ column and abundance relative to H nuclei are (0.5-1) × 1016 cm-2 and ~ 2 × 10-8, respectively. Additionally, in Arp 220, an extended low excitation component around the nuclear region is found to have OH+/H2O+ ~ 5-10. H3O+ is detected in both sources with N(H3O+) ~ (0.5-2) × 1016 cm-2, and in Arp 220 the pure inversion, metastable lines indicate a high rotational temperature of ~500 K, indicative of formation pumping and/or hot gas. Simple chemical models favor an ionization sequence dominated by H+ → O+ → OH+ → H2O+ → H3O+, and we also argue that the H+ production is most likely dominated by X-ray/cosmic ray ionization. The full set of observations and models leads us to propose that the molecular ions arise in a relatively low density (≳104 cm-3) interclump medium, in which case the ionization rate per H nucleus (including secondary ionizations) is ζ > 10-13 s-1, a lower limit that is several × 102 times the highest current rate estimates for Galactic regions. In Arp 220, our lower limit for ζ is compatible with estimates for the cosmic ray energy density inferred previously from the supernova rate and synchrotron radio emission, and also with the expected ionization rate produced by X-rays. In NGC 4418, we argue that X-ray ionization due to an active galactic nucleus is responsible for the molecular ion production. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

  17. Glass Composition-Dependent Silicate Absorption Peaks in FTIR Spectroscopy: Implications for Measuring Sample Thickness and Molecular H2O

    NASA Astrophysics Data System (ADS)

    McIntosh, I. M.; Nichols, A. R.; Schipper, C. I.; Stewart, R. B.

    2015-12-01

    Fourier-transform infrared spectroscopy (FTIR) is often used to measure the H2O and CO2 contents of volcanic glasses. A key advantage of FTIR over other analytical techniques is that it can reveal not only total H2O concentration but also H2O speciation, i.e. how much H2O is present as molecular H2O (H2Om) and how much as hydroxyl groups (OH) bound to the silicate network. This H2O speciation data can be used to investigate cooling rate and glass transition temperature of volcanic glasses, and to interpret H2O contents of pyroclasts affected by partial bubble resorption during cooling or secondary hydration after deposition. FTIR in transmitted light requires sample wafers polished on both sides of known thickness. Thickness is commonly measured using a micrometer but this may damage fragile samples and in samples with non-uniform thickness, e.g. vesicular samples, it is difficult to position at the exact location of FTIR analysis. Furthermore, in FTIR images or maps of such samples it is impractical to determine the thickness across the whole of the analysed area, resulting either in only a selection of the collected data being processed quantitatively and the rest being unused, or results being presented in terms of absorbance, which does not account for variations in thickness.It is known that FTIR spectra contain absorption peaks related to the glass aluminosilicate network at wavenumbers of ~2000, ~1830 and ~1600 cm-1 [1]. These have been shown to be proportional to sample thickness at the analysis location for one obsidian composition with up to 0.66 wt% H2O [2]. We test whether this calibration can be applied more widely by analysing a range of synthetic and natural glasses (andesitic to rhyolitic) to examine how the position and relative intensities of the different silicate absorption peaks vary with composition and H2O content. Our data show that even minor differences in composition necessitate a unique calibration. Furthermore, importantly we show how

  18. Utilization of membranes for H2O recycle system

    NASA Technical Reports Server (NTRS)

    Ohya, H.; Oguchi, M.

    1986-01-01

    Conceptual studies of closed ecological life support systems (CELSS) carried out at NAL in Japan for a water recycle system using membranes are reviewed. The system will treat water from shower room, urine, impure condensation from gas recycle system, and so on. The H2O recycle system is composed of prefilter, ultrafiltration membrane, reverse osmosis membrane, and distillator. Some results are shown for a bullet train of toilet-flushing water recycle equipment with an ultraviltration membrane module. The constant value of the permeation rate with a 4.7 square meters of module is about 70 1/h after 500th of operation. Thermovaporization with porous polytetrafluorocarbon membrane is also proposed to replce the distillator.

  19. Intermolecular potential for thermal H2O-He collisions

    NASA Technical Reports Server (NTRS)

    Palma, Amedeo; Green, Sheldon; Defrees, D. J.; Mclean, A. D.

    1988-01-01

    Theoretical potentials for rotational excitation of H2O by He were constructed via several methods, all of which start with a large basis set SCF interaction. The semiempirical Hartree-Fock with damped dispersion model adds a damped long-range attraction with parameters adjusted to fit experimental total differential cross sections. Purely ab initio potentials add correlation energies obtained via perturbation theory (MP2 and MP4) or a variational method (ICF1). Scattering calculations were performed on all surfaces to compare wih available beam scattering and pressure broadening data and to assess sensitivity of state-to-state rates to uncertainties in the potential. From comparison with the limited experimental data, the ICF1 surface appears to be marginally better than the MP4 surface. Thermal rates calculated from this surface should be accurate to better than 50 percent, at least for the larger, more important rates.

  20. Theoretical studies of photoexcitation and ionization in H2O

    NASA Technical Reports Server (NTRS)

    Diercksen, G. H. F.; Kraemer, W. P.; Rescigno, T. N.; Bender, C. F.; Mckoy, B. V.; Langhoff, S. R.; Langhoff, P. W.

    1982-01-01

    Theoretical studies using Franck-Condon and static-exchange approximations are reported for the complete dipole excitation and ionization spectrum in H2O, where (1) large Cartesian Gaussian basis sets are used to represent the required discrete and continuum electronic eigenfunctions at the ground state equilibrium geometry, and (2) previously devised moment-theory techniques are employed in constructing the continuum oscillator-strength densities from the calculated spectra. Comparisons are made of the calculated excitation and ionization profiles with recent experimental photoabsorption studies and corresponding spectral assignments, electron impact-excitation cross sections, and dipole and synchrotron-radiation studies of partial-channel photoionization cross sections. The calculated partial-channel cross sections are found to be atomic-like, and dominated by 2p-kd components. It is suggested that the latter transition couples with the underlying 1b(1)-kb(1) channel, accounting for a prominent feature in recent synchrotron-radiation measurements.

  1. H2O at the Phoenix landing site.

    PubMed

    Smith, P H; Tamppari, L K; Arvidson, R E; Bass, D; Blaney, D; Boynton, W V; Carswell, A; Catling, D C; Clark, B C; Duck, T; Dejong, E; Fisher, D; Goetz, W; Gunnlaugsson, H P; Hecht, M H; Hipkin, V; Hoffman, J; Hviid, S F; Keller, H U; Kounaves, S P; Lange, C F; Lemmon, M T; Madsen, M B; Markiewicz, W J; Marshall, J; McKay, C P; Mellon, M T; Ming, D W; Morris, R V; Pike, W T; Renno, N; Staufer, U; Stoker, C; Taylor, P; Whiteway, J A; Zent, A P

    2009-07-01

    The Phoenix mission investigated patterned ground and weather in the northern arctic region of Mars for 5 months starting 25 May 2008 (solar longitude between 76.5 degrees and 148 degrees ). A shallow ice table was uncovered by the robotic arm in the center and edge of a nearby polygon at depths of 5 to 18 centimeters. In late summer, snowfall and frost blanketed the surface at night; H(2)O ice and vapor constantly interacted with the soil. The soil was alkaline (pH = 7.7) and contained CaCO(3), aqueous minerals, and salts up to several weight percent in the indurated surface soil. Their formation likely required the presence of water. PMID:19574383

  2. First Principle Predictions of Isotopic Shifts in H2O

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Kwak, Dochan (Technical Monitor)

    2002-01-01

    We compute isotope independent first and second order corrections to the Born-Oppenheimer approximation for water and use them to predict isotopic shifts. For the diagonal correction, we use icMRCI wavefunctions and derivatives with respect to mass dependent, internal coordinates to generate the mass independent correction functions. For the non-adiabatic correction, we use scaled SCF/CIS wave functions and a generalization of the Handy method to obtain mass independent correction functions. We find that including the non-adiabatic correction gives significantly improved results compared to just including the diagonal correction when the Born-Oppenheimer potential energy surface is optimized for H2O-16. The agreement with experimental results for deuterium and tritium containing isotopes is nearly as good as our best empirical correction, however, the present correction is expected to be more reliable for higher, uncharacterized levels.

  3. Infrared spectrum and predissociation dynamics of H2O+ -Ar.

    PubMed

    Dopfer, O; Engel, V

    2004-12-22

    The infrared (IR) spectrum and vibrational predissociation of the proton-bound H(2)O(+)-Ar ionic complex are investigated within an ab initio and quantum dynamical study. For this purpose, a two-dimensional potential energy surface (2D PES) is determined as a function of the HO-H and OH-Ar coordinates. This PES is then employed in a wave-packet calculation to determine spectral properties of the system and to calculate the IR absorption spectrum. The vibrational energy levels and relative IR intensities agree well with the experimental spectrum reported earlier. On the other hand, the predissociation lifetimes in the nanosecond regime derived from the 2D PES are in disagreement with the experimental observations, indicating the importance of the neglected degrees of freedom for a correct description of the dynamics of the complex. PMID:15606253

  4. Experiments on H2-O2 MHD power generation

    NASA Astrophysics Data System (ADS)

    Smith, J. M.

    1980-06-01

    MHD power generation experiments utilizing a cesium-seeded H2-O2 working fluid have been carried out using a diverging area Hall duct having an entrance Mach number of 2. The experiments are conducted in a high-field strength cryomagnet facility at field strengths up to 5 tesla. The effects of power takeoff location, axial duct location within the magnetic field, generator loading, B-field strength, and electrode breakdown voltage were investigated. For the operating conditions of these experiments it is found that the power output increases with the square of the B-field and can be limited by choking of the channel or interelectrode voltage breakdown which occurs at Hall fields greater than 50 volts/insulator.

  5. Experiments on H2-O2MHD power generation

    NASA Technical Reports Server (NTRS)

    Smith, J. M.

    1980-01-01

    Magnetohydrodynamic power generation experiments utilizing a cesium-seeded H2-O2 working fluid were carried out using a diverging area Hall duct having an entrance Mach number of 2. The experiments were conducted in a high-field strength cryomagnet facility at field strengths up to 5 tesla. The effects of power takeoff location, axial duct location within the magnetic field, generator loading, B-field strength, and electrode breakdown voltage were investigated. For the operating conditions of these experiments, it is found that the power output increases with the square of the B-field and can be limited by choking of the channel or interelectrode voltage breakdown which occurs at Hall fields greater than 50 volts/insulator. Peak power densities of greater than 100 MW/cu M were achieved.

  6. Ferroelectricity in high-density H2O ice.

    PubMed

    Caracas, Razvan; Hemley, Russell J

    2015-04-01

    The origin of longstanding anomalies in experimental studies of the dense solid phases of H2O ices VII, VIII, and X is examined using a combination of first-principles theoretical methods. We find that a ferroelectric variant of ice VIII is energetically competitive with the established antiferroelectric form under pressure. The existence of domains of the ferroelectric form within anti-ferroelectric ice can explain previously observed splittings in x-ray diffraction data. The ferroelectric form is stabilized by density and is accompanied by the onset of spontaneous polarization. The presence of local electric fields triggers the preferential parallel orientation of the water molecules in the structure, which could be stabilized in bulk using new high-pressure techniques. PMID:25854247

  7. Energy transport in photoexcited crystals of K3[Tb(C2O4)3(H2O)].2H2O: Transfer from Tb3+ to Nd3+ and Eu3+

    NASA Astrophysics Data System (ADS)

    Kahwa, Ishenkumba A.; Parkes, Charmaine C.; McPherson, Gary L.

    1995-10-01

    The luminescence decay dynamics of Tb3+(5D4) and Eu(5D0) in triclinic (P1¯) crystalline K3[Ln(C2O4)3(H2O)].2H2O solids was studied between 10 and 298 K in order to establish the energy-transport characteristics. The luminescence decay rate of Tb3+ (740 s-1 for Ln=Tb3+) is temperature independent for the pure terbium complex; with introduction of Ln3+ dopants (e.g., Ln=Nd, Eu) faster decay rates which are temperature dependent are obtained. For the Eu3+ dopant, excitation buildup on the Eu3+(5D0) decay curve upon Tb3+(5D4) excitation confirms that energy transfer from Tb3+(5D4) to Ln3+ is active. The temperature dependence of the energy-transfer process in the K3[Eu0.83Tb0.17(C2O4)3(H2O)].2H2O mixed complex is well described by a relatively simple empirical expression based on Boltzmann's statistical dynamics of Eu3+ electronic energy among the 7FJ (J=0,1,2) terms. The limiting Eu3+-Tb3+ transfer rates are ~5.4×103 and 5.3×104 s-1 at 77 and 298 K, respectively. Energy migration on the terbium sublattice was confirmed by comparing Huber's [Phys. Rev. B 20, 2707 (1979)] trapping functions for K3[Eu0.4Tb0.6(C2O4)3(H2O)].2H2O and K3[Eu0.4Tb0.1Gd0.5(C2O4)3(H2O)].2H2O (Gd3+ serving as a scatterer for Tb3+ excitation). Although the structure of the complexes features a one-dimensional zigzag array of Ln3+ ions, energy transport is diffusive and not one dimensional.

  8. Quantification of the CO2 budget and H2O-CO2 systematics in subduction-zone magmas through the experimental hydration of melt inclusions in olivine at high H2O pressure

    NASA Astrophysics Data System (ADS)

    Mironov, Nikita; Portnyagin, Maxim; Botcharnikov, Roman; Gurenko, Andrey; Hoernle, Kaj; Holtz, François

    2015-09-01

    Reliable evaluation of CO2 contents in parental arc magmas, which can be preserved in melt inclusions in phenocrysts, is required to verify the proposed efficiency of CO2 recycling at convergent margins. Quantification of bulk CO2 concentration in melt inclusions requires their complete homogenization. Using samples from lavas from the Bulochka vent of Klyuchevskoy Volcano (Kamchatka), we applied a novel experimental approach to homogenize and re-equilibrate naturally dehydrated (<1 wt.% H2O) melt inclusions from high-Fo (85-91 mol.%) olivine. The experiments were performed at temperatures of 1150-1400 °C, pressures of up to 500 MPa, under dry to H2O-saturated conditions and with oxygen fugacity ranging from CCO to QFM+3.3. No homogenization was achieved at dry conditions. Complete dissolution of fluid bubbles (homogenization) in the melt inclusions was achieved at H2O pressures of 500 MPa and temperature of 1150 °C, when water content in the melt inclusions reached 4-5 wt.% H2O. The CO2 content in the homogenized inclusions is 3800 ± 140 ppm and CO2/Nb = 3000 ± 420, which are the highest values reported so far for the typical middle-K primitive arc melts and fall within the range of values inferred from the magmatic flux and volcanic gas data for primary arc magma compositions. About 83% of the CO2 in Klyuchevskoy magmas is likely to be derived from the subducting slab and can be attributed to flux melting with a fluid having a CO2/H2O ratio of ∼0.06. The H2O and CO2 contents in the melt inclusions after hydrous experiments were found to correlate positively with each other and negatively with the volume of fluid bubble, reflecting increasing internal pressure in melt inclusions with increasing melt hydration. Therefore, similar trends observed in some natural sets of melt inclusions can be attributed to a partial dehydration of melts after entrapment, operating simultaneously with or following post-entrapment crystallization. Our study implies that the

  9. A comparison of ATTREX H2O observations in the TTL with values derived from reanalysis-based back trajectories

    NASA Astrophysics Data System (ADS)

    Thornberry, T. D.; Rollins, A. W.; Bui, T. V.; Pfister, L.; Gao, R. S.

    2015-12-01

    Despite very low mixing ratios relative to the troposphere, water vapor in the lower stratosphere (LS) plays a significant role in Earth's radiative balance and climate system, and is an important constituent in stratospheric chemistry. The low H2O content of air entering the LS is established to first order by dehydration processes controlled by the cold temperatures of the tropical tropopause layer (TTL), especially over the western Pacific. Global climate models rely on parameterizations in order to simulate TTL dehydration processes and calculate the amount of H2O transported into the stratosphere. Here we present an analysis of in situ water vapor measurements in the western Pacific TTL from the NASA ATTREX campaign and compare them to reanalysis-based back trajectory calculations of LS H2O in order to investigate the efficiency of TTL dehydration processes and provide constraints on the representation of TTL dehydration in reanalyses and global models.

  10. Structure and Raman spectra of single crystal La 2(SO 4) 3 · 8H 2O

    NASA Astrophysics Data System (ADS)

    Vanderpool, Richard A.; Khan, Masood A.; Frech, Roger

    1991-05-01

    The room temperature polarized Raman spectra of single-crystal La 2(SO 4) 3 · 8H 2O have been measured in the range 5-4000 cm -1. The internal and external modes,based on a factor group analysis and comparison with Na 2SO 4 and La 2(SO 4) 3 · 9H 2O, have been assigned. A single-crystal X-ray diffraction study shows that La 2(SO 40 3 · 8H 2O crystallizes in the monoclinic space group Pn ( Z = 2) with cell dimensions a = 6.881(2) Å, b = 17.376(4) Å, c = 6.923(2) Å, and β = 92.34 (2)°. The structure was refined to a final R = 0.033 for 2333 observed reflections.

  11. Vesiculation in rhyolite at low H2O contents: A thermodynamic model

    NASA Astrophysics Data System (ADS)

    Ryan, Amy G.; Russell, James K.; Hess, Kai-Uwe; Phillion, Andre B.; Dingwell, Donald B.

    2015-12-01

    We present experimental data on the thermodynamics and kinetics of bubble nucleation and growth in weakly H2O-oversaturated rhyolitic melts. The high-temperature (900-1100°C) experiments involve heating of rhyolitic obsidian from Hrafntinnuhryggur, Krafla, Iceland to above their glass transition temperature (Tg ˜ 690°C) at 0.1 MPa for times of 0.25-24 h. During experiments, the rhyolite cores increase in volume as H2O vapor-filled bubbles nucleate and expand. The extent of vesiculation, as tracked by porosity, is mapped in temperature-time (T-t) space. At constant temperature and for a characteristic dwell time, the rhyolite cores achieve a maximum volume where the T-t conditions reach thermochemical equilibrium. For each T-t snapshot of vesiculation, we use 3-D analysis of X-ray computed tomographic (XCT) images of the quenched cores to obtain the bubble number density (BND) and bubble-size distribution (BSD). BNDs for the experimental cores are insensitive to T and t, indicating a single nucleation event. All BSDs converge to a common distribution, independent of T, melt viscosity (η), or initial degree of saturation, suggesting a common growth process. We use these data to calibrate an empirical model for predicting the rates and amounts of vesiculation in rhyolitic melts as a function of η and thermochemical affinity (A): two computable parameters that are dependent on T, pressure and H2O content. The model reproduces the experimental data set and data from the literature to within experimental error, and has application to natural volcanic systems where bubble formation and growth are not diffusion limited (e.g., lavas, domes, ignimbrites, conduit infill).

  12. Electrolysis of H2O and CO2 in an oxygen-ion conducting solid oxide electrolyzer with a La0.2Sr0.8TiO3+δ composite cathode

    NASA Astrophysics Data System (ADS)

    Li, Shisong; Li, Yuanxin; Gan, Yun; Xie, Kui; Meng, Guangyao

    2012-11-01

    Solid oxide electrolyzers have attracted a great deal of interest in recent years because they can convert electrical energy into chemical energy with high efficiency. Ni/YSZ cathodes are generally utilized for high temperature electrolysis of H2O and CO2 in oxygen-ion conducting solid oxide electrolyzers; however, such electrodes can only operate under reducing conditions. In an atmosphere without a flow of reducing gas, cathodes based on La0.2Sr0.8TiO3+δ (LST) are a promising alternative. Solid Oxide Electrolyzers with LST cathodes without pre-reduction were used at 700 °C for the electrolysis of 3%H2O/97%N2 and 100%CO2, and promising polarization impedance data were obtained in both atmospheres. The electrochemical results indicated that the electrochemical reduction of the La0.2Sr0.8TiO3+δ cathode was the main process at low electrical voltages, while the electrolysis was the main process at high voltages because ion transportation in the electrolyte limited the overall efficiency. The electrolysis of H2O was determined to be more efficient than the electrolysis of CO2 under the same conditions. The Faraday efficiencies of H2O and CO2 were 85.0% and 24.7%, respectively, at 700 °C and a 2 V applied potential.

  13. Behavior of Ni2+ cations in aqueous and alcohol solutions of NiCl2 · 6H2O

    NASA Astrophysics Data System (ADS)

    Petkova, P.; Nedkov, V.; Vasilev, P.; Ismailov, I.

    2014-09-01

    We have investigated the optical properties of Ni2+ cations in aqueous and alcohol solutions of NiCl2 · 6H2O at room temperature. We measured the absorption spectra of these two types of solutions in the spectral region 395-795 nm. The Racah’s parameters and the exchange integrals of the aqueous complex [Ni(H2O)6]2+ have been calculated. The parameters Dq, Dt and Ds are also calculated on the basis of our experimental data. The parameters δσ and δπ, connected with the symmetry of the complex, are determined.

  14. Monitoring dehydration of the organic-inorganic [(C3H7)4N][SnCl5(H2O)]·2H2O compound using simultaneous thermal and Raman studies

    NASA Astrophysics Data System (ADS)

    Hajlaoui, S.; Chaabane, I.; Guidara, K.; Bulou, A.

    2016-07-01

    In this work we report the experimental studies of the structural phase transition in the [(C3H7)4N]SnCl5(H2O)]·2H2O compound by differential scanning calorimetric (DSC) and Raman spectroscopic. The X-ray powder diffraction study of the [(C3H7)4N][SnCl5(H2O)]·2H2O sample at room temperature showed that this compound is monoclinic and has P121/c1 space group. Differential scanning calorimetric disclosed two types of phase transitions in the temperature range 356-376 (T1) K and at 393 K (T2) characterized, by a loss of water molecules and probably a reconstruction of new anionic parts after T2 transition. The Raman scattering spectra recorded at various temperatures in the wavenumber range from 100 to 3800 cm- 1 covering the domains of existence of changes in the vicinity of the two phase transitions detected by DSC measurement. A detailed study of the spectral parameters (wave number, reduced intensity and the full width at half maximum) as a function of temperature of a chosen band, associated with (νs(Snsbnd O) + νs(Snsbnd Cl)), based on an order-disorder model allowed us to obtain information relative to the activation energy and correlation length.

  15. Monitoring dehydration of the organic-inorganic [(C3H7)4N][SnCl5(H2O)]·2H2O compound using simultaneous thermal and Raman studies.

    PubMed

    Hajlaoui, S; Chaabane, I; Guidara, K; Bulou, A

    2016-07-01

    In this work we report the experimental studies of the structural phase transition in the [(C3H7)4N]SnCl5(H2O)]·2H2O compound by differential scanning calorimetric (DSC) and Raman spectroscopic. The X-ray powder diffraction study of the [(C3H7)4N][SnCl5(H2O)]·2H2O sample at room temperature showed that this compound is monoclinic and has P121/c1 space group. Differential scanning calorimetric disclosed two types of phase transitions in the temperature range 356-376 (T1) K and at 393K (T2) characterized, by a loss of water molecules and probably a reconstruction of new anionic parts after T2 transition. The Raman scattering spectra recorded at various temperatures in the wavenumber range from 100 to 3800cm(-1) covering the domains of existence of changes in the vicinity of the two phase transitions detected by DSC measurement. A detailed study of the spectral parameters (wave number, reduced intensity and the full width at half maximum) as a function of temperature of a chosen band, associated with (νs(SnO)+νs(SnCl)), based on an order-disorder model allowed us to obtain information relative to the activation energy and correlation length. PMID:27070530

  16. Kinetic Studies of Iron Deposition Catalyzed by Recombinant Human Liver Heavy, and Light Ferritins and Azotobacter Vinelandii Bacterioferritin Using O2 and H2O2 as Oxidants

    NASA Technical Reports Server (NTRS)

    Bunker, Jared; Lowry, Thomas; Davis, Garrett; Zhang, Bo; Brosnahan, David; Lindsay, Stuart; Costen, Robert; Choi, Sang; Arosio, Paolo; Watt, Gerald D.

    2005-01-01

    The discrepancy between predicted and measured H2O2 formation during iron deposition with recombinant heavy human liver ferritin (rHF) was attributed to reaction with the iron protein complex [Biochemistry 40 (2001) 10832-10838]. This proposal was examined by stopped-flow kinetic studies and analysis for H2O2 production using (1) rHF, and Azotobacter vinelandii bacterial ferritin (AvBF), each containing 24 identical subunits with ferroxidase centers; (2) site-altered rHF mutants with functional and dysfunctional ferroxidase centers; and (3) rccombinant human liver light ferritin (rLF), containing 110 ferroxidase center. For rHF, nearly identical pseudo-first-order rate constants of 0.18 per second at pH 7.5 were measured for Fe(2+) oxidation by both O2 and H2O2, but for rLF, the rate with O2 was 200-fold slower than that for H2O2 (k-0.22 per second). A Fe(2+)/O2 stoichiometry near 2.4 was measured for rHF and its site altered forms, suggesting formation of H2O2. Direct measurements revealed no H2O2 free in solution 0.5-10 min after all Fe(2+) was oxidized at pH 6.5 or 7.5. These results are consistent with initial H2O2 formation, which rapidly reacts in a secondary reaction with unidentified solution components. Using measured rate constants for rHF, simulations showed that steady-state H2O2 concentrations peaked at 14 pM at approx. 600 ms and decreased to zero at 10-30 s. rLF did not produce measurable H2O2 but apparently conducted the secondary reaction with H2O2. Fe(2+)/O2 values of 4.0 were measured for AvBF. Stopped-flow measurements with AvBF showed that both H2O2 and O2 react at the same rate (k=0.34 per second), that is faster than the reactions with rHF. Simulations suggest that AvBF reduces O2 directly to H2O without intermediate H2O2 formation.

  17. Kinetic studies of iron deposition catalyzed by recombinant human liver heavy and light ferritins and Azotobacter vinelandii bacterioferritin using O2 and H2O2 as oxidants.

    PubMed

    Bunker, Jared; Lowry, Thomas; Davis, Garrett; Zhang, Bo; Brosnahan, David; Lindsay, Stuart; Costen, Robert; Choi, Sang; Arosio, Paolo; Watt, Gerald D

    2005-04-22

    The discrepancy between predicted and measured H(2)O(2) formation during iron deposition with recombinant heavy human liver ferritin (rHF) was attributed to reaction with the iron protein complex [Biochemistry 40 (2001) 10832-10838]. This proposal was examined by stopped-flow kinetic studies and analysis for H(2)O(2) production using (1) rHF, and Azotobacter vinelandii bacterial ferritin (AvBF), each containing 24 identical subunits with ferroxidase centers; (2) site-altered rHF mutants with functional and dysfunctional ferroxidase centers; and (3) recombinant human liver light ferritin (rLF), containing no ferroxidase center. For rHF, nearly identical pseudo-first-order rate constants of 0.18 s(-1) at pH 7.5 were measured for Fe(2+) oxidation by both O(2) and H(2)O(2), but for rLF, the rate with O(2) was 200-fold slower than that for H(2)O(2) (k = 0.22 s(-1)). A Fe(2+)/O(2) stoichiometry near 2.4 was measured for rHF and its site altered forms, suggesting formation of H(2)O(2). Direct measurements revealed no H(2)O(2) free in solution 0.5-10 min after all Fe(2+) was oxidized at pH 6.5 or 7.5. These results are consistent with initial H(2)O(2) formation, which rapidly reacts in a secondary reaction with unidentified solution components. Using measured rate constants for rHF, simulations showed that steady-state H(2)O(2) concentrations peaked at 14 muM at approximately 600 ms and decreased to zero at 10-30 s. rLF did not produce measurable H(2)O(2) but apparently conducted the secondary reaction with H(2)O(2). Fe(2+)/O(2) values of 4.0 were measured for AvBF. Stopped-flow measurements with AvBF showed that both H(2)O(2) and O(2) react at the same rate (k = 0.34 s(-1)), that is faster than the reactions with rHF. Simulations suggest that AvBF reduces O(2) directly to H(2)O without intermediate H(2)O(2) formation. PMID:15829358

  18. Ion irradiation of crystalline H 2O-ice: Effect on the 1.65-μm band

    NASA Astrophysics Data System (ADS)

    Mastrapa, Rachel M. E.; Brown, Robert H.

    2006-07-01

    We have found that 0.8 MeV proton irradiation of crystalline H 2O-ice results in temperature dependent amorphization. The H 2O-ice's phase was determined using the near infrared spectrum from 1.0 μm (10,000 cm -1) to 2.5 μm (4000 cm -1). In crystalline H 2O-ice, the 1.65-μm (6061 cm -1) band is strong while it is nearly absent in the amorphous spectrum [Schmitt, B., Quirico, E., Trotta, F., Grundy, W.M., 1998. In: Schmitt, B., de Bergh, C., Festou, M. (Eds.), Solar System Ices. Kluwer Academic, Norwell, MA, 1998, pp. 199-240]. In this experiment, at low temperatures (9, 25, and 40 K), irradiation of crystalline H 2O-ice produced the amorphous H 2O-ice's spectrum. However, at 50 K, some crystalline absorptions persisted after irradiation and at 70 and 100 K the crystalline spectrum showed only slight changes after irradiation. Our results agree with previous H 2O-ice irradiation studies examining the crystalline peaks near 44 and 62 μm by Moore and Hudson [Moore, M.H., Hudson, R.L., 1992. Astrophys. J. 401, 353-360] and near 3.07 μm by Strazzulla et al. [Strazzulla, G., Baratta, G.A., Leto, G., Foti, G., 1992. Europhys. Lett. 18, 517-522] and by Leto and Baratta [Leto, G., Baratta, G.A., 2003. Astron. Astrophys. 397, 7-13]. We present a method of measuring band areas to quantify the phase and radiation dose of icy Solar System surfaces.

  19. Biological dosimetry after H2O2/L-histidine treatment

    NASA Astrophysics Data System (ADS)

    Hausmann, Michael; Lentfer, Heiko; Wolf, Dietmar; Bauer, Eckhard; Aldinger, Klaus; Greulich, Karl-Otto; Cremer, Christoph G.

    1998-01-01

    In biological dosimetry after radiation or chemical exposure, it has been well established to estimate exposure doses from the relative rate of aberrant chromosomes, especially dicentric chromosomes in a given number of cells. For this purpose, dose-efficiency curves depending on laboratory parameters (e.g. preparation technique, analysis procedure etc.) have to be measured under standard conditions. For statistical reasons, a high number of chromosomes or cells, respectively, has to be evaluated. For a Chinese hamster cell line (CO60) as a typical model system in mutation research, a dose efficiency relation after H2O2/L-histidine treatment of the cells was determined using the Heidelberg slit-scan flow fluorometer. This technique has the advantage that several thousand chromosomes can be automatically analyzed in a very short time. As expected, for low doses of H2O2/L-histidine exposure, a nearly linear dependence of the relative number of dicentric chromosomes to the concentration of H2O2 was obtained. In order to correlate the relative number of dicentric chromosomes to the relative number of double strand breaks, the cells were analyzed by the technique of the neutral comet assay. The dose dependent `tail moment' obtained from the comet assay also showed a linear behavior. This confirmed the results obtained by slit-scan flow fluorometry. Furthermore, the linear dependence of the dose efficiency curve was well compatible to results obtained by visual counting by means of a fluorescence microscope. In this case chromosome 1 of the Chinese hamster cell line DON was specifically labelled by fluorescence in situ hybridization.

  20. ISO-SWS Observations of CO_2 and H_2O in R Cassiopeiae

    NASA Astrophysics Data System (ADS)

    Markwick, A. J.; Millar, T. J.

    2000-07-01

    We present ISO-SWS spectra of the O-rich Mira variable R Cas, showing CO_2 in absorption and emission, and H_2O in absorption. The CO_2 absorption feature is the 0110-0000 ro-vibrational band at 14.97 μm. The emission features are the 1000-0110 and 1110-0220 ro-vibrational transitions at 13.87 and 13.48 μm respectively. The water absorption spectrum shows the nu_1 and nu_3 ro-vibrational bands in the 2.75-3 μm region. Using LTE models, we derive physical parameters for the features. We find the CO_2 emission temperature to be ~ 1100 K. We discuss the nature of the CO_2 feature at 15 μm and show that it can be modeled as an emission/absorption band by deviating from thermal equilibrium for the population of the 0110 vibrational level. The H_2O absorption spectrum is shown to arise from gas at different temperatures, but can be fit reasonably well with two components at T=950 K and T=250 K. The CO_2 emission and hot H_2O absorption temperatures are similar, suggesting that these features probe the same region of the inner envelope. We discuss the inner envelope chemistry using molecular equilibrium calculations and recent modeling work by Duari et al. (1999), and find our observations consistent with the results. We also report the detection of the CO_2 0110-0000 ro-vibrational band in absorption towards another oxygen-rich Mira, IRC+10011. Based on observations with ISO, an ESA project with instruments funded by ESA Member States (especially the PI countries: France, Germany, the Netherlands and the United Kingdom) with the participation of ISAS and NASA. The SWS is a joint project of SRON and MPE.

  1. An experimental study iof the diffusion of C and O in calcite in mixed Co2-H2O fluids.

    SciTech Connect

    Labotka, Theodore C.; Cole, David; Fayek, Mostafa; Chacko, Thomas {nmn}

    2011-01-01

    The diffusivity of C and O in calcite in mixed CO2-H2O fluid was determined over the range in xCO2 from 1.0 to about 0.2 at 700 C, 100 MPa, with selected experiments conducted at pressures to 250 MPa and temperatures of 600 and 800 C. The diffusivity of C, DC, varies little with xCO2, although there is some evidence for a slight increase in DC from 5 10 18 to 5 10 17 cm2/s with decreasing xCO2. Our data and those of others are consistent with a model for DC 1/fCO2. Despite the large uncertainty, we observed that the diffusivity of O, DO, increases from 2 10 16 to 5 10 14 cm2/s with xCO2 decreasing from 1.0 to 0. There is a good correlation at 700 C between log DO and log fH2O regardless of the total pressure, matching the observations of previous workers. The data are consistent with a simple two-component model for the diffusion of O in calcite, one component for diffusion in the presence of CO2 and one in the presence of H2O: DO = DOCO2 + DOH2O aH2O. The activity of H2O is relative to the fugacity at 100 MPa, 700 C. DOCO2 is 3.45 10 16, and DOH2O is 3.8 10 14 cm2/s. The data indicate that the rate of diffusion of C and O in calcite is controlled by reactions at the surface of calcite. Adsorption of H2O and the creation of vacancies at the surface account for the dependence of the diffusivity on the fugacity of the fluid components. There is little evidence that H itself diffuses into calcite. With this model and the values of DO in pure CO2 (Labotka et al. 2000) and in pure H2O (Farver 1994), the value of DO is predicted over the temperature range 600 800 C and pH2O up to 300 MPa, the range of the data. Calculated closure temperatures for diffusive exchange of O between calcite and fluid are reduced by about 150 C in the presence of an aqueous fluid.

  2. I + (H2O)2 → HI + (H2O)OH Forward and Reverse Reactions. CCSD(T) Studies Including Spin-Orbit Coupling.

    PubMed

    Wang, Hui; Li, Guoliang; Li, Qian-Shu; Xie, Yaoming; Schaefer, Henry F

    2016-03-01

    The potential energy profile for the atomic iodine plus water dimer reaction I + (H2O)2 → HI + (H2O)OH has been explored using the "Gold Standard" CCSD(T) method with quadruple-ζ correlation-consistent basis sets. The corresponding information for the reverse reaction HI + (H2O)OH → I + (H2O)2 is also derived. Both zero-point vibrational energies (ZPVEs) and spin-orbit (SO) coupling are considered, and these notably alter the classical energetics. On the basis of the CCSD(T)/cc-pVQZ-PP results, including ZPVE and SO coupling, the forward reaction is found to be endothermic by 47.4 kcal/mol, implying a significant exothermicity for the reverse reaction. The entrance complex I···(H2O)2 is bound by 1.8 kcal/mol, and this dissociation energy is significantly affected by SO coupling. The reaction barrier lies 45.1 kcal/mol higher than the reactants. The exit complex HI···(H2O)OH is bound by 3.0 kcal/mol relative to the asymptotic limit. At every level of theory, the reverse reaction HI + (H2O)OH → I + (H2O)2 proceeds without a barrier. Compared with the analogous water monomer reaction I + H2O → HI + OH, the additional water molecule reduces the relative energies of the entrance stationary point, transition state, and exit complex by 3-5 kcal/mol. The I + (H2O)2 reaction is related to the valence isoelectronic bromine and chlorine reactions but is distinctly different from the F + (H2O)2 system. PMID:26562487

  3. The distribution of H2O between silicate melt and nominally anhydrous peridotite and the onset of hydrous melting in the deep upper mantle

    NASA Astrophysics Data System (ADS)

    Novella, Davide; Frost, Daniel J.; Hauri, Erik H.; Bureau, Helene; Raepsaet, Caroline; Roberge, Mathilde

    2014-08-01

    The partitioning of H2O between a mantle peridotite assemblage and low degree hydrous melt has been investigated at 6 GPa (corresponding to ∼180 km depth) at a temperature of 1400 °C. Peridotite mineral phases were analysed from 6 melting experiments performed in a natural chemical system. The experiments contained ∼80 wt% of a low degree hydrous melt that was obtained through a series of experiments where the melt composition was iteratively adjusted until saturation with the appropriate peridotite assemblage was achieved. The melt is fluid-undersaturated at the conditions of the experiment. Ion microprobe measurements of the mineral phases indicate olivine H2O concentrations of 434±61 ppm wt and average clinopyroxene (cpx) concentrations of 1268±173 ppm wt H2O. Orthopyroxene (opx) and garnet contain 700±46 ppm wt and 347±83 ppm wt H2O, respectively. The H2O content of the hydrous melts was determined by mass balance to be 11±0.5 wt% H2O. H2O partition coefficients between minerals and melt (DH2Omin/melt=XH2Omin/XH2Omelt) are 0.0040±0.0006 for olivine, 0.0064±0.0004 for opx, 0.0115±0.0016 for cpx and 0.0032±0.0008 for garnet. Using the determined H2O partition coefficients the onset and extent of melting at conditions equivalent to 180 km below mid-ocean ridges was determined as a function of mantle H2O content. Current estimates for the H2O content of the depleted mantle (50-200 ppm wt H2O) are insufficient to induce mantle melting at this depth, which requires ∼700 ppm wt H2O to produce 0.1% melting and 1600 ppm wt H2O for 1% melting, along an adiabat with a potential temperature of 1327 °C. Melting can occur at these conditions within the mantle source of ocean island basalts, which are estimated to contain up to 900 ppm wt H2O. If adiabatic temperatures are 200 °C higher within such plume related sources, then melt fractions of over 1% can be reached at 180 km depth. In addition, a model for the distribution of H2O between peridotite mineral

  4. Probing active galactic nuclei with H2O megamasers.

    PubMed Central

    Moran, J; Greenhill, L; Herrnstein, J; Diamond, P; Miyoshi, M; Nakai, N; Inque, M

    1995-01-01

    the disk must be <1000 K and the toroidal magnetic field component must be <250 mG. If the molecular mass density in the disk is 10(10) cm-3, then the disk mass is approximately 10(4) M[symbol: see text], and the disk is marginally stable as defined by the Toomre stability parameter Q (Q = 6 at the inner edge and 1 at the outer edge). The inward drift velocity is predicted to be <0.007 km.s-1, for a viscosity parameter of 0.1, and the accretion rate is <7 x 10(-5) M[symbol: see text].yr-1. At this value the accretion would be sufficient to power the nuclear x-ray source of 4 x 10(40) ergs-1 (1 erg = 0.1 microJ). The volume of individual maser components may be as large as 10(46) cm3, based on the velocity gradients, which is sufficient to supply the observed luminosity. The pump power undoubtedly comes from the nucleus, perhaps in the form of x-rays. The warp may allow the pump radiation to penetrate the disk obliquely [Neufeld, D. A. & Maloney, P. R. (1995) Astrophys. J. Lett. 447, L17-L19]. A total of 15 H2O megamasers have been identified out of >250 galaxies searched. Galaxy NGC4258 may be the only case where conditions are optimal to reveal a well-defined nuclear disk. Future measurement of proper motions and accelerations for NGC4258 will yield an accurate distance and a more precise definition of the dynamics of the disk Images Fig. 6 PMID:11607612

  5. Atmospheric lidar research applying to H2O, O2 and aerosols

    NASA Technical Reports Server (NTRS)

    Mcilrath, T. J.; Wilkerson, T. D.

    1977-01-01

    Experimental research on a near infrared tunable dye laser was reported, and theoretical simulations were presented for various lidar configurations. The visible and nearinfrared wavelengths considered were suitable for observations of aerosols, water vapor, molecular oxygen pressure and temperature in the troposphere and above. The first phase of development work was described on a ruby pumped, tunable dye laser for the wavelength region 715 to 740 nanometers. Lidar simulations were summarized for measurements of H2O and for two color lidar observations of aerosols in the atmosphere.

  6. Carbonate-H2O2 Leaching for Sequestering Uranium from Seawater

    SciTech Connect

    Pan, Horng-Bin; Weisheng, Liao; Wai, Chien; Oyola, Yatsandra; Janke, Christopher James; Tian, Guoxin; Rao, Linfeng

    2014-01-01

    Uranium adsorbed on amidoxime-based polyethylene fiber in simulated seawater can be quantitatively eluted at room temperature using 1M Na2CO3 containing 0.1 M H2O2. This efficient elution process is probably due to formation of an extremely stable uranyl-peroxo-carbonato complex in the carbonate solution. After washing with water, the sorbent can be reused with little loss of uranium loading capacity. Possible existence of this stable uranyl species in ocean water is also discussed.

  7. Atmospheric pressure plasma jet utilizing Ar and Ar/H2O mixtures and its applications to bacteria inactivation

    NASA Astrophysics Data System (ADS)

    Cheng, Cheng; Shen, Jie; Xiao, De-Zhi; Xie, Hong-Bing; Lan, Yan; Fang, Shi-Dong; Meng, Yue-Dong; Chu, Paul K.

    2014-07-01

    An atmospheric pressure plasma jet generated with Ar with H2O vapor is characterized and applied to inactivation of Bacillus subtilis spores. The emission spectra obtained from Ar/H2O plasma shows a higher intensity of OH radicals compared to pure argon at a specified H2O concentration. The gas temperature is estimated by comparing the simulated spectra of the OH band with experimental spectra. The excitation electron temperature is determined from the Boltzmann's plots and Stark broadening of the hydrogen Balmer Hβ line is applied to measure the electron density. The gas temperature, excitation electron temperature, and electron density of the plasma jet decrease with the increase of water vapor concentration at a fixed input voltage. The bacteria inactivation rate increases with the increase of OH generation reaching a maximum reduction at 2.6% (v/v) water vapor. Our results also show that the OH radicals generated by the Ar/H2O plasma jet only makes a limited contribution to spore inactivation and the shape change of the spores before and after plasma irradiation is discussed.

  8. Simultaneous mapping of H 2O and H 2O 2 on Mars from infrared high-resolution imaging spectroscopy

    NASA Astrophysics Data System (ADS)

    Encrenaz, T.; Greathouse, T. K.; Richter, M. J.; Bézard, B.; Fouchet, T.; Lefèvre, F.; Montmessin, F.; Forget, F.; Lebonnois, S.; Atreya, S. K.

    2008-06-01

    New maps of martian water vapor and hydrogen peroxide have been obtained in November-December 2005, using the Texas Echelon Cross Echelle Spectrograph (TEXES) at the NASA Infra Red Telescope facility (IRTF) at Mauna Kea Observatory. The solar longitude L was 332° (end of southern summer). Data have been obtained at 1235-1243 cm -1, with a spectral resolution of 0.016 cm -1 ( R=8×10). The mean water vapor mixing ratio in the region [0°-55° S; 345°-45° W], at the evening limb, is 150±50 ppm (corresponding to a column density of 8.3±2.8 pr-μm). The mean water vapor abundance derived from our measurements is in global overall agreement with the TES and Mars Express results, as well as the GCM models, however its spatial distribution looks different from the GCM predictions, with evidence for an enhancement at low latitudes toward the evening side. The inferred mean H 2O 2 abundance is 15±10 ppb, which is significantly lower than the June 2003 result [Encrenaz, T., Bézard, B., Greathouse, T.K., Richter, M.J., Lacy, J.H., Atreya, S.K., Wong, A.S., Lebonnois, S., Lefèvre, F., Forget, F., 2004. Icarus 170, 424-429] and lower than expected from the photochemical models, taking in account the change in season. Its spatial distribution shows some similarities with the map predicted by the GCM but the discrepancy in the H 2O 2 abundance remains to be understood and modeled.

  9. Solid organic residues produced by irradiation of hydrocarbon-containing H2O and H2O/NH3 ices - Infrared spectroscopy and astronomical implications

    NASA Technical Reports Server (NTRS)

    Khare, B. N.; Thompson, W. R.; Murray, B. G. J. P. T.; Chyba, C. F.; Sagan, C.

    1989-01-01

    Plasma-discharge irradiations were conducted for the methane clathrate expected in outer solar system satellites and cometary nuclei; also irradiated were ices prepared from other combinations of H2O with CH4, C2H6, or C2H2. Upon evaporation of the yellowish-to-tan irradiated ices, it is found that a colored solid film adheres to the walls of the reaction vessel at room temperature. These organic films are found to exhibit IR band identifiable with alkane, aldehide, alcohol, and perhaps alkene, as well as substituted aromatic functional groups. These spectra are compared with previous studies of UV- or photon-irradiated nonclathrated hydrocarbon-containing ices.

  10. Far-infrared CO and H2O emission in intermediate-mass protostars

    NASA Astrophysics Data System (ADS)

    Matuszak, M.; Karska, A.; Kristensen, L. E.; Herczeg, G. J.; Tychoniec, Ł.; van Kempen, T. A.; Fuente, A.

    2015-06-01

    Context. Intermediate-mass young stellar objects (YSOs) provide a link to understanding how feedback from shocks and UV radiation scales from low- to high-mass star forming regions. Aims: Our aim is to analyze excitation of CO and H2O in deeply embedded intermediate-mass YSOs and compare it with similar studies on low-mass and high-mass YSOs. Methods: Herschel/PACS spectral maps are analyzed for six YSOs with bolometric luminosities of Lbol ~ 102-103L⊙. The maps cover spatial scales of ~104 AU in several CO and H2O lines located in the ~55-210 μm range. Results: Rotational diagrams of CO show two temperature components at Trot ~ 320 K and Trot ~ 700-800 K, comparable to low- and high-mass protostars probed at similar spatial scales. The diagrams for H2O show a single component at Trot ~ 130 K, as seen in low-mass protostars, and about 100 K lower than in high-mass protostars. Since the uncertainties in Trot are on the same order as the difference between the intermediate and high-mass protostars, we cannot conclude whether the change in rotational temperature occurs at a specific luminosity or whether the change is more gradual from low- to high-mass YSOs. Conclusions: Molecular excitation in intermediate-mass protostars is comparable to the central 103 AU of low-mass protostars and consistent within the uncertainties with the high-mass protostars probed at 3 × 103 AU scales, suggesting similar shock conditions in all those sources. Appendix A is available in electronic form at http://www.aanda.org

  11. Self-sufficing H2O2-responsive nanocarriers through tumor-specific H2O2 production for synergistic oxidation-chemotherapy.

    PubMed

    Li, Junjie; Ke, Wendong; Wang, Lei; Huang, Mingming; Yin, Wei; Zhang, Ping; Chen, Qixian; Ge, Zhishen

    2016-03-10

    One of distinct features in tumor tissues is the elevated concentration of reactive oxygen species (ROS) during tumor immortality, proliferation and metastasis. However, ROS-responsive materials are rarely utilized in the field of in vivo tumoral ROS-responsive applications due to the fact that the intrinsic ROS level in the tumors could not escalate to an adequate level that the developed materials can possibly respond. Herein, palmitoyl ascorbate (PA) as a prooxidant for hydrogen peroxide (H2O2) production in tumor tissue is strategically compiled into a H2O2-responsive camptothecin (CPT) polymer prodrug micelle, which endowed the nanocarriers with self-sufficing H2O2 stimuli in tumor tissues. Molecular oncology manifests the hallmarks of tumoral physiology with deteriorating propensity in eliminating hazardous ROS. H2O2 production was demonstrated to specifically sustain in tumors, which not only induced tumor cell apoptosis by elevated oxidation stress but also served as autochthonous H2O2 resource to trigger CPT release for chemotherapy. Excess H2O2 and released CPT could penetrate into cells efficiently, which showed synergistic cytotoxicity toward cancer cells. Systemic therapeutic trial revealed potent tumor suppression of the proposed formulation via synergistic oxidation-chemotherapy. This report represents a novel nanomedicine platform combining up-regulation of tumoral H2O2 level and self-sufficing H2O2-responsive drug release to achieve novel synergistic oxidation-chemotherapy. PMID:26806789

  12. Forsterite solubility in NaCl-H2O fluids at upper mantle P-T conditions

    NASA Astrophysics Data System (ADS)

    Wykes, J. L.; Newton, R. C.; Manning, C. E.

    2011-12-01

    Portions of the mantle wedge in subduction zones may be metasomatized by aqueous fluids. Olivine is the most abundant mineral in the upper mantle, so an understanding of its solubility in aqueous fluids is a necessary foundation for understanding metasomatic processes in the mantle wedge. We determined the solubility of forsterite in H2O and H2O-NaCl fluids at 1.0 GPa and 800-900°C, using a hydrothermal piston-cylinder and weight loss methods. Experiments consisted of a single synthetic forsterite crystal sealed in Pt tubing with H2O or H2O and NaCl. Run durations were at least 48 hrs at 800°C and 23 hours at 900°C. At 800°C, forsterite dissolution was very slightly incongruent, yielding minor brucite + fluid; forsterite solubility was congruent at 900°C where brucite is unstable. We observe low solubility of forsterite in pure H2O at 800°C and 1.0 GPa of 0.0034(1) molal (m). This is approximately three times greater than the solubility of corundum and 370 times less than that of quartz at equivalent conditions. The SiO2 concentration in H2O in equilibrium with forsterite-enstatite at 800°C, 1.0 GPa is 0.297(2) molal, ~87 times greater than that in equilibrium with forsterite alone; at 900°C, 1.0 GPa a forsterite-enstatite assemblage yields mSiO2 ~111 times greater than forsterite. In NaCl-H2O solutions, forsterite solubility was congruent and increased with NaCl mole fraction over the range of fluid compositions investigated, with a solubility of mfo = 0.042(1) at XNaCl = 0.471 (74.2 wt% NaCl) and 800°C-a 12-fold increase in solubility. At 900°C, forsterite solubility increases to mfo = 0.090(1) at XNaCl = 0.450 (72.4 wt% NaCl), an increase of 7 times relative to the pure H2O solubility. At both temperatures, the relative increase in solubility compared to that in pure H2O (X/X0) is concave downwards as a function of XNaCl in the fluid, with a steep increase at low XNaCl and a maximum at XNaCl~0.3. The concave downwards form is a result of the interplay

  13. H2O2 levels in rainwater collected in south Florida and the Bahama Islands

    NASA Technical Reports Server (NTRS)

    Zika, R.; Saltzman, E.; Chameides, W. L.; Davis, D. D.

    1982-01-01

    Measurements of H2O2 in rainwater collected in Miami, Florida, and the Bahama Islands area indicate the presence of H2O2 concentration levels ranging from 100,000 to 700,000 M. No systematic trends in H2O2 concentration were observed during an individual storm, in marked contrast to the behavior of other anions for example, NO3(-), SO4(-2), and Cl(-). The data suggest that a substantial fraction of the H2O2 found in precipitation is generated by aqueous-phase reactions within the cloudwater rather than via rainout and washout of gaseous H2O2.

  14. Increasing the ordering temperatures in oxalate-based 3D chiral magnets: the series [Ir(ppy)2(bpy)][M(II)M(III)(ox)3] x 0.5 H2O (M(II)M(III) = MnCr, FeCr, CoCr, NiCr, ZnCr, MnFe, FeFe); bpy = 2,2'-bipyridine; ppy = 2-phenylpyridine; ox = oxalate dianion).

    PubMed

    Clemente-León, Miguel; Coronado, Eugenio; Gómez-García, Carlos J; Soriano-Portillo, Alejandra

    2006-07-10

    The synthesis, structure, and physical properties of a novel series of oxalate-based bimetallic magnets obtained by using the Ir(ppy)2(bpy)]+ cation as a template of the bimetallic [M(II)M(III)(ox)3]- network are reported. The compounds can be formulated as [Ir(ppy)2(bpy)][M(II)Cr(III)(ox)3] x 0.5 H2O (M(II) = Ni, Mn, Co, Fe, and Zn) and [Ir(ppy)2(bpy)]-[M(II)Fe(III)(ox)3] x 0.5 H2O (M(II) = Fe, Mn) and crystallize in the chiral cubic space group P4(1)32 or P4(3)32. They show the well-known 3D chiral structure formed by M(II) and M(III) ions connected through oxalate anions with [Ir(ppy)2(bpy)]+ cations and water molecules in the holes left by the oxalate network. The M(II)Cr(III) compounds behave as soft ferromagnets with ordering temperatures up to 13 K, while the Mn(II)Fe(III) and Fe(II)Fe(III) compounds behave as a weak ferromagnet and a ferrimagnet, respectively, with ordering temperatures of 31 and 28 K. These values represent the highest ordering temperatures so far reported in the family of 3D chiral magnets based on bimetallic oxalate complexes. PMID:16813431

  15. Formation of Submicron Magnesite during Reaction of Natural Forsterite in H2O-Saturated Supercritical CO2

    SciTech Connect

    Qafoku, Odeta; Hu, Jian Z.; Hess, Nancy J.; Hu, Mary Y.; Ilton, Eugene S.; Feng, Ju; Arey, Bruce W.; Felmy, Andrew R.

    2014-06-01

    Natural forsterite was reacted in a) liquid water saturated with supercritical CO2 (scCO2) and in b) H2O-saturated scCO2 at 35-80 °C and 90 atm. The solid reaction products were analyzed with nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), and confocal Raman spectroscopy. Two carbonate phases, nesquehonite (MgCO3.3H2O) and magnesite (MgCO3), were identified with the proportions of the two phases depending on experimental conditions. In water saturated with scCO2, nesquehonite was the dominant carbonate phase at 35-80 °C with only a limited number of large, micron size magnesite particles forming at the highest temperature, 80 °C. In contrast, in H2O-saturated scCO2 magnesite formation was identified at all three temperatures: 35 °, 50 °, and 80 °C. Magnesite was the dominant carbonation reaction product at 50 ° and 80 °C; but nesquehonite was dominant at 35 °C. The magnesite particles formed under H2O-saturated scCO2 conditions exhibited an extremely uniform submicron grain-size and nearly identical rhombohedral morphologies at all temperatures. The distribution and form of the particles were not consistent with epitaxial nucleation and growth on the forsterite surface.

  16. OH and H2O on Vesta and on the Moon: A comparative analysis

    NASA Astrophysics Data System (ADS)

    Combe, J.; McCord, T. B.; De Sanctis, M.; Ammannito, E.; Hayne, P. O.; Bandfield, J. L.; Pieters, C. M.; Palomba, E.; Longobardo, A.; Prettyman, T. H.; Marchi, S.; Capaccioni, F.; Capria, M.; Mittlefehldt, D. W.; Sunshine, J. M.; Tosi, F.; Turrini, D.; Zambon, F.; Raymond, C. A.; Russell, C. T.

    2012-12-01

    Searching for OH and H2O on Vesta and on the Moon is key [1] because the presence of these molecules at the surface of objects in the inner solar system is fundamental for understanding the formation of water in the early history of the solar system, as well as its implications on the mineralogical, thermodynamical, and geological evolution of the planets [2, 3]. Vesta is mineralogically differentiated, more evolved than most of the asteroids, but not as much as a planet [4, 5]. The surface of Vesta shows very strong pyroxene absorption bands in reflectance spectra [6 - 8], and the howardite, eucrite, diogenite (HED) meteorites that are of Vestan origin are also pyroxene-rich [9 - 13], which strongly suggests that the surface of Vesta is mostly made of basalt. This basaltic-rich surface composition of Vesta is one similarity with the surface of the Moon, where OH and H2O have been detected by imaging spectroscopy in the near-infrared [14 - 16]. On Vesta, the possible origins for OH and H2O are the same as what has been suggested for the Moon [17]: 1) indigenous to the object, 2) in-fall of hydrated exogenous material, and 3) implantation of solar wind protons. The objective of this study is to derive abundance estimates for OH and H2O at the surface of Vesta, and to compare them with abundances found on the Moon. The analysis of OH and H2O at the surface of Vesta is done with the Visible and Infrared mapping spectrometer (VIR) [18] onboard the Dawn orbiter using reflectance spectra between 0.25 and 5.1 μm. We are also analyzing again data from the Moon Mineralogy Mapper (M3) a thermal emission correction based on modeling of brightness temperature as function of the surface roughness [19]. VIR has detected an absorption band at 2.8 μm, attributed to OH [11, 12, 13], in coherent spatial units that have been observed multiple times. Associations with surface morphological features are complex. No correlation with temperature or with illumination suggests that the

  17. H2O-CO2-S fluid triggering the 1991 Mount Pinatubo climactic eruption (Philippines)

    NASA Astrophysics Data System (ADS)

    Borisova, Anastassia Y.; Toutain, Jean-Paul; Dubessy, Jean; Pallister, John; Zwick, Antoine; Salvi, Stefano

    2014-02-01

    The factors that trigger explosive eruptions often remain elusive because of the lack of direct data from representative samples. Here, we report the first micro-Raman spectroscopy measurements of fluid and multiphase inclusions trapped in quartz xenocrysts and microlites from andesitic lavas and basaltic enclaves of the 1991 Mount Pinatubo eruption. Our analyses reveal two-phase H2O-CO2-S inclusions containing a CO2-dominated phase and an aqueous sulfate-bearing liquid phase and, less commonly, anhydrite (CaSO4(solid)). The two fluid phases are low-temperature products of a supercritical H2O-CO2-S fluid which was associated with a hydrous silicate melt prior to eruption. The average density of the CO2 phase is 0.4 ± 0.2 g/cm3 at room temperature, corresponding to a supercritical fluid density of 0.6 ± 0.1 g/cm3 at the conditions of entrapment at 760-1000 °C and up to ˜260 MPa. For the first time, a dense CO2-bearing fluid is reported in Mount Pinatubo volcanic samples. We suggest that this hybrid H2O-CO2-S fluid originated from mixing between sulfur-rich basaltic and hydrous dacitic magmas, as the former was intruded into and interacted with the pre-eruptive Mount Pinatubo dacite magma reservoir, at depths of at least 10 km. Thermodynamic modeling demonstrates that part of the SO2 liberated from the intruded basaltic magma was consumed via interaction with the aqueous fluid-saturated dacitic magma according to the reaction 4SO2 basalt + 4H2Odacite = 3HSO4 - + H2S + 3H+, yielding early Cu-rich sulfides, late abundant anhydrite, and SO4-rich apatites, which are commonly found in the Mount Pinatubo dacites. We suggest that this hybrid H2O-CO2-S fluid played an important role in triggering the 1991 climactic eruption.

  18. Transit of H2O2 across the endoplasmic reticulum membrane is not sluggish.

    PubMed

    Appenzeller-Herzog, Christian; Bánhegyi, Gabor; Bogeski, Ivan; Davies, Kelvin J A; Delaunay-Moisan, Agnès; Forman, Henry Jay; Görlach, Agnes; Kietzmann, Thomas; Laurindo, Francisco; Margittai, Eva; Meyer, Andreas J; Riemer, Jan; Rützler, Michael; Simmen, Thomas; Sitia, Roberto; Toledano, Michel B; Touw, Ivo P

    2016-05-01

    Cellular metabolism provides various sources of hydrogen peroxide (H2O2) in different organelles and compartments. The suitability of H2O2 as an intracellular signaling molecule therefore also depends on its ability to pass cellular membranes. The propensity of the membranous boundary of the endoplasmic reticulum (ER) to let pass H2O2 has been discussed controversially. In this essay, we challenge the recent proposal that the ER membrane constitutes a simple barrier for H2O2 diffusion and support earlier data showing that (i) ample H2O2 permeability of the ER membrane is a prerequisite for signal transduction, (ii) aquaporin channels are crucially involved in the facilitation of H2O2 permeation, and (iii) a proper experimental framework not prone to artifacts is necessary to further unravel the role of H2O2 permeation in signal transduction and organelle biology. PMID:26928585

  19. Distance-dependent radiation chemistry: Oxidation versus hydrogenation of CO in electron-irradiated H2O/CO/H2O ices

    SciTech Connect

    Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven; Kimmel, Gregory A.

    2014-11-26

    Electron-stimulated oxidation of CO in layered H2O/CO/H2O ices was investigated with infrared reflection-absorption spectroscopy (IRAS) as function of the distance of the CO layer from the water/vacuum interface. The results show that while both oxidation and reduction reactions occur within the irradiated water films, there are distinct regions where either oxidation or reduction reactions are dominant. At depths less than ~ 15 ML, CO oxidation dominates over the sequential hydrogenation of CO to methanol (CH3OH), and CO2 is the major product of CO oxidation, consistent with previous observations. At its highest yield, CO2 accounts for ~45% of all the reacted CO. Another oxidation product is identified as the formate anion (HCO2-). In contrast, for CO buried more than ~ 35 ML below the water/vacuum interface, the CO-to-methanol conversion efficiency is close to 100%. Production of CO2 and formate are not observed for the more deeply buried CO layers, where hydrogenation dominates. Experiments with CO dosed on pre-irradiated ASW samples suggest that OH radicals are primarily responsible for the oxidation reactions. Possible mechanisms of CO oxidation, involving primary and secondary processes of water radiolysis at low temperature, are discussed. The observed distance-dependent radiation chemistry results from the higher mobility of hydrogen atoms that are created by the interaction of the 100 eV electrons with the water films. These hydrogen atoms, which are primarily created at or near the water/vacuum interface, can desorb from or diffuse into the water films, while the less-mobile OH radicals remain in the near-surface zone resulting in preferential oxidation reactions there. The diffusing hydrogen atoms are responsible for the hydrogenation reactions that are dominant for the more deeply buried CO layers.

  20. The H_2O and O_2 exospheres of Jupiter's moon Ganymede.

    NASA Astrophysics Data System (ADS)

    Plainaki, C.; Milillo, A.; Massetti, S.; Mura, A.; Jia, X.; Orsini, S.; Mangano, V.; De Angelis, E.; Lazzarotto, F.; Rispoli, R.

    A simulation of the H_2O and O_2 exospheres of Jupiter' moon Ganymede, through the application of a 3D Monte Carlo modeling technique, is presented. Our model takes into consideration the combined effect on the exosphere generation of the main surface release processes (i.e. sputtering, sublimation and radiolysis) and the surface precipitation of the energetic ions of Jupiter's magnetosphere constrained strongly by Ganymede's intrinsic magnetic field. In order to model the magnetospheric ion precipitation to Ganymede's surface, we used as an input the electric and magnetic fields from the global MHD model of Ganymede's magnetosphere (Jia et al., 2009). The exospheric model described in this paper is based on EGEON, a single-particle Monte Carlo model already applied for a Galilean satellite \\citep{PC10,PC12,PC13}. We find that at small altitudes above the moon.s subsolar point the main contribution to the neutral environment comes from sublimated H_2O whereas the spatial distribution of the directly sputtered-H_2O molecules exhibits a close correspondence with the plasma precipitation region and extends at high altitudes, being, therefore, well differentiated from the sublimated water. Moreover, we find that the O_2 exosphere comprises two different regions: the first one is an homogeneous, relatively dense, thermal-O_2 region extending to some 100s of km above the surface, whereas the second one is less homogeneous and consists of more energetic O_2 molecules sputtered directly from the surface after water-dissociation by ions has taken place; the spatial distribution of the energetic surface-released O_2 molecules depends both on the impacting plasma properties and the moon's surface temperature distribution.

  1. Metabolic control of resistance of human epithelial cells to H2O2 and NO stresses.

    PubMed Central

    Le Goffe, Claire; Vallette, Geneviève; Charrier, Laetitia; Candelon, Thierry; Bou-Hanna, Chantal; Bouhours, Jean-François; Laboisse, Christian L

    2002-01-01

    The carbon flux through the oxidative branch of the pentose phosphate pathway (PPP) can be viewed as an integrator of the antioxidant mechanisms via the generation of NADPH. It could therefore be used as a control point of the cellular response to an oxidative stress. Replacement of glucose by galactose sensitized the human epithelial cell line HGT-1 to H2O2 stress. Here we demonstrate that, due to the restricted galactose flux into the PPP, the H2O2 stress led to early cellular blebbing followed by cell necrosis, these changes being associated with a fall in the NADPH/NADP+ ratio and GSH depletion. H2O2 cytotoxicity was prevented by adding 2-deoxyglucose (2dGlc). This protection was associated with an increased flow of 2-deoxyglucose 6-phosphate into the oxidative branch of the PPP together with the prevention of the NADPH/NADP+ fall and the maintenance of intracellular GSH redox homoeostasis. Inhibitors of enzyme pathways connecting the PPP to GSH recycling abolished the 2dGlc protection. In carbohydrate-free culture conditions, 2dGlc dose-dependent protective effect was paralleled by a dose-dependent influx of 2dGlc into the PPP leading to the maintenance of the intracellular redox status. By contrast, in Glc-fed cells, the PPP was not a control point of the cellular resistance to H2O2 stress as they maintained a high NADPH/NADP+ ratio. Both 2dGlc and Glc inhibited, through the maintenance of GSH redox status, NO cytotoxicity on galactose-containing Dulbecco's modified Eagle's medium (Gal-DMEM)-fed cells. 2dGlc did not prevent the fall of ATP content in NO-treated Gal-DMEM-fed cells, indicating that NO cytotoxicity was essentially due to the disruption of GSH redox homoeostasis and not to the alteration of ATP production by the mitochondrial respiratory chain. The maintenance of ATP content in NO-treated glucose-fed cells was due to their ability to derive their energy from anaerobic glycolysis. In conclusion, Gal-DMEM and 2dGlc-supplemented Gal-DMEM provide a

  2. Removing polysaccharides-and saccharides-related coloring impurities in alkyl polyglycosides by bleaching with the H2O2/TAED/NaHCO3 system.

    PubMed

    Yanmei, Liu; Jinliang, Tao; Jiao, Sun; Wenyi, Chen

    2014-11-01

    The effect of H2O2/TAED/NaHCO3 system, namely NaHCO3 as alkaline agent with the (tetra acetyl ethylene diamine (TAED)) TAED-activated peroxide system, bleaching of alkyl polyglycosides solution was studied by spectrophotometry. The results showed that the optimal bleaching conditions about H2O2/TAED/NaHCO3 system bleaching of alkyl polyglycosides solution were as follows: molar ratio of TAED to H2O2 was 0.06, addition of H2O2 was 8.6%, addition of NaHCO3 was 3.2%, bleaching temperature of 50-65 °C, addition of MgO was 0.13%, and bleaching time was 8h. If too much amount of NaHCO3 was added to the system and maintained alkaline pH, the bleaching effect would be greatly reduced. Fixing molar ratio of TAED to H2O2 and increasing the amount of H2O2 were beneficial to improve the whiteness of alkyl polyglycosides, but adding too much amount of H2O2 would reduce the transparency. In the TAED-activated peroxide system, NaHCO3 as alkaline agent and buffer agent, could overcome the disadvantage of producing black precipitates when NaOH as alkaline agent. PMID:25129762

  3. Probing the status of felsic magma reservoirs: Constraints from the P-T-H2O dependences of electrical conductivity of rhyolitic melt

    NASA Astrophysics Data System (ADS)

    Guo, Xuan; Zhang, Li; Behrens, Harald; Ni, Huaiwei

    2016-01-01

    Electrical conductivity of rhyolitic melts, combined with magnetotelluric data, can provide important constraints for the physicochemical conditions of active felsic magma reservoirs. Previous experimental investigations are limited to low H2O concentration (<3 wt% H2O) and low pressure (<0.2 GPa for hydrous melts). We here report new results from electrical conductivity measurements of peralkaline rhyolitic melts with 4.7 wt% Na2O and 0.1-7.9 wt% H2O at 868-1665 K and 0.5-1.0 GPa in piston cylinder apparatuses using sweeping-frequency impedance analyses. Logarithmic electrical conductivity (σ) is found to correlate linearly with H2O concentration and reciprocal temperature, and the influence of H2O has been considerably underestimated by previous work. The negative pressure effect on electrical conductivity appears to attenuate with increasing H2O concentration. Based on the new data, we develop the following electrical conductivity model for peralkaline rhyolitic melts under conditions up to 1665 K, 1.0 GPa, and 8 wt% H2O:

  4. Photoelectron spectroscopic study of the hydrated nucleoside anions: Uridine-(H2O)n=0-2, cytidine-(H2O)n=0-2, and thymidine-(H2O)n=0,1

    NASA Astrophysics Data System (ADS)

    Li, Xiang; Wang, Haopeng; Bowen, Kit H.

    2010-10-01

    The hydrated nucleoside anions, uridine-(H2O)n=0-2, cytidine-(H2O)n=0-2, and thymidine-(H2O)n=0,1, have been prepared in beams and studied by anion photoelectron spectroscopy in order to investigate the effects of a microhydrated environment on parent nucleoside anions. Vertical detachment energies (VDEs) were measured for all eight anions, and from these, estimates were made for five sequential anion hydration energies. Excellent agreement was found between our measured VDE value for thymidine-(H2O)1 and its calculated value in the companion article by S. Kim and H. F. Schaefer III.

  5. A thermodynamical model for the surface tension of silicate melts in contact with H2O gas

    USGS Publications Warehouse

    Colucci, Simone; Battaglia, Maurizio; Trigila, Raffaello

    2016-01-01

    Surface tension plays an important role in the nucleation of H2O gas bubbles in magmatic melts and in the time-dependent rheology of bubble-bearing magmas. Despite several experimental studies, a physics based model of the surface tension of magmatic melts in contact with H2O is lacking. This paper employs gradient theory to develop a thermodynamical model of equilibrium surface tension of silicate melts in contact with H2O gas at low to moderate pressures. In the last decades, this approach has been successfully applied in studies of industrial mixtures but never to magmatic systems. We calibrate and verify the model against literature experimental data, obtained by the pendant drop method, and by inverting bubble nucleation experiments using the Classical Nucleation Theory (CNT). Our model reproduces the systematic decrease in surface tension with increased H2O pressure observed in the experiments. On the other hand, the effect of temperature is confirmed by the experiments only at high pressure. At atmospheric pressure, the model shows a decrease of surface tension with temperature. This is in contrast with a number of experimental observations and could be related to microstructural effects that cannot be reproduced by our model. Finally, our analysis indicates that the surface tension measured inverting the CNT may be lower than the value measured by the pendant drop method, most likely because of changes in surface tension controlled by the supersaturation.

  6. Magnetic Phase Transition of the Mixed Antiferromagnets Ni1-xMxCl2·2H2O (M=Co, Mn)

    NASA Astrophysics Data System (ADS)

    Hamasaki, T.; Zenmyo, K.; Kubo, H.

    2012-12-01

    Mixed antiferromagnets Ni1-xMxCl2·2H2O (M=Co, Mn) were prepared. The crystal structure of NiCl2-2H2O is a little different from that of CoCl2·2H2O and MnCl2·2H2O. In order to examine how Co or Mn spins in NiCl2·2H2O crystal structure behave, we determined precisely the phase transition temperatures by measuring the specific heats and have obtained the concentration dependence of the phase transition temperature. Substitution of Co for Ni increases a little the transition temperature and contrary to this the substitution of Mn decreases the transition temperature rapidly. The results are discussed on the basis of molecular field theory. In the case of M=Co, the concentration dependence of the phase transition temperature is well explained by molecular field theory. But, in the case of M=Mn, the molecular field theory cannot explain it sufficiently. Thus Mn spins in NiCl2·2H2O crystal show the peculiar behavior. We suppose that this may be attributed to a kind of the instability of Mn spins.

  7. Possibility of H2O2 decomposition in thin liquid films on Mars

    NASA Astrophysics Data System (ADS)

    Kereszturi, Akos; Gobi, Sandor

    2014-11-01

    In this work the pathways and possibilities of H2O2 decomposition on Mars in microscopic liquid interfacial water were analyzed by kinetic calculations. Thermal and photochemical driven decomposition, just like processes catalyzed by various metal oxides, is too slow compared to the annual duration while such microscopic liquid layers exist on Mars today, to produce substantial decomposition. The most effective analyzed process is catalyzed by Fe ions, which could decompose H2O2 under pH<4.5 with a half life of 1-2 days. This process might be important during volcanically influenced periods when sulfur release produces acidic pH, and rotational axis tilt change driven climatic changes also influence the volatile circulation and spatial occurrence just like the duration of thin liquid layer. Under current conditions, using the value of 200 K as the temperature in interfacial water (at the southern hemisphere), and applying Phoenix lander's wet chemistry laboratory results, the pH is not favorable for Fe mobility and this kind of decomposition. Despite current conditions (especially pH) being unfavorable for H2O2 decomposition, microscopic scale interfacial liquid water still might support the process. By the reaction called heterogeneous catalysis, without acidic pH and mobile Fe, but with minerals surfaces containing Fe decomposition of H2O2 with half life of 20 days can happen. This duration is still longer but not several orders than the existence of springtime interfacial liquid water on Mars today. This estimation is relevant for activation energy controlled reaction rates. The other main parameter that may influence the reaction rate is the diffusion speed. Although the available tests and theoretical calculations do not provide firm values for the diffusion speed in such a “2-dimensional” environment, using relevant estimations this parameter in the interfacial liquid layer is smaller than in bulk water. But the 20 days' duration mentioned above is still

  8. The Elevation of Boiling Points in H_2O and D_2O Electrolytes

    NASA Astrophysics Data System (ADS)

    Miles, M. H.; Arman, H. D.; Carrick, J. D.; Gren, C. K.; Haggerty, K. A.; Kim, H. Y.; Ky, A. G.; Markham, J. E.; Meeks, C. F.; Noga, D. E.

    2002-03-01

    The excess enthalpy effect in cold fusion experiments for Pd/D_2O systems is subject to positive feedback, i.e., increasing the cell temperature increases the excess enthalpy . Therefore, the largest excess enthalpy effects are often observed near or at the boiling point corresponding to that of the electrolyte solution in the cell(M.H. Miles, M. Fleischmann and M.A. Imam, "Calorimetric Analysis of a Heavy Water Electrolysis Experiment Using a Pd-B Alloy Cathode", Naval Research Lab Mem. Rep.,#6320-01-8526, pp. 27-30 (2001).). However, the actual boiling point increases as the D_2O content of the cell decreases. The purpose of this project will be to compare experimental values of the change in temperature ΔT obtained using H_2O and D_2O solutions with theoretical values of ΔT calculated by assuming ideal solutions. The emphasis will be on higher concentrations as well as on saturated solutions where ΔT values may be quite large. Preliminary results for LiOH in H_2O show reasonable agreement with ideal solution ΔT values up to LiOH concentrations of 1.0 molal (m).

  9. A kinetic study of the reactions of Fe+ with N2O, N2, O2, CO2 and H2O, and the ligand-switching reactions Fe+.X + Y --> Fe+.Y + X (X = N2, O2, CO2; Y = O2, H2O).

    PubMed

    Vondrak, T; Woodcock, K R I; Plane, J M C

    2006-01-28

    A series of reactions involving Fe(+) ions were studied by the pulsed laser ablation of an iron target, with detection of ions by quadrupole mass spectrometry at the downstream end of a fast flow tube. The reactions of Fe(+) with N(2)O, N(2) and O(2) were studied in order to benchmark this new technique. Extending measurements of the rate coefficient for Fe(+) + N(2)O from 773 K to 185 K shows that the reaction exhibits marked non-Arrhenius behaviour, which appears to be explained by excitation of the N(2)O bending vibrational modes. The recombination of Fe(+) with CO(2) and H(2)O in He was then studied over a range of pressure and temperature. The data were fitted by RRKM theory combined with ab initio quantum calculations on Fe(+).CO(2) and Fe(+).H(2)O, yielding the following results (120-400 K and 0-10(3) Torr). For Fe(+) + CO(2): k(rec,0) = 1.0 x 10(-29) (T/300 K)(-2.31) cm(6) molecule(-2) s(-1); k(rec,infinity) = 8.1 x 10(-10) cm(3) molecule(-1) s(-1). For Fe(+) + H(2)O: k(rec,0) = 5.3 x 10(-29) (T/300 K)(-2.02) cm(6) molecule(-2) s(-1); k(rec,infinity) = 2.1 x 10(-9) (T/300 K)(-0.41) cm(3) molecule(-1) s(-1). The uncertainty in these rate coefficients is determined using a Monte Carlo procedure. A series of exothermic ligand-switching reactions were also studied at 294 K: k(Fe(+).N(2) + O(2)) = (3.17 +/- 0.41) x 10(-10), k(Fe(+).CO(2) + O(2)) = (2.16 +/- 0.35) x 10(-10), k(Fe(+).N(2) + H(2)O) = (1.25 +/- 0.14) x 10(-9) and k(Fe(+).O(2) + H(2)O) = (8.79 +/- 1.30) x 10(-10) cm(3) molecule(-1) s(-1), which are all between 36 and 52% of their theoretical upper limits calculated from long-range capture theory. Finally, the role of these reactions in the chemistry of meteor-ablated iron in the upper atmosphere is discussed. The removal rates of Fe(+) by N(2), O(2), CO(2) and H(2)O at 90 km altitude are approximately 0.1, 0.07, 3 x 10(-4) and 1 x 10(-6) s(-1), respectively. The initially formed Fe(+).N(2) and Fe(+).O(2) are converted into the H(2)O complex at

  10. On photochemical heating of cometary comae - The cases of H2O and CO-rich comets

    NASA Technical Reports Server (NTRS)

    Ip, W.-H.

    1983-01-01

    It is found that the effect of energy addition due to photochemical processes in the cometary coma on the heating and accelerating of the expanding neutral gas is limited by the kinematic property of the energy transfer from the energetic fragments to the bulk flow. The effective scale length of the photochemical zone for an H2O comet is estimated to be only 10% of the dimension of the collision region due to the large mass ratio of H atom and H2O molecule. When this physical property is taken into consideration, the H2O gas is found to be expanding at a highly supersonic speed. In addition, it is shown that the addition of a mixture of CO and/or CO2 molecules in a medium-bright comet with total production rate of 10 to the 29th molecules/s would not change this conclusion since the photodissiation length scales of these molecules are a factor of 10-30 larger than that of the H2O molecules. Thus, most of the CO and CO2 molecules will be dissociated outside of the collision zone without depositing the excess kinetic energy to the neutral atmosphere. However, if the gas production rate is controlled by CO or CO2, the dimension of the collision zone of a CO comet at 1 AU will be increased by a factor of seven. The photochemical heating due to CO dissociation would thus be more effective, causing the atmospheric flow to be weakly supersonic. It is concluded that the neutral gas outflows from H2O comets and CO comets could be substantially different.

  11. Ionic strength dependence of the oxidation of SO2 by H2O2 in sodium chloride particles

    NASA Astrophysics Data System (ADS)

    Ali, H. M.; Iedema, M.; Yu, X.-Y.; Cowin, J. P.

    2014-06-01

    The reaction of sulfur dioxide and hydrogen peroxide in the presence of deliquesced (>75% RH) sodium chloride (brine) particles was studied by utilizing a cross flow mini-reactor. The reaction kinetics were followed by observing chloride depletion in particles by computer-controlled scanning electron microscope with energy dispersive X-ray analysis, namely CCSEM/EDX. The reactions take place in concentrated mixed salt brine aerosols, for which no complete kinetic equilibrium data previously existed. We measured the Henry's law solubility of H2O2 in brine solutions to close that gap. We also calculated the reaction rate as the particle transforms continuously from concentrated NaCl brine to, eventually, a mixed NaHSO4 plus H2SO4 brine solution. The reaction rate of the SO2 oxidation by H2O2 was found to be influenced by the change in ionic strength as the particle undergoes compositional transformation, following closely the dependence of the third order rate constant on ionic strength as predicted using established rate equations. This is the first study that has measured the ionic strength dependence of sulfate formation (in non-aqueous media) from oxidation of mixed salt brine aerosols in the presence of H2O2. It also gives the first report of the dependence of the Henry's law constant of H2O2 on ionic strength.

  12. Role of peroxiredoxin 2 in H2O2‑induced oxidative stress of primary Leydig cells.

    PubMed

    Duan, Ting; Fan, Kai; Chen, Shengrong; Yao, Qi; Zeng, Rong; Hong, Zhiwei; Peng, Longping; Shao, Yong; Yao, Bing

    2016-06-01

    Late‑onset hypogonadism is defined as a condition caused by a decline in the levels of testosterone with aging. One of the major factors contributing to the low levels of testosterone is the accumulation of reactive oxygen species (ROS) in Leydig cells during the ageing process. Peroxiredoxin 2 (Prdx2), a member of the peroxiredoxin family, is an antioxidant protein, the predominant function of which is to neutralize ROS. However, its role in Leydig cells remains to be elucidated. In the present study, primary Leydig cells were exposed to low concentrations of hydrogen peroxide (H2O2) to induce oxidative stress. Cell apoptosis was measured using an Annexin V fluorescein isothiocyanate/propidium iodide apoptosis detection kit and flow cytometry. The level of testosterone was determined by radioimmunoassay, and the mRNA and protein expression levels of Prdx2 were detected by reverse transcription‑polymerase chain reaction and western blotting, respectively. The results revealed a significant increase in cell apoptosis and decrease in testosterone production. In addition, the expression of Prdx2 was decreased by H2O2 in a dose‑ and time‑dependent manner, and this decrease may have been caused by the induction of its molecular structure transformation due to H2O2 elimination. The above findings indicated that Prdx2 may prevent H2O2 accumulation in Leydig cells, and may be important in oxidative stress‑induced apoptosis and decreased testosterone production. PMID:27082744

  13. Seasonal change in CO2 and H2O exchange between grassland and atmosphere

    NASA Astrophysics Data System (ADS)

    Saigusa, N.; Liu, S.; Oikawa, T.; Watanabe, T.

    1996-03-01

    The seasonal change in CO2 flux over an artificial grassland was analyzed from the ecological and meteorological point of view. This grassland contains C3 and C4 plants; the three dominant species belonging to the Gramineae; Festuca elatior (C3) dominated in early spring, and Imperata cylindrica (C4) and Andropogon virginicus (C4) grew during early summer and became dominant in mid-summer. CO2 flux was measured by the gradient method, and the routinely observed data for the surface-heat budget were used to analyze the CO2 and H2O exchange between the grassland and atmosphere. From August to October in 1993, CO2 flux was reduced to around half under the same solar-radiation conditions, while H2O flux decreased 20% during the same period. The monthly values of water use efficiency, i.e., ratio of CO2 flux to H2O flux decreased from 5.8 to 3.3 mg CO2/g H2O from August to October, the Bowen ratio increased from 0.20 to 0.30, and the ratio of the bulk latent heat transfer coefficient CE to the sensible heat transfer coefficient CH was maintained around 0.40-0.50. The increase in the Bowen ratio was explained by the decrease in air temperature from 22.3 °C in August to 16.6 °C in October without considering biological effects such as stomatal closure on the individual leaves. The nearly constant CE/CH ratios suggested that the contribution ratio of canopy resistance to aerodynamic resistance did not change markedly, although the meteorological conditions changed seasonally. The decrease in the water use efficiency, however, suggested that the photosynthetic rate decreased for individual leaves from August to October under the same radiation conditions. Diurnal variations of CO2 exchange were simulated by the multi-layer canopy model taking into account the differences in the stomatal conductance and photosynthetic pathway between C3 and C4 plants. The results suggested that C4 plants played a major role in the CO2 exchange in August, the contribution of C4 plants

  14. Intrinsic peroxidase-like catalytic activity of nitrogen-doped graphene quantum dots and their application in the colorimetric detection of H2O2 and glucose.

    PubMed

    Lin, Liping; Song, Xinhong; Chen, Yiying; Rong, Mingcong; Zhao, Tingting; Wang, Yiru; Jiang, Yaqi; Chen, Xi

    2015-04-15

    In this paper, the highly intrinsic peroxidase-like catalytic activity of nitrogen-doped graphene quantum dots (N-GQDs) is revealed. This activity was greatly dependent on pH, temperature and H2O2 concentration. The experimental results showed that the stable N-GQDs could be used for the detection of H2O2 and glucose over a wide range of pH and temperature, offering a simple, highly selective and sensitive approach for their colorimetric sensing. The linearity between the analyte concentration and absorption ranged from 20 to 1170 μM for H2O2 and 25 to 375 μM for glucose with a detection limit of 5.3 μM for H2O2 and 16 μM for glucose. This assay was also successfully applied to the detection of glucose concentrations in diluted serum and fruit juice samples. PMID:25818144

  15. Comparison of the efficiency of *OH radical formation during ozonation and the advanced oxidation processes O3/H2O2 and UV/H2O2.

    PubMed

    Rosenfeldt, Erik J; Linden, Karl G; Canonica, Silvio; von Gunten, Urs

    2006-12-01

    Comparison of advanced oxidation processes (AOPs) can be difficult due to physical and chemical differences in the fundamental processes used to produce OH radicals. This study compares the ability of several AOPs, including ozone, ozone+H2O2, low pressure UV (LP)+H2O2, and medium pressure UV (MP)+H2O2 in terms of energy required to produce OH radicals. Bench scale OH radical formation data was generated for each AOP using para-chlorobenzoic acid (pCBA) as an OH radical probe compound in three waters, Lake Greifensee water, Lake Zurich water, and a simulated groundwater. Ozone-based AOPs were found to be more energy efficient than the UV/H2O2 process at all H2O2 levels, and the addition of H2O2 in equimolar concentration resulted in 35% greater energy consumption over the ozone only process. Interestingly, the relatively high UV/AOP operational costs were due almost exclusively to the cost of hydrogen peroxide while the UV portion of the UV/AOP process typically accounted for less than 10 percent of the UV/AOP cost and was always less than the ozone energy cost. As the *OH radical exposure increased, the energy gap between UV/H2O2 AOP and ozone processes decreased, becoming negligible in some water quality scenarios. PMID:17078993

  16. Distance and kinematics of IRAS 19134+2131 revealed by H2O maser observations

    NASA Astrophysics Data System (ADS)

    Imai, H.; Sahai, R.; Morris, M.

    2008-07-01

    Using the VLBA, we have observed H2O maser emission in the pre-planetary nebula, IRAS 19134+2131 (I1913), in which the H2O maser spectrum has two groups of emission features separated in radial velocity by ~100 km s-1. The morphology and 3-D kinematics indicate the existence of a fast collimated flow with a dynamical age of only ~40 years. Such a “water fountain” source is a signature of the recent operation of a stellar jet, that may be responsible for the final shape of the planetary nebula into which I1913 is expected to evolve. We have also estimated the distance to I1913 (~8 kpc) on the basis of an annual parallax and the kinematics of IRAS 19134+2131 in our Galaxy. I1913 may be a component in the “thick disk” or the Galactic “warp”, whose kinematics is different from that of the Galactic “thin” disk. These results are reported in Imai, Sahai & Morris (2007).

  17. Ultrafast phosphate hydration dynamics in bulk H2O

    NASA Astrophysics Data System (ADS)

    Costard, Rene; Tyborski, Tobias; Fingerhut, Benjamin P.; Elsaesser, Thomas

    2015-06-01

    Phosphate vibrations serve as local probes of hydrogen bonding and structural fluctuations of hydration shells around ions. Interactions of H2PO4- ions and their aqueous environment are studied combining femtosecond 2D infrared spectroscopy, ab-initio calculations, and hybrid quantum-classical molecular dynamics (MD) simulations. Two-dimensional infrared spectra of the symmetric ( ν S ( PO2 - ) ) and asymmetric ( ν A S ( PO2 - ) ) PO 2- stretching vibrations display nearly homogeneous lineshapes and pronounced anharmonic couplings between the two modes and with the δ(P-(OH)2) bending modes. The frequency-time correlation function derived from the 2D spectra consists of a predominant 50 fs decay and a weak constant component accounting for a residual inhomogeneous broadening. MD simulations show that the fluctuating electric field of the aqueous environment induces strong fluctuations of the ν S ( PO2 - ) and ν A S ( PO2 - ) transition frequencies with larger frequency excursions for ν A S ( PO2 - ) . The calculated frequency-time correlation function is in good agreement with the experiment. The ν ( PO2 - ) frequencies are mainly determined by polarization contributions induced by electrostatic phosphate-water interactions. H2PO4-/H2O cluster calculations reveal substantial frequency shifts and mode mixing with increasing hydration. Predicted phosphate-water hydrogen bond (HB) lifetimes have values on the order of 10 ps, substantially longer than water-water HB lifetimes. The ultrafast phosphate-water interactions observed here are in marked contrast to hydration dynamics of phospholipids where a quasi-static inhomogeneous broadening of phosphate vibrations suggests minor structural fluctuations of interfacial water.

  18. Speciation and diffusion profiles of H2O in water-poor beryl: comparison with cordierite

    NASA Astrophysics Data System (ADS)

    Della Ventura, G.; Radica, F.; Bellatreccia, F.; Freda, C.; Cestelli Guidi, M.

    2015-10-01

    This paper reports on water speciation and diffusion in synthetic beryl samples treated in CO2-rich atmosphere, at 700 MPa and 700 and 800 °C, respectively. The study has been conducted by means of polarized FTIR (Fourier transform infrared) integrated with FPA (focal plane array) imaging. As expected, the infrared spectra show the presence of CO2 but also of minor H2O interpreted as resulting from moisture present in the starting materials used for the experiments. FPA-FTIR images show that H2O diffuses into the beryl matrix along the structural channels oriented parallel to [001]. Spectra collected along profiles parallel to the c-axis show subtle changes as a function of the distance from the crystal edge; these changes can be correlated to a progressive change in the H2O coordination environment in the channel, as a response to the varying H2O/alkali ratio. In particular, the data show that when 2H2O > Na+ apfu (atoms per formula unit), H2O can assume both type I and type II orientation; in the latter case, each Na cation coordinates two H2O[II] molecules (doubly coordinated H2O). If 2H2O < Na+ apfu, then H2O[II] molecules are singly coordinated to each Na cation. The same type of feature is observed and commented for the structurally related cordierite. Diffusion coefficients and activation energies have been also determined for both types of water molecules.

  19. Real-time monitoring of basal H2O2 levels with peroxiredoxin-based probes.

    PubMed

    Morgan, Bruce; Van Laer, Koen; Owusu, Theresa N E; Ezeriņa, Daria; Pastor-Flores, Daniel; Amponsah, Prince Saforo; Tursch, Anja; Dick, Tobias P

    2016-06-01

    Genetically encoded probes based on the H2O2-sensing proteins OxyR and Orp1 have greatly increased the ability to detect elevated H2O2 levels in stimulated or stressed cells. However, these proteins are not sensitive enough to monitor metabolic H2O2 baseline levels. Using yeast as a platform for probe development, we developed two peroxiredoxin-based H2O2 probes, roGFP2-Tsa2ΔCR and roGFP2-Tsa2ΔCPΔCR, that afford such sensitivity. These probes are ∼50% oxidized under 'normal' unstressed conditions and are equally responsive to increases and decreases in H2O2. Hence, they permit fully dynamic, real-time measurement of basal H2O2 levels, with subcellular resolution, in living cells. We demonstrate that expression of these probes does not alter endogenous H2O2 homeostasis. The roGFP2-Tsa2ΔCR probe revealed real-time interplay between basal H2O2 levels and partial oxygen pressure. Furthermore, it exposed asymmetry in H2O2 trafficking between the cytosol and mitochondrial matrix and a strong correlation between matrix H2O2 levels and cellular growth rate. PMID:27089028

  20. Thermal Reactions of H2O2 on Icy Satellites and Small Bodies: Descent with Modification?

    NASA Technical Reports Server (NTRS)

    Hudson, Reggie L.; Loeffler, Mark J.

    2012-01-01

    Magnetospheric radiation drives surface and near-surface chemistry on Europa, but below a few meters Europa's chemistry is hidden from direct observation . As an example, surface radiation chemistry converts H2O and SO2 into H2O2 and (SO4)(sup 2-), respectively, and these species will be transported downward for possible thermally-driven reactions. However, while the infrared spectra and radiation chemistry of H2O2-containing ices are well documented, this molecule's thermally-induced solid-phase chemistry has seldom been studied. Here we report new results on thermal reactions in H2O + H2O2 + SO2 ices at 50 - 130 K. As an example of our results, we find that warming H2O + H2O2 + SO2 ices promotes SO2 oxidation to (SO4)(sup 2-). These results have implications for the survival of H2O2 as it descends, with modification, towards a subsurface ocean on Europa. We suspect that such redox chemistry may explain some of the observations related to the presence and distribution of H2O2 across Europa's surface as well as the lack of H2O2 on Ganymede and Callisto.

  1. Hydrogen peroxide (H2O2) controls axon pathfinding during zebrafish development.

    PubMed

    Gauron, Carole; Meda, Francesca; Dupont, Edmond; Albadri, Shahad; Quenech'Du, Nicole; Ipendey, Eliane; Volovitch, Michel; Del Bene, Filippo; Joliot, Alain; Rampon, Christine; Vriz, Sophie

    2016-06-15

    It is now becoming evident that hydrogen peroxide (H2O2), which is constantly produced by nearly all cells, contributes to bona fide physiological processes. However, little is known regarding the distribution and functions of H2O2 during embryonic development. To address this question, we used a dedicated genetic sensor and revealed a highly dynamic spatio-temporal pattern of H2O2 levels during zebrafish morphogenesis. The highest H2O2 levels are observed during somitogenesis and organogenesis, and these levels gradually decrease in the mature tissues. Biochemical and pharmacological approaches revealed that H2O2 distribution is mainly controlled by its enzymatic degradation. Here we show that H2O2 is enriched in different regions of the developing brain and demonstrate that it participates to axonal guidance. Retinal ganglion cell axonal projections are impaired upon H2O2 depletion and this defect is rescued by H2O2 or ectopic activation of the Hedgehog pathway. We further show that ex vivo, H2O2 directly modifies Hedgehog secretion. We propose that physiological levels of H2O2 regulate RGCs axonal growth through the modulation of Hedgehog pathway. PMID:27158028

  2. Using H2O and trace element ratios to produce a spatial map of magmatic H2O contents throughout the Trans-Mexican Volcanic Belt

    NASA Astrophysics Data System (ADS)

    Johnson, E. R.; Wallace, P. J.; Manea, V. C.

    2007-12-01

    Along with fluids, trace elements are released during dehydration of subducting sediment and altered oceanic crust. Large ion lithophile elements are typically fluid mobile, and thus may be used as tracers for fluid fluxing. We used melt inclusion H2O and trace element data from nine cinder cones across the subduction-related Michoacan-Guanajuato Volcanic Field (MGVF) of central Mexico to assess the fluid mobility of trace element species. We found correlations between H2O and Sr/La, Ba/Nb, Ba/Y, Pb/Y, Sr/Ti, suggesting that Sr, Ba, and Pb are present in fluids released from the downgoing slab. Additionally, we used regression lines for these correlations to estimate magmatic H2O for cinder cones across Mexico. We have applied the Sr/La and Sr/Ti relationships to the extensive dataset of cinder cone lava and scoria analyses from the MGVF by Hasenaka and Carmichael (1985). In order to see 2-D spatial patterns in H2O across the MGVF, we plotted the localities and the calculated H2O contents on a digital elevation model of Mexico. Initial results from this modeling show that, like our melt inclusion data, magmatic H2O contents are generally high (>3 wt%) across a broad region from the volcanic front to ~100 km behind the front. High H2O concentrations (4-6 wt%) are most abundant along the volcanic front, whereas much lower values (1-2 wt%) occur in an extensional region far behind the front. The relationship between H2O and trace element ratios can also be extended to other regions of Mexico, as the correlation between H2O/La and Sr/La is consistent to the east in the Chichinautzin Volcanic Field (Cervantes and Wallace, 2003) and to the west in the Colima Graben. Using analyses from these and other regions, we have created a spatial map of H2O contents across the Trans- Mexican Volcanic Belt, enabling us to see trends both along and across the arc. We can then use these spatial maps to relate patterns in H2O content to subduction processes such as arc migration over

  3. Hydrocalcite (CaCO3 * H2O) and Nesquehonite (MgCO3 * 3H2O) in Carbonate Scales.

    PubMed

    Marschner, H

    1969-09-12

    Hydrocalcite (CaCO(3) * H(2)O) with exactly one molecule of hydrate water is the main component of carbonate scales deposited from cold water in contact with air. When the magnesium content of the water is high, the hydrocalcite occurs together with MgCO(3) * 3H(2)O (nesquehonite). From the conditions under which hydrocalcite is transformed into calcite and aragonite, it appears that in some cases aragonite in nature may be formed by way of an intermediary of CaCO(3) * H(2)O. PMID:17779803

  4. H 2O in basalt and basaltic andesite glass inclusions from four subduction-related volcanoes

    NASA Astrophysics Data System (ADS)

    Sisson, T. W.; Layne, G. D.

    1993-06-01

    Total dissolved H 2O and major element abundances were measured in basalt and basaltic andesite glass inclusions in olivine phenocrysts from Quaternary eruptions of four subduction-related volcanoes to test the hypothesis that low-MgO high-alumina basalts contain high H 2O at depth [1] and to reveal any petrogenetically significant correlations between arc basalt compositions and H 2O contents. Total dissolved H 2O (combined molecular H 2O and OH groups) measured by ion microprobe in mafic glass inclusions from the 1974 eruption of Fuego, Guatemala, reaches 6.2 wt.%. Dissolved H 2O contents decrease in more evolved Fuego glasses. Correlations of H 2O with MgO, Na 2O, K 2O, S and Cl indicate that aqueous fluid exsolution during magma ascent forced crystallization and differentiation of residual liquids. Low-K 2O magnesian high-alumina basalt glass inclusions from the 3 ka eruption of Black Crater (Medicine Lake volcano, California) have low H 2O contents, near 0.2 wt.%, which are consistent with the MORB-like character of these and other primitive lavas of the Medicine Lake region. Basalt and basaltic andesite glass inclusions from Copco Cone and Goosenest volcano on the Cascade volcanic front north of Mt. Shasta have H 2O contents of up to 3.3 wt.%. The range of H 2O contents in Cascade mafic magmas is too large to have resulted solely from enrichment by crystallization and indicates the participation of an H 2O-rich component in magma generation or crustal-level modification. Whereas fluid-absent melting of amphibole-bearing peridotite can account for the H 2O in most mafic arc liquids, the very high H 2O/alkali ratios of the 1974 Fuego eruptives suggest that an aqueous fluid was involved in the generation of Fuego basalts.

  5. The Photochemistry of Pyrimidine in Pure H2O Ice Subjected to Different Radiation Environments and the Formation of Uracil

    NASA Technical Reports Server (NTRS)

    Nuevo, M.; Chen, Y.-J.; Materese. C. K..; Hu, W.-J.; Qiu, J.-M.; Wu, S.-R.; Fung, H.-S.; Sandford, S. A.; Chu, C.-C.; Yih, T.-S.; Wu, R.; Ip, W.-H.

    2013-01-01

    Nucleobases are N-heterocycles which are the informational subunits of DNA and RNA. They include pyrimidine bases (uracil, cytosine, and thymine) and purine bases (adenine and guanine). Nucleobases have been detected in several meteorites, although no Nheterocycles have been observed in space to data. Laboratory experiments showed that the ultraviolet (UV) irradiation of pyrimidine in pure H2O ice at low temperature (<=20 K) leads to the formation of pyrimidine derivatives including the nucleobase uracil and its precursor 4(3H)-pyrimidone. These results were confirmed by quantum chemical calculations. When pyrimidine is mixed with combinations of H2O, NH3, CH3OH, and CH4 ices under similar conditions, uracil and cytosine are formed. In the present work we study the formation of 4(3H)-pyrimidone and uracil from the irradiation of pyrimidine in H2O ice with high-energy UV photons (Lyman , He I, and He II lines) provided by a synchrotron source. The photo-destruction of pyrimidine in these H2O ices as well as the formation yields for 4(3H)-pyrimidone and uracil are compared with our previous results in order to study the photo-stability of pyrimidine and the production efficiency of uracil as a function of the photon energy.

  6. Long-term monitoring and interpretation of flares in the H2O maser emission of IRAS 16293-2422

    NASA Astrophysics Data System (ADS)

    Colom, P.; Lekht, E. E.; Pashchenko, M. I.; Rudnitskii, G. M.; Tolmachev, A. M.

    2016-08-01

    The results of a study of the H2O and OH maser emission from the cool IR source IRAS 16293-2422 are presented. The observations analyzed were obtained in H2O lines with the 22-m telescope of the Pushchino Radio Astronomy Observatory during 1999-2015 and in OH lines with the Nanç ay radio telescope (France). A large number of very strong flares of the H2O maser were detected, reaching fluxes of tens of thousands of Jansky. Individual features can form organized structures resembling chains ˜2 AU in length with a radial-velocity gradient along them. The observed drift of the H2O emission (2003-2004) in space and velocity (from 4.3 to 5.3 km/s) is not due solely to proper motion of the features. The other origin of the drift is a drift of the emission maximum during a flare as the shock consecutively excites spatially separated features in the structure in the form of a chain. The OH-line observations at 18 cm show that the emission remains unpolarized and thermal, with a line width of 0.7 km/s, which corresponds to a cloud temperature of ˜30 K.

  7. Influence of isotopic disorder on solid state amorphization and polyamorphism in solid H2O -D2O solutions

    NASA Astrophysics Data System (ADS)

    Gromnitskaya, E. L.; Danilov, I. V.; Lyapin, A. G.; Brazhkin, V. V.

    2015-10-01

    We present a low-temperature and high-pressure ultrasonic study of elastic properties of isotopic H2O-D2O solid solutions, comparing their properties with those of the isotopically pure H2O and D2O ices. Measurements were carried out for solid state amorphization (SSA) from 1h to high-density amorphous (HDA) ice upon compression up to 1.8 GPa at 77 K and for the temperature-induced (77 -190 K ) u-HDA (unrelaxed HDA) → e-HDA (expanded HDA) → low-density amorphous (LDA )→1 c cascade of ice transformations near room pressure. There are many similarities in the elasticity behaviour of H2O ,D2O , and H2O-D2O solid solutions, including the softening of the shear elastic modulus as a precursor of SSA and the HDA →LDA transition. We have found significant isotopic effects during H/D substitution, including elastic softening of H2O -D2O solid solutions with respect to the isotopically pure ices in the case of the bulk moduli of ices 1c and 1h and for both bulk and shear elastic moduli of HDA ice at high pressures (>1 GPa ) . This softening is related to the configurational isotopic disorder in the solid solutions. At low pressures, the isotope concentration dependence of the elastic moduli of u-HDA ice changes remarkably and becomes monotonic with pronounced change of the bulk modulus (≈20 %) .

  8. Functionalization of graphene by atmospheric pressure plasma jet in air or H2O2 environments

    NASA Astrophysics Data System (ADS)

    Huang, Weixin; Ptasinska, Sylwia

    2016-03-01

    The functionalization of graphene, which deforms its band structure, can result in a metal-semiconductor transition. In this work, we report a facile strategy to oxidize single-layer graphene using an atmospheric pressure plasma jet (APPJ) that generates a variety of reactive plasma species at close to ambient temperature. We systematically characterized the oxygen content and chemical structure of the graphene films after plasma treatment under different oxidative conditions (ambient air atmosphere or hydrogen peroxide solution) by X-ray Photoelectron Spectroscopy (XPS). Plasma-treated graphene films containing more than 40% oxygen were obtained in both oxidative environments. Interestingly, prolonged irradiation led to the reduction of graphene oxides. N-doping of graphene also occurred during the APPJ treatment in H2O2 solution; the nitrogen content of the doped graphene was dependent on the duration of irradiation and reached up to 8.1% within 40 min. Moreover, the H2O2 solution served as a buffer layer that prevented damage to the graphene during plasma irradiation. Four-point probe measurement revealed an increase in sheet resistance of the plasma-treated graphene, indicating the transition of the material property from semi-metallic to semiconducting.

  9. Whiteness improvement of citric acid crosslinked cotton fabrics: H2O2 bleaching under alkaline condition.

    PubMed

    Tang, Peixin; Ji, Bolin; Sun, Gang

    2016-08-20

    Polycarboxylic acids have been employed as formaldehyde-free crosslinking agents in anti-wrinkle treatment for cotton fabrics. Cotton fabrics treated by citric acid (CA) catalyzed with effective catalysts have shown satisfactory anti-wrinkle properties. Meanwhile, CA is a natural-based and environmental friendly compound. However, the yellowing of CA treated fabrics is a stumbling block for its practical application. Due to the fact that CA firstly forms aconitic acid (AA) before forming anhydrides, the cause of the yellowing, hydrogen peroxide (H2O2) bleaching was adopted to treat the CA treated fabrics in order to break the CC bond structure and reduce the yellow color but retaining the desired anti-wrinkle properties. Thermogravimetric analysis and Fourier transformed infrared spectroscopy were employed to investigate the reactions. The results revealed that the H2O2 bleaching can effectively improve the whiteness and also maintain a good anti-wrinkle performance of the CA treated fabrics under an appropriate bleaching temperature and time. PMID:27178918

  10. Second critical endpoint in the peridotite-H2O system

    NASA Astrophysics Data System (ADS)

    Mibe, Kenji; Kanzaki, Masami; Kawamoto, Tatsuhiko; Matsukage, Kyoko N.; Fei, Yingwei; Ono, Shigeaki

    2007-03-01

    The second critical endpoint in the peridotite-H2O system has been determined using an X-ray radiography technique together with a Kawai-type, double-stage, multianvil system driven by DIA-type cubic press (SPEED-1500) installed at SPring-8, Japan. The pressure of the second critical endpoint was determined by the appearance and disappearance of round shape in the radiographic images with changing the experimental pressure. In the experiments up to 3.6 GPa, two fluid phases (i.e., aqueous fluid and hydrous silicate melt) were observed. At 4.0 GPa, however, we could not distinguish these two phases in the radiographic images. These observations indicate the second critical endpoint occurs at around 3.8 GPa and 1000°C (corresponding to a depth of ˜110 km) in the peridotite-H2O system. Our experimental results suggest that hydrous silicate melt and aqueous fluid in the Earth's mantle become indistinguishable from each other and that melting temperature of hydrous mantle peridotite can no longer be defined beyond this critical condition. This position of the second critical endpoint could explain the previously observed drastic changes in composition and connectivity of aqueous fluid in mantle peridotite at around 3-4 GPa and could play an important role in magmatism and chemical evolution of the Earth's interior.

  11. A Laser Photoacoustic Analysis of Residual CO2 and H2O in Larch Stems

    PubMed Central

    Ageev, Boris; Ponomarev, Yurii; Sapozhnikova, Valeria; Savchuk, Dmitry

    2014-01-01

    Every so often, the results obtained from investigations into the effects of varying environmental conditions on the tree growth rate at the same sites and on the change in the carbon balance in plants, using traditional methods, are found to differ widely. We believe that the reason for the ambiguity of the data has to do with failure to account for the role of the residual CO2 (and H2O) in the tree wood exhibiting a climate response. In our earlier work, the results of a laser photoacoustic gas analysis of CO2 and H2O vacuum-desorbed from disc tree rings of evergreen conifer trees were presented. In this paper, laser photoacoustic measurements of tree ring gases in deciduous conifer trees and CO2 carbon isotope composition determined by means of a mass spectrometer are given. Conclusions are made regarding the response of annual larch CO2 disc tree ring distributions to climatic parameters (temperatures and precipitation). The data about the CO2 disc content for different sites are compared. PMID:25808838

  12. Volumetric Properties and Fluid Phase Equilibria of CO2 + H2O

    SciTech Connect

    Capobianco, Ryan; Gruszkiewicz, Miroslaw {Mirek} S; Wesolowski, David J; Cole, David R; Bodnar, Robert

    2013-01-01

    The need for accurate modeling of fluid-mineral processes over wide ranges of temperature, pressure and composition highlighted considerable uncertainties of available property data and equations of state, even for the CO2 + H2O binary system. In particular, the solubility, activity, and ionic dissociation equilibrium data for the CO2-rich phase, which are essential for understanding dissolution/precipitation, fluid-matrix reactions, and solute transport, are uncertain or missing. In this paper we report the results of a new experimental study of volumetric and phase equilibrium properties of CO2 + H2O, to be followed by measurements for bulk and confined multicomponent fluid mixtures. Mixture densities were measured by vibrating tube densimetry (VTD) over the entire composition range at T = 200 and 250 C and P = 20, 40, 60, and 80 MPa. Initial analysis of the mutual solubilities, determined from volumetric data, shows good agreement with earlier results for the aqueous phase, but finds that the data of Takenouchi and Kennedy (1964) significantly overestimated the solubility of water in supercritical CO2 (by a factor of more than two at 200 C). Resolving this well-known discrepancy will have a direct impact on the accuracy of predictive modeling of CO2 injection in geothermal reservoirs and geological carbon sequestration through improved equations of state, needed for calibration of predictive molecular-scale models and large-scale reactive transport simulations.

  13. Cryo-chamber simulation of stratospheric H2SO4/H2O particles: Composition analysis and model comparison

    NASA Astrophysics Data System (ADS)

    Zink, Peter; Knopf, Daniel A.; Schreiner, Jochen; Mauersberger, Konrad; Möhler, Ottmar; Saathoff, Harald; Seifert, Marco; Tiede, Ralph; Schurath, Ulrich

    2002-06-01

    The combination of a large aerosol chamber and a recently developed Aerosol Composition Mass Spectrometer (ACMS) was used to investigate sulfuric acid aerosols at low temperatures. Concentrations of condensed phase H2SO4 and H2O were determined with an accuracy of better than 4 wt.%. Simultaneous measurements of temperature, partial pressure of water, total sulfate amount and particle size distribution permit to calculate the particle equilibrium composition. The model description of Carslaw et al. [1995a] for H2SO4/H2O solutions was confirmed in the composition range from 35 to 68 wt.% H2SO4 for temperatures between 188 and 236 K, extending the experimental verification to lower temperatures. Although the sub-micron particles were up to 25 K super-cooled with respect to solid sulfuric acid hydrates such as the tetrahydrate (SAT), they remained liquid for days.

  14. Dissociative excitation transfer in the reaction of O2(a(1)Delta(g)) with OH- (H2O)(1,2) clusters.

    PubMed

    Viggiano, Albert A; Midey, Anthony; Eyet, Nicole; Bierbaum, Veronica M; Troe, Jürgen

    2009-09-01

    Rate constants for the dissociation of OH(-)(H(2)O) and OH(-)(H(2)O)(2) by transfer of electronic energy from O(2)(a(1)Delta(g)) were measured. Values of 1.8x10(-11) and 2.2x10(-11) cm(3) molecule(-1) s(-1), respectively, at 300 K were derived and temperature dependences were obtained from 300 to 500 K for OH(-)(H(2)O) and from 300 to 400 K for OH(-)(H(2)O)(2). Dissociative excitation transfer with OH(-)(H(2)O) is slightly endothermic and the reaction appears to have a positive temperature dependence, but barely outside the uncertainty range. In contrast, the reaction of OH(-)(H(2)O)(2) is exothermic and appears to have a negative temperature dependence. The rate constants are analyzed in terms of unimolecular rate theory, which suggests that the dissociation is prompt and is not affected by collisions with the helium buffer gas. PMID:19739854

  15. Vibrational spectra of Cs2Cu(SO4)2·6H2O and Cs2Cu(SeO4)2·nH2O (n = 4, 6) with a crystal structure determination of the Tutton salt Cs2Cu(SeO4)2·6H2O

    NASA Astrophysics Data System (ADS)

    Wildner, M.; Marinova, D.; Stoilova, D.

    2016-02-01

    The solubility in the three-component systems Cs2SO4-CuSO4-H2O and Cs2SeO4-CuSeO4-H2O have been studied at 25 °C. The experimental results show that double salts, Cs2Cu(SO4)2·6H2O and Cs2Cu(SeO4)2·4H2O, crystallize from the ternary solutions within large concentration ranges. Crystals of Cs2Cu(SeO4)2·6H2O were synthesized at somewhat lower temperatures (7-8 °C). The thermal dehydration of the title compounds was studied by TG, DTA and DSC methods and the respective dehydration schemes are proposed. The calculated enthalpies of dehydration (ΔHdeh) have values of: 434.2 kJ mol-1 (Cs2Cu(SeO4)2·6H2O), 280.9 kJ mol-1 (Cs2Cu(SeO4)2·4H2O), and 420.2 kJ mol-1 (the phase transition of Cs2Cu(SO4)2·6H2O into Cs2Cu(SO4)2·H2O). The crystal structure of Cs2Cu(SeO4)2ṡ6H2O was determined from single crystal X-ray diffraction data. It belongs to the group of Tutton salts, crystallizing isotypic to the respective sulfate in a monoclinic structure which is characterized by isolated Cu(H2O)6 octahedra and SeO4 tetrahedra, interlinked by hydrogen bonds and [9]-coordinated Cs+ cations. Infrared spectra of the cesium copper compounds are presented and discussed with respect to both the normal modes of the tetrahedral ions and the water molecules. The analysis of the infrared spectra of the double compounds reveals that the distortion of the selenate tetrahedra in Cs2Cu(SeO4)2·4H2O is stronger than those in Cs2Cu(SeO4)2·6H2O in agreement with the structural data. Matrix-infrared spectroscopy was applied to confirm this claim - Δν3 for SO4 2 - ions matrix-isolated in Cs2Cu(SeO4)2·6H2O has a value of 35 cm-1 and that of the same ions included in Cs2Cu(SeO4)2·4H2O - 84 cm-1. This spectroscopic finding is due to the formation of strong covalent bands Cu-OSO3 on one hand, and on the other to the stronger deformation of the host SeO4 2 - tetrahedra in Cs2Cu(SeO4)2·4H2O as compared to those in Cs2Cu(SeO4)2·6H2O. The strength of the hydrogen bonds as deduced from

  16. Effect of chirality on the dynamics of domain walls in the molecular ferrimagnet [MnII(H L-pn)(H2O)][MnIII(CN)6] · 2H2O

    NASA Astrophysics Data System (ADS)

    Mushenok, F. B.; Morgunov, R. B.; Koplak, O. V.; Kirman, M. V.

    2012-04-01

    The contributions from modes of switching, sliding, creep, and Debye relaxation of pinned domain walls to the low-frequency magnetic properties of the chiral and racemic molecular ferrimagnets [MnII(H L-pn)(H2O)][MnIII(CN)6] · 2H2O have been separated. It has been found that the chirality of the atomic and spin structures affects the temperatures of the transitions from the sliding mode to the creep mode and from the creep mode to the mode of Debye relaxation. In the chiral crystals, transitions to the creep and Debye relaxation modes have been observed at temperatures T = 7 and 5 K, respectively. In the racemic crystals, these transitions have been observed at temperatures T = 13 and 9 K, respectively, all other factors being equal.

  17. Experimental and theoretical studies of H2O oxidation by neutral Ti2O4,5 clusters under visible light irradiation.

    PubMed

    Yin, Shi; Bernstein, Elliot R

    2014-07-21

    A new photo excitation fast flow reactor system is constructed and used to investigate reactions of neutral TimOn clusters with H2O under visible (532 nm) light irradiation. Single photon ionization at 118 nm (10.5 eV) is used to detect neutral cluster distributions through time of flight mass spectrometry. TimOn clusters are generated through laser ablation of a titanium target in the presence of 4% O2/He carrier gas. Association products Ti2O4(H2O) and Ti2O5(H2O) are observed for reactions of H2O and TimOn clusters without irradiation. Under 532 nm visible light irradiation of the fast flow reactor, only the Ti2O5(H2O) feature disappears. This light activated reaction suggests that visible radiation can induce chemistry for Ti2O5(H2O), but not for Ti2O4(H2O). Density functional theory (DFT) and time-dependent (TD) DFT calculations are performed to explore the ground and first excited state potential energy surfaces (PES) for the reaction Ti2O5 + H2O → Ti2O4 + H2O2. A high barrier (1.33 eV) and a thermodynamically unfavorable (1.14 eV) pathway are obtained on the ground state PES for the Ti2O5 + H2O reaction; the reaction is also thermodynamically unfavorable (1.54 eV) on the first singlet excited state PES. The reaction is proposed to occur on the ground state PES through a conical intersection ((S1/S0)CI), and to generate products Ti2O4 and H2O2 on the ground state PES. This mechanism is substantiated by a multi-reference ab initio calculation at the complete active space self-consistent field (CASSCF) level. The S0-S1 vertical excitation energy of Ti2O4 (3.66 eV) is much higher than the 532 nm photon energy (2.33 eV), suggesting this visible light driven reaction is unfavorable for the Ti2O4 cluster. The TDDFT calculated optical absorption spectra of Ti2O4 and Ti2O5 further indicate that Ti2O5 like structures on a titanium oxide surface are the active catalytic sites for visible light photo-catalytic oxidation of water. PMID:24898817

  18. The Paradox of a Wet (High H2O) and Dry (Low H2O/Ce) Mantle: High Water Concentrations in Mantle Garnet Pyroxenites from Hawaii

    NASA Technical Reports Server (NTRS)

    Peslier, Anne H.; Bizimis, Michael

    2013-01-01

    Water dissolved as trace amounts in anhydrous minerals has a large influence on the melting behavior and physical properties of the mantle. The water concentration of the oceanic mantle is inferred from the analyses of Mid-Ocean Ridge Basalt (MORB) and Oceanic Island Basalt (OIB). but there is little data from actual mantle samples. Moreover, enriched mineralogies (pyroxenites, eclogites) are thought as important sources of heterogeneity in the mantle, but their water concentrations and their effect on the water budget and cycling in the mantle are virtually unknown. Here, we analyzed by FTIR water in garnet clinopyroxenite xenoliths from Salt Lake Crater, Oahu, Hawaii. These pyroxenites are high-pressure (>20kb) crystal fractionates from alkalic melts. The clinopyroxenes (cpx) have 260 to 576 ppm wt H2O, with the least differentiated samples (Mg#>0.8) in the 400-500 ppm range. Orthopyroxene (opx) contain 117-265 ppm H2O, about half of that of cpx, consistent with other natural sample studies, but lower than cpx/opx equilibrium from experimental data. The pyroxenite cpx and opx H2O concentrations are at the high-end of on-and off-craton peridotite xenolith concentrations and those of Hawaiian spinel peridotites. In contrast, garnet has extremely low water contents (<5ppm H2O). There is no correlation between H2O in cpx and lithophile element concentrations. Phlogopite is present in some samples, and its modal abundance shows a positive correlation in Mg# with cpx, implying equilibrium. However, there is no correlation between H2O concentrations and or the presence of phlogopite. These data imply that cpx and opx may be at water saturation, far lower than experimental data suggest. Reconstructed bulk rock pyroxenite H2O ranges from 200-460 ppm (average 331 +/- 75 ppm), 2 to 8 times higher than H2O estimates for the MORB source (50-200 ppm), but in the range of E-MORB, OIB and the source of rejuvenated Hawaiian magmas. The average bulk rock pyroxenite H2O/Ce is 69

  19. Experimental determination of the H2O + 15 wt% NaCl and H2O + 25 wt% NaCl liquidi to 1.4 GPa

    NASA Astrophysics Data System (ADS)

    Valenti, P.; Schmidt, C.

    2009-12-01

    The binary H2O+NaCl is one of the most important model systems for chloridic fluids in many geologic environments such as the Earth’s crust, upper mantle, and subducting slabs, and is also applicable to