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Sample records for modeling hydrogen water

  1. Hydrogen-Bonding Polarizable Intermolecular Potential Model for Water.

    PubMed

    Jiang, Hao; Moultos, Othonas A; Economou, Ioannis G; Panagiotopoulos, Athanassios Z

    2016-12-08

    A polarizable intermolecular potential model with short-range directional hydrogen-bonding interactions was developed for water. The model has a rigid geometry, with bond lengths and angles set to experimental gas-phase values. Dispersion interactions are represented by the Buckingham potential assigned to the oxygen atom, whereas electrostatic interactions are modeled by Gaussian charges. Polarization is handled by a Drude oscillator site, using a negative Gaussian charge attached to the oxygen atom by a harmonic spring. An explicit hydrogen-bonding term is included in the model to account for the effects of charge transfer. The model parameters were optimized to density, configurational energy, pair correlation function, and the dielectric constant of water under ambient conditions, as well as the minimum gas-phase dimer energy. Molecular dynamics and Gibbs ensemble Monte Carlo simulations were performed to evaluate the new model with respect to the thermodynamic and transport properties over a wide range of temperature and pressure conditions. Good agreement between model predictions and experimental data was found for most of the properties studied. The new model yields better performance relative to the majority of existing models and outperforms the BK3 model, which is one of the best polarizable models, for vapor-liquid equilibrium properties, whereas the new model is not better than the BK3 model for representation of other properties. The model can be efficiently simulated with the thermalized Drude oscillator algorithm, resulting in computational costs only 3 times higher than those of the nonpolarizable TIP4P/2005 model, whereas having significantly improved properties. Because it involves only a single Drude oscillator site, the new model is significantly faster than polarizable models with multiple sites. With the explicit inclusion of hydrogen-bond interactions, the model may provide a better description of the phase behavior of aqueous mixtures.

  2. Modeling of biomass to hydrogen via the supercritical water pyrolysis process

    SciTech Connect

    Divilio, R.J.

    1998-08-01

    A heat transfer model has been developed to predict the temperature profile inside the University of Hawaii`s Supercritical Water Reactor. A series of heat transfer tests were conducted on the University of Hawaii`s apparatus to calibrate the model. Results of the model simulations are shown for several of the heat transfer tests. Tests with corn starch and wood pastes indicated that there are substantial differences between the thermal properties of the paste compared to pure water, particularly near the pseudo critical temperature. The assumption of constant thermal diffusivity in the temperature range of 250 to 450 C gave a reasonable prediction of the reactor temperatures when paste is being fed. A literature review is presented for pyrolysis of biomass in water at elevated temperatures up to the supercritical range. Based on this review, a global reaction mechanism is proposed. Equilibrium calculations were performed on the test results from the University of Hawaii`s Supercritical Water Reactor when corn starch and corn starch and wood pastes were being fed. The calculations indicate that the data from the reactor falls both below and above the equilibrium hydrogen concentrations depending on test conditions. The data also indicates that faster heating rates may be beneficial to the hydrogen yield. Equilibrium calculations were also performed to examine the impact of wood concentration on the gas mixtures produced. This calculation showed that increasing wood concentrations favors the formation of methane at the expense of hydrogen.

  3. Transfer Hydrogenation in Water.

    PubMed

    Wu, Xiaofeng; Wang, Chao; Xiao, Jianliang

    2016-12-01

    This article provides an account of our group's efforts in developing aqueous-phase transfer hydrogenation reactions. It is comprised of mainly two parts. The first part concentrates on asymmetric transfer hydrogenation in water, enabled by Noyori-Ikariya catalysts, while the second part is concerned with the achiral version of the reaction catalysed by a new class of catalysts, iridacycles. A range of substrates are featured, including various carbonyl compounds and N-heterocycles.

  4. Simulation of the effect of hydrogen bonds on water activity of glucose and dextran using the Veytsman model.

    PubMed

    De Vito, Francesca; Veytsman, Boris; Painter, Paul; Kokini, Jozef L

    2015-03-06

    Carbohydrates exhibit either van der Waals and ionic interactions or strong hydrogen bonding interactions. The prominence and large number of hydrogen bonds results in major contributions to phase behavior. A thermodynamic framework that accounts for hydrogen bonding interactions is therefore necessary. We have developed an extension of the thermodynamic model based on the Veytsman association theory to predict the contribution of hydrogen bonds to the behavior of glucose-water and dextran-water systems and we have calculated the free energy of mixing and its derivative leading to chemical potential and water activity. We compared our calculations with experimental data of water activity for glucose and dextran and found excellent agreement far superior to the Flory-Huggins theory. The validation of our calculations using experimental data demonstrated the validity of the Veytsman model in properly accounting for the hydrogen bonding interactions and successfully predicting water activity of glucose and dextran. Our calculations of the concentration of hydrogen bonds using the Veytsman model were instrumental in our ability to explain the difference between glucose and dextran and the role that hydrogen bonds play in contributing to these differences. The miscibility predictions showed that the Veytsman model is also able to correctly describe the phase behavior of glucose and dextran.

  5. Hydrogen and water reactor safety: proceedings

    SciTech Connect

    Not Available

    1982-01-01

    Separate abstracts were prepared for papers presented in the following areas of interest: 1) hydrogen research programs; 2) hydrogen behavior during light water reactor accidents; 3) combustible gas generation; 4) hydrogen transport and mixing; 5) combustion modeling and experiments; 6) accelerated flames and detonations; 7) combustion mitigation and control; and 8) equipment survivability.

  6. Role of hydrogen bonds in hydrophobicity: the free energy of cavity formation in water models with and without the hydrogen bonds.

    PubMed

    Madan, B; Lee, B

    1994-08-01

    The free energies of cavity formation in water with and without hydrogen bonding potential were computed from the results of a set of Monte Carlo simulation calculations on pure liquid TIP4P water model and on the same model but with the electrostatic charges turned off (Lennard-Jones liquid). The free energies of cavity formation in the Lennard-Jones liquids are higher than or approximately equal to those in TIP4P water, depending, respectively, on whether the Lennard-Jones size parameter sigma is set equal to 3.15 A, which is the value of sigma for TIP4P water, or to 2.8 A, which is the commonly assumed value for the oxygen-oxygen distance between two hydrogen-bonded water molecules. This result indicates that changes in the hydrogen-bonded structure of water and/or in the orientational degree of freedom of water are not essential features in the production of the large free energy change upon cavity formation.

  7. Process for exchanging hydrogen isotopes between gaseous hydrogen and water

    SciTech Connect

    Hindin, Saul G.; Roberts, George W.

    1980-08-12

    A process for exchanging isotopes of hydrogen, particularly tritium, between gaseous hydrogen and water is provided whereby gaseous hydrogen depeleted in tritium and liquid or gaseous water containing tritium are reacted in the presence of a metallic catalyst.

  8. Water incorporation in spinel: modelling hydrogen storage in the transition zone

    NASA Astrophysics Data System (ADS)

    Bromiley, Geoffrey; Nestola, Fabrizio; Redfern, Simon A. T.; Zhang, Ming

    2010-05-01

    Under conditions of the lower part of Earth's mantle transition zone, (Mg,Fe)2SiO4 adopts a spinel type structure as the mineral ringwoodite. This structure, although nominally anhydrous, has the capacity to incorporate significant amounts of water (up to several weight percent) in the form of structurally-incorporated OH groups. This has led to the suggestion that a significant volume of water could be incorporated in Earth's mantle transition zone, and even that this reservoir might be connected to water present on the surface of the Earth. Characterising the cause and effects of hydrogen incorporation in ringwoodite remains difficult due to the high-pressure/temperature conditions under which it is stable. In order to characterise mechanisms for H incorporation in spinel-type structures we have investigated H incorporation in natural and synthetic MgAl2O4 spinel in a series of high-pressure/temperature annealing experiments. In contrast to most other nominally anhydrous minerals, natural spinel appears to be completely anhydrous. On the other hand, non-stoichiometric Al-rich synthetic (defect) spinel can accommodate several hundred ppm water in the form of structurally-incorporated hydrogen. Infrared (IR) spectra of hydrated defect spinel contain one main O-H stretching band at 3343-3352 cm-1 and a doublet consisting of two distinct O-H bands at 3505-3517 cm-1 and 3557-3566 cm-1. IR spectra and structural refinements based on single-crystal X-ray data are consistent with hydrogen incorporation in defect spinel onto both octahedral and tetrahedral O-O edges. Fine structure of O-H bands in IR spectra can be explained by partial coupling of interstitial hydrogen with cation vacancies, or by the effects of Mg-Al disorder on the tetrahedral site. The concentration of cation vacancies in defect spinel is a major control on hydrogen affinity. The commercial availability of large single crystals of defect spinel coupled with high water solubility and similarities in

  9. Improved Screened Hydrogenic Model

    SciTech Connect

    Nishikawa, T.

    1996-05-01

    Screened Hydrogenic Model is widely used for energy level calculation in hydrodynamic code of inertial confinement fusion because Screened Hydrogenic Model is simple algebraic calculation. More{close_quote}s Screened Hydrogenic Model and his screening constants are usually used to calculate opacity and equation of state. By the use of his model, energy level can be consistently calculated with ion{close_quote}s total energy. But his model take into account the principal quantum number dependence only and cannot reproduce hydrogenic energy levels. As the precise experiment about opacity measurement is performed, it becomes clear that his model is not enough to use for opacity calculation. In this paper, his model is improved in the framework of Screened Hydrogenic Model. The improved model can reproduce the hydrogenic energy levels and include azimuthal quantum number dependence and the effect from another quantum state (a kind of inner quantum number). Screening constants are fitted by spectroscopic data and sophisticate calculations. By the use of improved model, energy levels are calculated more accurately for low-{ital z} ions. {copyright} {ital 1996 American Institute of Physics.}

  10. Hydrogen Water Chemistry Technology in Boiling Water Reactors

    SciTech Connect

    Lin, Chien C

    2000-04-15

    Modification of coolant chemistry by feedwater hydrogen addition in boiling water reactors (BWRs), generally called hydrogen water chemistry (HWC), is a viable option to mitigate the intergranular stress corrosion cracking problems for operating BWRs. Some fundamentals in HWC technologies as known today are reviewed. Several full-scale HWC test results are analyzed, and the roles that hydrogen plays in HWC technology are identified and quantitatively evaluated. Some deficiencies in water radiolysis modeling for BWR applications under HWC conditions and the impact of {sup 16}N radiation field increase in the main steam line are also discussed.

  11. Hydrogen-rich Water Exerting a Protective Effect on Ovarian Reserve Function in a Mouse Model of Immune Premature Ovarian Failure Induced by Zona Pellucida 3

    PubMed Central

    He, Xin; Wang, Shu-Yu; Yin, Cheng-Hong; Wang, Tong; Jia, Chan-Wei; Ma, Yan-Min

    2016-01-01

    Background: Premature ovarian failure (POF) is a disease that affects female fertility but has few effective treatments. Ovarian reserve function plays an important role in female fertility. Recent studies have reported that hydrogen can protect male fertility. Therefore, we explored the potential protective effect of hydrogen-rich water on ovarian reserve function through a mouse immune POF model. Methods: To set up immune POF model, fifty female BALB/c mice were randomly divided into four groups: Control (mice consumed normal water, n = 10), hydrogen (mice consumed hydrogen-rich water, n = 10), model (mice were immunized with zona pellucida glycoprotein 3 [ZP3] and consumed normal water, n = 15), and model-hydrogen (mice were immunized with ZP3 and consumed hydrogen-rich water, n = 15) groups. After 5 weeks, mice were sacrificed. Serum anti-Müllerian hormone (AMH) levels, granulosa cell (GC) apoptotic index (AI), B-cell leukemia/lymphoma 2 (Bcl-2), and BCL2-associated X protein (Bax) expression were examined. Analyses were performed using SPSS 17.0 (SPSS Inc., Chicago, IL, USA) software. Results: Immune POF model, model group exhibited markedly reduced serum AMH levels compared with those of the control group (5.41 ± 0.91 ng/ml vs. 16.23 ± 1.97 ng/ml, P = 0.033) and the hydrogen group (19.65 ± 7.82 ng/ml, P = 0.006). The model-hydrogen group displayed significantly higher AMH concentrations compared with that of the model group (15.03 ± 2.75 ng/ml vs. 5.41 ± 0.91 ng/ml, P = 0.021). The GC AI was significantly higher in the model group (21.30 ± 1.74%) than those in the control (7.06 ± 0.27%), hydrogen (5.17 ± 0.41%), and model-hydrogen groups (11.24 ± 0.58%) (all P < 0.001). The GC AI was significantly higher in the model-hydrogen group compared with that of the hydrogen group (11.24 ± 0.58% vs. 5.17 ± 0.41%, P = 0.021). Compared with those of the model group, ovarian tissue Bcl-2 levels increased (2.18 ± 0.30 vs. 3.01 ± 0.33, P = 0.045) and the Bax

  12. Hydrogen and Oxygen Isotope Ratios in Body Water and Hair: Modeling Isotope Dynamics in Nonhuman Primates

    PubMed Central

    O’Grady, Shannon P.; Valenzuela, Luciano O.; Remien, Christopher H.; Enright, Lindsey E.; Jorgensen, Matthew J.; Kaplan, Jay R.; Wagner, Janice D.; Cerling, Thure E.; Ehleringer, James R.

    2012-01-01

    The stable isotopic composition of drinking water, diet, and atmospheric oxygen influence the isotopic composition of body water (2H/1H, 18O/16O expressed as δ2H and δ18O). In turn, body water influences the isotopic composition of organic matter in tissues, such as hair and teeth, which are often used to reconstruct historical dietary and movement patterns of animals and humans. Here, we used a nonhuman primate system (Macaca fascicularis) to test the robustness of two different mechanistic stable isotope models: a model to predict the δ2H and δ18O values of body water and a second model to predict the δ2H and δ18O values of hair. In contrast to previous human-based studies, use of nonhuman primates fed controlled diets allowed us to further constrain model parameter values and evaluate model predictions. Both models reliably predicted the δ2H and δ18O values of body water and of hair. Moreover, the isotope data allowed us to better quantify values for two critical variables in the models: the δ2H and δ18O values of gut water and the 18O isotope fractionation associated with a carbonyl oxygen-water interaction in the gut (αow). Our modeling efforts indicated that better predictions for body water and hair isotope values were achieved by making the isotopic composition of gut water approached that of body water. Additionally, the value of αow was 1.0164, in close agreement with the only other previously measured observation (microbial spore cell walls), suggesting robustness of this fractionation factor across different biological systems. PMID:22553163

  13. Hydrogen and oxygen isotope ratios in body water and hair: modeling isotope dynamics in nonhuman primates.

    PubMed

    O'Grady, Shannon P; Valenzuela, Luciano O; Remien, Christopher H; Enright, Lindsey E; Jorgensen, Matthew J; Kaplan, Jay R; Wagner, Janice D; Cerling, Thure E; Ehleringer, James R

    2012-07-01

    The stable isotopic composition of drinking water, diet, and atmospheric oxygen influence the isotopic composition of body water ((2)H/(1)H, (18)O/(16)O expressed as δ(2) H and δ(18)O). In turn, body water influences the isotopic composition of organic matter in tissues, such as hair and teeth, which are often used to reconstruct historical dietary and movement patterns of animals and humans. Here, we used a nonhuman primate system (Macaca fascicularis) to test the robustness of two different mechanistic stable isotope models: a model to predict the δ(2)H and δ(18)O values of body water and a second model to predict the δ(2)H and δ(18)O values of hair. In contrast to previous human-based studies, use of nonhuman primates fed controlled diets allowed us to further constrain model parameter values and evaluate model predictions. Both models reliably predicted the δ(2)H and δ(18)O values of body water and of hair. Moreover, the isotope data allowed us to better quantify values for two critical variables in the models: the δ(2)H and δ(18)O values of gut water and the (18)O isotope fractionation associated with a carbonyl oxygen-water interaction in the gut (α(ow)). Our modeling efforts indicated that better predictions for body water and hair isotope values were achieved by making the isotopic composition of gut water approached that of body water. Additionally, the value of α(ow) was 1.0164, in close agreement with the only other previously measured observation (microbial spore cell walls), suggesting robustness of this fractionation factor across different biological systems.

  14. Tuning the Liquid-Liquid Transition by Modulating the Hydrogen-Bond Angular Flexibility in a Model for Water

    NASA Astrophysics Data System (ADS)

    Smallenburg, Frank; Sciortino, Francesco

    2015-07-01

    We propose a simple extension of the well known ST2 model for water [F. H. Stillinger and A. Rahman, J. Chem. Phys. 60, 1545 (1974)] that allows for a continuous modification of the hydrogen-bond angular flexibility. We show that the bond flexibility affects the relative thermodynamic stability of the liquid and of the hexagonal (or cubic) ice. On increasing the flexibility, the liquid-liquid critical point, which in the original ST2 model is located in the no-man's land (i.e., the region where ice is the thermodynamically stable phase) progressively moves to a temperature where the liquid is more stable than ice. Our study definitively proves that the liquid-liquid transition in the ST2 model is a genuine phenomenon, of high relevance in all tetrahedral network-forming liquids, including water.

  15. Water reactive hydrogen fuel cell power system

    DOEpatents

    Wallace, Andrew P; Melack, John M; Lefenfeld, Michael

    2014-11-25

    A water reactive hydrogen fueled power system includes devices and methods to combine reactant fuel materials and aqueous solutions to generate hydrogen. The generated hydrogen is converted in a fuel cell to provide electricity. The water reactive hydrogen fueled power system includes a fuel cell, a water feed tray, and a fuel cartridge to generate power for portable power electronics. The removable fuel cartridge is encompassed by the water feed tray and fuel cell. The water feed tray is refillable with water by a user. The water is then transferred from the water feed tray into the fuel cartridge to generate hydrogen for the fuel cell which then produces power for the user.

  16. Water reactive hydrogen fuel cell power system

    DOEpatents

    Wallace, Andrew P; Melack, John M; Lefenfeld, Michael

    2014-01-21

    A water reactive hydrogen fueled power system includes devices and methods to combine reactant fuel materials and aqueous solutions to generate hydrogen. The generated hydrogen is converted in a fuel cell to provide electricity. The water reactive hydrogen fueled power system includes a fuel cell, a water feed tray, and a fuel cartridge to generate power for portable power electronics. The removable fuel cartridge is encompassed by the water feed tray and fuel cell. The water feed tray is refillable with water by a user. The water is then transferred from the water feed tray into a fuel cartridge to generate hydrogen for the fuel cell which then produces power for the user.

  17. Water's dual nature and its continuously changing hydrogen bonds.

    PubMed

    Henchman, Richard H

    2016-09-28

    A model is proposed for liquid water that is a continuum between the ordered state with predominantly tetrahedral coordination, linear hydrogen bonds and activated dynamics and a disordered state with a continuous distribution of multiple coordinations, multiple types of hydrogen bond, and diffusive dynamics, similar to that of normal liquids. Central to water's heterogeneous structure is the ability of hydrogen to donate to either one acceptor in a conventional linear hydrogen bond or to multiple acceptors as a furcated hydrogen. Linear hydrogen bonds are marked by slow, activated kinetics for hydrogen-bond switching to more crowded acceptors and sharp first peaks in the hydrogen-oxygen radial distribution function. Furcated hydrogens, equivalent to free, broken, dangling or distorted hydrogens, have barrierless, rapid kinetics and poorly defined first peaks in their hydrogen-oxygen radial distribution function. They involve the weakest donor in a local excess of donors, such that barrierless whole-molecule vibration rapidly swaps them between the linear and furcated forms. Despite the low number of furcated hydrogens and their transient existence, they are readily created in a single hydrogen-bond switch and free up the dynamics of numerous surrounding molecules, bringing about the disordered state. Hydrogens in the ordered state switch with activated dynamics to make the non-tetrahedral coordinations of the disordered state, which can also combine to make the ordered state. Consequently, the ordered and disordered states are both connected by diffusive dynamics and differentiated by activated dynamics, bringing about water's continuous heterogeneity.

  18. Modelling Hydrogen Reduction and Hydrodeoxygenation of Oxygenates

    SciTech Connect

    Zhao, Y.; Xu, Q.; Cheah, S.

    2013-01-01

    Based on Density Functional Theory (DFT) simulations, we have studied the reduction of nickel oxide and biomass derived oxygenates (catechol, guaiacol, etc.) in hydrogen. Both the kinetic barrier and thermodynamic favorability are calculated with respect to the modeled reaction pathways. In early-stage reduction of the NiO(100) surface by hydrogen, the pull-off of the surface oxygen atom and simultaneous activation of the nearby Ni atoms coordinately dissociate the hydrogen molecules so that a water molecule can be formed, leaving an oxygen vacancy on the surface. In hydrogen reaction with oxygenates catalyzed by transition metals, hydrogenation of the aromatic carbon ring normally dominates. However, selective deoxygenation is of particular interest for practical application such as biofuel conversion. Our modeling shows that doping of the transition metal catalysts can change the orientation of oxygenates adsorbed on metal surfaces. The correlation between the selectivity of reaction and the orientation of adsorption are discussed.

  19. Tetrahedrality and hydrogen bonds in water

    NASA Astrophysics Data System (ADS)

    Székely, Eszter; Varga, Imre K.; Baranyai, András

    2016-06-01

    We carried out extensive calculations of liquid water at different temperatures and pressures using the BK3 model suggested recently [P. T. Kiss and A. Baranyai, J. Chem. Phys. 138, 204507 (2013)]. In particular, we were interested in undercooled regions to observe the propensity of water to form tetrahedral coordination of closest neighbors around a central molecule. We compared the found tetrahedral order with the number of hydrogen bonds and with the partial pair correlation functions unfolded as distributions of the closest, the second closest, etc. neighbors. We found that contrary to the number of hydrogen bonds, tetrahedrality changes substantially with state variables. Not only the number of tetrahedral arrangements increases with lowering the pressure, the density, and the temperature but the domain size of connecting tetrahedral structures as well. The difference in tetrahedrality is very pronounced between the two sides of the Widom line and even more so between the low density amorphous (LDA) and high density amorphous (HDA) phases. We observed that in liquid water and in HDA, the 5th water molecule, contrary to ice and LDA, is positioned between the first and the second coordination shell. We found no convincing evidence of structural heterogeneity or regions referring to structural transition.

  20. Hydrogen Production by Water Biophotolysis

    SciTech Connect

    Ghirardi, Maria L.; King, Paul W.; Mulder, David W.; Eckert, Carrie; Dubini, Alexandra; Maness, Pin-Ching; Yu, Jianping

    2014-01-22

    The use of microalgae for production of hydrogen gas from water photolysis has been studied for many years, but its commercialization is still limited by multiple challenges. Most of the barriers to commercialization are attributed to the existence of biological regulatory mechanisms that, under anaerobic conditions, quench the absorbed light energy, down-regulate linear electron transfer, inactivate the H2-producing enzyme, and compete for electrons with the hydrogenase. Consequently, the conversion efficiency of absorbed photons into H2 is significantly lower than its estimated potential of 12–13 %. However, extensive research continues towards addressing these barriers by either trying to understand and circumvent intracellular regulatory mechanisms at the enzyme and metabolic level or by developing biological systems that achieve prolonged H2 production albeit under lower than 12–13 % solar conversion efficiency. This chapter describes the metabolic pathways involved in biological H2 photoproduction from water photolysis, the attributes of the two hydrogenases, [FeFe] and [NiFe], that catalyze biological H2 production, and highlights research related to addressing the barriers described above. These highlights include: (a) recent advances in improving our understanding of the O2 inactivation mechanism in different classes of hydrogenases; (b) progress made in preventing competitive pathways from diverting electrons from H2 photoproduction; and (c) new developments in bypassing the non-dissipated proton gradient from down-regulating photosynthetic electron transfer. As an example of a major success story, we mention the generation of truncated-antenna mutants in Chlamydomonas and Synechocystis that address the inherent low-light saturation of photosynthesis. In addition, we highlight the rationale and progress towards coupling biological hydrogenases to non-biological, photochemical charge-separation as a means to bypass the barriers of photobiological

  1. Effect of water on hydrogen permeability

    NASA Technical Reports Server (NTRS)

    Hulligan, David; Tomazic, William A.

    1987-01-01

    Doping of hydrogen with CO and CO2 was developed to reduce hydrogen permeation in Stirling engines by forming a low permeability oxide coating on the inner surface of the heater head tubes. Although doping worked well, under certain circumstances the protective oxide could be chemically reduced by the hydrogen in the engine. Some oxygen is required in the hydrogen to prevent reduction. Eventually, all the oxygen in the hydrogen gas - whatever its source - shows up as water. This is the result of hydrogen reducing the CO, CO2, or the protective inner surface oxides. This water can condense in the engine system under the right conditions. If the concentration of water vapor is reduced to a low enough level, the hydrogen can chemically reduce the oxide coating, resulting in an increase in permeability. This work was done to define the minimum water content required to avoid this reduction in the oxide coating. The results of this testing show that a minimum of approximately 750 ppm water is required to prevent an increase in permeability of CG-27, a high temperature metal alloy selected for Stirling engine heater tubes.

  2. Thermochemical Production of Hydrogen from Water.

    ERIC Educational Resources Information Center

    Bamberger, C. E.; And Others

    1978-01-01

    Discusses the possible advantages of decomposing water by means of thermochemical cycles. Explains that, if energy consumption can be minimized, this method is capable of producing hydrogen more efficiently than electrolysis. (GA)

  3. Mathematical model of water transport in Bacon and alkaline matrix-type hydrogen-oxygen fuel cells

    NASA Technical Reports Server (NTRS)

    Prokopius, P. R.; Easter, R. W.

    1972-01-01

    Based on general mass continuity and diffusive transport equations, a mathematical model was developed that simulates the transport of water in Bacon and alkaline-matrix fuel cells. The derived model was validated by using it to analytically reproduce various Bacon and matrix-cell experimental water transport transients.

  4. Modeling the Hydrogen Bond within Molecular Dynamics

    ERIC Educational Resources Information Center

    Lykos, Peter

    2004-01-01

    The structure of a hydrogen bond is elucidated within the framework of molecular dynamics based on the model of Rahman and Stillinger (R-S) liquid water treatment. Thus, undergraduates are exposed to the powerful but simple use of classical mechanics to solid objects from a molecular viewpoint.

  5. Hydrogen production from water: Recent advances in photosynthesis research

    SciTech Connect

    Greenbaum, E.; Lee, J.W.

    1997-12-31

    The great potential of hydrogen production by microalgal water splitting is predicated on quantitative measurement of the algae`s hydrogen-producing capability, which is based on the following: (1) the photosynthetic unit size of hydrogen production; (2) the turnover time of photosynthetic hydrogen production; (3) thermodynamic efficiencies of conversion of light energy into the Gibbs free energy of molecular hydrogen; (4) photosynthetic hydrogen production from sea water using marine algae; (5) the potential for research advances using modern methods of molecular biology and genetic engineering to maximize hydrogen production. ORNL has shown that sustained simultaneous photoevolution of molecular hydrogen and oxygen can be performed with mutants of the green alga Chlamydomonas reinhardtii that lack a detectable level of the Photosystem I light reaction. This result is surprising in view of the standard two-light reaction model of photosynthesis and has interesting scientific and technological implications. This ORNL discovery also has potentially important implications for maximum thermodynamic conversion efficiency of light energy into chemical energy by green plant photosynthesis. Hydrogen production performed by a single light reaction, as opposed to two, implies a doubling of the theoretically maximum thermodynamic conversion efficiency from {approx}10% to {approx}20%.

  6. First Self-Consistent, Two-Layer Model of Near-Surface Water-Equivalent-Hydrogen on Mars

    NASA Astrophysics Data System (ADS)

    Feldman, W. C.; Pathare, A.; Prettyman, T. H.; Maurice, S.

    2015-12-01

    This study uses 9.5 years of Mars Odyssey Neutron Spectrometer (MONS) data [1]. We have used the epithermal and fast neutron count rates to determine the water-equivalent-hydrogen (WEH) content of an upper layer, Wup, having thickness D. The "crossover" technique we utilized is an improvement over previous work [2,3]. We then used Monte Carlo simulated grids of epithermal and thermal count rates spanning Wup = 1% to 15% [4] to determine the WEH content, Wdn, of a semi-infinite lower layer buried at depth, D. We also advance upon previous work by using improved deconvolution methods to reduce spatial blurring in fast and epithermal maps [5]. The resultant count-rates were digitized into a 2°x2°cylindrical grid for all WEH computations. Two sets of WEH maps will be shown. The first uses the one-layer model developed initially by Feldman et al. [6]. Comparison of the undeconvolved and deconvolved versions clearly illustrates the improvement obtained by deconvolution. We will also present the full two layer maps of Wup, Wdn, and D for the deconvolved data sets, which show: 1) contrary to our previous preliminary mapping [3], the fresh icy mid-latitude craters identified by [7] are NOT exclusively found in regions with average Wdn values that exceed the pore-filling threshold for regolith ice; 2) a maximum Wdn of about 80% by weight at the Phoenix site; 3) an isolated Wdn maximum just east of Gale crater that is centered on Aeolis Mensae; 4) a resolved Wdn maximum that overlays the Orsen Wells crater on Xanthe Terra; 5) Wdn local maxima that hug the western flanks of Olympus Mons and Elysium Mons, and 6) several Wdn maxima that cover Arabia Terra. We will present and interpret regional maps of all of these features. Refs: [1] Maurice et al. JGR, 2011; [2] Feldman et al. JGR, 2011; [3] Pathare et al. 8th Mars Conf., 2014; [4] Prettyman et al. JGR, 2004 [5] Prettyman et al. JGR, 2009; [6] Feldman et al. JGR, 2004; [7] Dundas et al. JGR, 2014.

  7. Hydrogen peroxide evolution during V-UV photolysis of water.

    PubMed

    Azrague, Kamal; Bonnefille, Eric; Pradines, Vincent; Pimienta, Véronique; Oliveros, Esther; Maurette, Marie-Thérèse; Benoit-Marquié, Florence

    2005-05-01

    Hydrogen peroxide evolution during the vacuum-ultraviolet (V-UV, 172 nm) photolysis of water is considerably affected by the presence of oxalic acid (employed as a model water pollutant) and striking differences are observed in the absence and in the presence of dioxygen.

  8. Hydrogen and Water: An Engineering, Economic and Environmental Analysis

    SciTech Connect

    Simon, A J; Daily, W; White, R G

    2010-01-06

    The multi-year program plan for the Department of Energy's Hydrogen and Fuel Cells Technology Program (USDOE, 2007a) calls for the development of system models to determine economic, environmental and cross-cutting impacts of the transition to a hydrogen economy. One component of the hydrogen production and delivery chain is water; water's use and disposal can incur costs and environmental consequences for almost any industrial product. It has become increasingly clear that due to factors such as competing water demands and climate change, the potential for a water-constrained world is real. Thus, any future hydrogen economy will need to be constructed so that any associated water impacts are minimized. This, in turn, requires the analysis and comparison of specific hydrogen production schemes in terms of their water use. Broadly speaking, two types of water are used in hydrogen production: process water and cooling water. In the production plant, process water is used as a direct input for the conversion processes (e.g. steam for Steam Methane Reforming {l_brace}SMR{r_brace}, water for electrolysis). Cooling water, by distinction, is used indirectly to cool related fluids or equipment, and is an important factor in making plant processes efficient and reliable. Hydrogen production further relies on water used indirectly to generate other feedstocks required by a hydrogen plant. This second order indirect water is referred to here as 'embedded' water. For example, electricity production uses significant quantities of water; this 'thermoelectric cooling' contributes significantly to the total water footprint of the hydrogen production chain. A comprehensive systems analysis of the hydrogen economy includes the aggregate of the water intensities from every step in the production chain including direct, indirect, and embedded water. Process and cooling waters have distinct technical quality requirements. Process water, which is typically high purity (limited dissolved

  9. Microstructure and hydrogen bonding in water-acetonitrile mixtures.

    PubMed

    Mountain, Raymond D

    2010-12-16

    The connection of hydrogen bonding between water and acetonitrile in determining the microheterogeneity of the liquid mixture is examined using NPT molecular dynamics simulations. Mixtures for six, rigid, three-site models for acetonitrile and one water model (SPC/E) were simulated to determine the amount of water-acetonitrile hydrogen bonding. Only one of the six acetonitrile models (TraPPE-UA) was able to reproduce both the liquid density and the experimental estimates of hydrogen bonding derived from Raman scattering of the CN stretch band or from NMR quadrupole relaxation measurements. A simple modification of the acetonitrile model parameters for the models that provided poor estimates produced hydrogen-bonding results consistent with experiments for two of the models. Of these, only one of the modified models also accurately determined the density of the mixtures. The self-diffusion coefficient of liquid acetonitrile provided a final winnowing of the modified model and the successful, unmodified model. The unmodified model is provisionally recommended for simulations of water-acetonitrile mixtures.

  10. Observations of Hydrogen and Oxygen Isotopes in Leaf Water Confirm the Craig-Gordon Model under Wide-Ranging Environmental Conditions1

    PubMed Central

    Roden, John S.; Ehleringer, James R.

    1999-01-01

    The Craig-Gordon evaporative enrichment model of the hydrogen (δD) and oxygen (δ18O) isotopes of water was tested in a controlled-environment gas exchange cuvette over a wide range (400‰ δD and 40‰ δ18O) of leaf waters. (Throughout this paper we use the term “leaf water” to describe the site of evaporation, which should not be confused with “bulk leaf water” a term used exclusively for uncorrected measurements obtained from whole leaf water extractions.) Regardless of how the isotopic composition of leaf water was achieved (i.e. by changes in source water, atmospheric vapor δD or δ18O, vapor pressure gradients, or combinations of all three), a modified version of the Craig-Gordon model was shown to be sound in its ability to predict the δD and δ18O values of water at the site of evaporation. The isotopic composition of atmospheric vapor was shown to have profound effects on the δD and δ18O of leaf water and its influence was dependent on vapor pressure gradients. These results have implications for conditions in which the isotopic composition of atmospheric vapor is not in equilibrium with source water, such as experimental systems that grow plants under isotopically enriched water regimes. The assumptions of steady state were also tested and found not to be a major limitation for the utilization of the leaf water model under relatively stable environmental conditions. After a major perturbation in the δD and δ18O of atmospheric vapor, the leaf reached steady state in approximately 2 h, depending on vapor pressure gradients. Following a step change in source water, the leaf achieved steady state in 24 h, with the vast majority of changes occurring in the first 3 h. Therefore, the Craig-Gordon model is a useful tool for understanding the environmental factors that influence the hydrogen and oxygen isotopic composition of leaf water as well as the organic matter derived from leaf water. PMID:10444100

  11. Hydrogen isotope separation from water

    DOEpatents

    Jensen, R.J.

    1975-09-01

    A process for separating tritium from tritium-containing water or deuterium enrichment from water is described. The process involves selective, laser-induced two-photon excitation and photodissociation of those water molecules containing deuterium or tritium followed by immediate reaction of the photodissociation products with a scavenger gas which does not substantially absorb the laser light. The reaction products are then separated from the undissociated water. (auth)

  12. HYDROGEN ELECTROLYZER FLOW DISTRIBUTOR MODEL

    SciTech Connect

    Shadday, M

    2006-09-28

    The hybrid sulfur process (HyS) hydrogen electrolyzer consists of a proton exchange membrane (PEM) sandwiched between two porous graphite layers. An aqueous solution of sulfuric acid with dissolved SO{sub 2} gas flows parallel to the PEM through the porous graphite layer on the anode side of the electrolyzer. A flow distributor, consisting of a number of parallel channels acting as headers, promotes uniform flow of the anolyte fluid through the porous graphite layer. A numerical model of the hydraulic behavior of the flow distributor is herein described. This model was developed to be a tool to aid the design of flow distributors. The primary design objective is to minimize spatial variations in the flow through the porous graphite layer. The hydraulic data from electrolyzer tests consists of overall flowrate and pressure drop. Internal pressure and flow distributions are not measured, but these details are provided by the model. The model has been benchmarked against data from tests of the current electrolyzer. The model reasonably predicts the viscosity effect of changing the fluid from water to an aqueous solution of 30 % sulfuric acid. The permeability of the graphite layer was the independent variable used to fit the model to the test data, and the required permeability for a good fit is within the range literature values for carbon paper. The model predicts that reducing the number of parallel channels by 50 % will substantially improve the uniformity of the flow in the porous graphite layer, while maintaining an acceptable pressure drop across the electrolyzer. When the size of the electrolyzer is doubled from 2.75 inches square to 5.5 inches square, the same number of channels as in the current design will be adequate, but it is advisable to increase the channel cross-sectional flow area. This is due to the increased length of the channels.

  13. Modelling of zirconium alloy hydrogenation

    NASA Astrophysics Data System (ADS)

    Zaika, Yury V.; Rodchenkova, Natalia I.

    2016-11-01

    Zirconium alloys are the construction materials for critical elements in active zones of nuclear power reactors. During the operation of reactors such materials are subject to hydrogenation. Hydrogenation results in a decrease of alloy plasticity and cracking resistance. The formation of brittle hydrides at crack tips can result in severe embrittlement. One of the most important requirements for the reactor's active zone materials is low hydrogen absorptivity. The mathematical model of hydride layer formation and growth is developed. The problem is to determine the dynamics of the free boundary of phase interface and the distributions of hydrogen concentration in hydride and in solution. Iterative computational algorithm for solving the nonlinear boundary-value problem with the Stefan condition based on implicit difference schemes is developed.

  14. Hydrogen bonding and induced dipole moments in water: predictions from the Gaussian charge polarizable model and Car-Parrinello molecular dynamics.

    PubMed

    Dyer, Peter J; Cummings, Peter T

    2006-10-14

    We compare a new classical water model, which features Gaussian charges and polarizability (GCPM) with ab initio Car-Parrinello molecular dynamics (CPMD) simulations. We compare the total dipole moment, the total dipole moment distribution, and degree of hydrogen bonding at ambient to supercritical conditions. We also compared the total dipole moment calculated from both the electron density (partitioning the electron density among molecules based on a zero electron flux condition), and from the center of localized Wannier function centers (WFCs). Compared to CPMD, we found that GCPM overpredicts the dipole moment derived by partitioning the electron density and underpredicts that obtained from the WFCs, but exhibits similar trends and distribution of values. We also found that GCPM predicted similar degrees of hydrogen bonding compared to CPMD and has a similar structure.

  15. Effect Of Water On Permeation By Hydrogen

    NASA Technical Reports Server (NTRS)

    Tomazic, William A.; Hulligan, David

    1988-01-01

    Water vapor in working fluid equilibrates with permeability-reducing oxides in metal parts. Report describes study of effects of water on permeation of heater-head tubes by hydrogen in Stirling engine. Experiments performed to determine minimum concentration of oxygen and/or oxygen-bearing gas maintaining oxide coverage adequate for low permeability. Tests showed 750 ppm or more of water effective in maintaining stable, low permeability.

  16. Hydrogen bonds in methane-water clusters.

    PubMed

    Salazar-Cano, Juan-Ramón; Guevara-García, Alfredo; Vargas, Rubicelia; Restrepo, Albeiro; Garza, Jorge

    2016-08-24

    Characterization of hydrogen bonds in CH4-(H2O)12 clusters was carried out by using several quantum chemistry tools. An initial stochastic search provided around 2 500 000 candidate structures, then, using a convex-hull polygon criterion followed by gradient based optimization under the Kohn-Sham scheme, a total of 54 well defined local minima were located in the Potential Energy Surface. These structures were further analyzed through second-order many-body perturbation theory with an extended basis set at the MP2/6-311++G(d,p) level. Our analysis of Gibbs energies at several temperatures clearly suggests a structural preference toward compact water clusters interacting with the external methane molecule, instead of the more commonly known clathrate-like structures. This study shows that CH4-(H2O)12 clusters may be detected at temperatures up to 179 K, this finding provides strong support to a recently postulated hypothesis that suggests that methane-water clusters could be present in Mars at these conditions. Interestingly, we found that water to water hydrogen bonding is strengthened in the mixed clusters when compared to the isolated water dimer, which in turn leads to a weakening of the methane to water hydrogen bonding when compared to the CH4-(H2O) dimer. Finally, our evidence places a stern warning about the abilities of popular geometrical criteria to determine the existence of hydrogen bonds.

  17. Thermochemical method for producing hydrogen from water

    SciTech Connect

    Fujii, K.; Kondo, W.; Kumagai, T.

    1980-02-12

    A closed system for obtaining hydrogen from water is provided by combining a first step of obtaining hydrogen by reacting water and ferrous halide, a second step of converting triiron tetraoxide produced as a by-product in the first step to ferrous sulfate, a third step of obtaining oxygen and by-products by thermally decomposing said ferrous sulfate, and a fourth step of returning said by-products by thermally decomposing said ferrous sulfate, and a fourth step of returning said by-products obtained in the third step to any of the previous steps.

  18. Modeling efficiency and water balance in PEM fuel cell systems with liquid fuel processing and hydrogen membranes

    NASA Astrophysics Data System (ADS)

    Pearlman, Joshua B.; Bhargav, Atul; Shields, Eric B.; Jackson, Gregory S.; Hearn, Patrick L.

    Integrating PEM fuel cells effectively with liquid hydrocarbon reforming requires careful system analysis to assess trade-offs associated with H 2 production, purification, and overall water balance. To this end, a model of a PEM fuel cell system integrated with an autothermal reformer for liquid hydrocarbon fuels (modeled as C 12H 23) and with H 2 purification in a water-gas-shift/membrane reactor is developed to do iterative calculations for mass, species, and energy balances at a component and system level. The model evaluates system efficiency with parasitic loads (from compressors, pumps, and cooling fans), system water balance, and component operating temperatures/pressures. Model results for a 5-kW fuel cell generator show that with state-of-the-art PEM fuel cell polarization curves, thermal efficiencies >30% can be achieved when power densities are low enough for operating voltages >0.72 V per cell. Efficiency can be increased by operating the reformer at steam-to-carbon ratios as high as constraints related to stable reactor temperatures allow. Decreasing ambient temperature improves system water balance and increases efficiency through parasitic load reduction. The baseline configuration studied herein sustained water balance for ambient temperatures ≤35 °C at full power and ≤44 °C at half power with efficiencies approaching ∼27 and ∼30%, respectively.

  19. Hydrogen-Rich Water Intake Accelerates Oral Palatal Wound Healing via Activation of the Nrf2/Antioxidant Defense Pathways in a Rat Model

    PubMed Central

    Orihuela-Campos, Rita Cristina; Fukui, Makoto; Ito, Hiro-O

    2016-01-01

    The wound healing process attempts to restore the integrity and function of the injured tissue. Additionally, proinflammatory cytokines, growth factors, and oxidative stress play important roles in wound healing. The aim of this study was to determine whether hydrogen-rich water intake induces the activation of the Nrf2/antioxidant defense pathway in rat palatal tissue, thereby reducing systemic oxidative stress and proinflammatory cytokine levels and promoting healing-associated genes. A circular excisional wound was created in the oral palatal region, and the wound healing process was observed. The rats were divided into two experimental groups in which either hydrogen-rich water or distilled water was consumed. In the drinking hydrogen-rich water, the palatal wound healing process was accelerated compared to that in the control group. As molecular hydrogen upregulated the Nrf2 pathway, systemic oxidative stresses were decreased by the activation of antioxidant activity. Furthermore, hydrogen-rich water intake reduced proinflammatory cytokine levels and promoted the expression of healing-associated factors in rat palatal tissue. In conclusion, hydrogen-rich water intake exhibited multiple beneficial effects through activation of the Nrf2/antioxidant defense pathway. The results of this study support the hypothesis that oral administration of hydrogen-rich water benefits the wound healing process by decreasing oxidative stress and inflammatory responses. PMID:26798423

  20. Hydrogen-Rich Water Intake Accelerates Oral Palatal Wound Healing via Activation of the Nrf2/Antioxidant Defense Pathways in a Rat Model.

    PubMed

    Tamaki, Naofumi; Orihuela-Campos, Rita Cristina; Fukui, Makoto; Ito, Hiro-O

    2016-01-01

    The wound healing process attempts to restore the integrity and function of the injured tissue. Additionally, proinflammatory cytokines, growth factors, and oxidative stress play important roles in wound healing. The aim of this study was to determine whether hydrogen-rich water intake induces the activation of the Nrf2/antioxidant defense pathway in rat palatal tissue, thereby reducing systemic oxidative stress and proinflammatory cytokine levels and promoting healing-associated genes. A circular excisional wound was created in the oral palatal region, and the wound healing process was observed. The rats were divided into two experimental groups in which either hydrogen-rich water or distilled water was consumed. In the drinking hydrogen-rich water, the palatal wound healing process was accelerated compared to that in the control group. As molecular hydrogen upregulated the Nrf2 pathway, systemic oxidative stresses were decreased by the activation of antioxidant activity. Furthermore, hydrogen-rich water intake reduced proinflammatory cytokine levels and promoted the expression of healing-associated factors in rat palatal tissue. In conclusion, hydrogen-rich water intake exhibited multiple beneficial effects through activation of the Nrf2/antioxidant defense pathway. The results of this study support the hypothesis that oral administration of hydrogen-rich water benefits the wound healing process by decreasing oxidative stress and inflammatory responses.

  1. Photoassisted generation of hydrogen from water

    SciTech Connect

    Mueller-westerhoff, U.T.; Nazzal, A.I.

    1983-04-12

    Hydrogen is generated from water containing acid by passing electric current through it, using as the cathode a semiconductor exposed to light and having a transition metal metallocenophane compound attached to the surface of the cathode by means of a polymer.

  2. Renewable hydrogen production by photosynthetic water splitting

    SciTech Connect

    Greenbaum, E.; Lee, J.W.

    1998-06-01

    This mission-oriented research project is focused on the production of renewable hydrogen. The authors have demonstrated that certain unicellular green algae are capable of sustained simultaneous photoproduction of hydrogen and oxygen by light-activated photosynthetic water splitting. It is the goal of this project to develop a practical chemical engineering system for the development of an economic process that can be used to produce renewable hydrogen. There are several fundamental problems that need to be solved before the application of this scientific knowledge can be applied to the development a practical process: (I) maximizing net thermodynamic conversion efficiency of light energy into hydrogen energy, (2) development of oxygen-sensitive hydrogenase-containing mutants, and (3) development of bioreactors that can be used in a real-world chemical engineering process. The authors are addressing each of these problems here at ORNL and in collaboration with their research colleagues at the National Renewable Energy Laboratory, the University of California, Berkeley, and the University of Hawaii. This year the authors have focused on item 1 above. In particular, they have focused on the question of how many light reactions are required to split water to molecular hydrogen and oxygen.

  3. Quantum Cluster Equilibrium Theory Applied in Hydrogen Bond Number Studies of Water. 1. Assessment of the Quantum Cluster Equilibrium Model for Liquid Water.

    PubMed

    Lehmann, S B C; Spickermann, C; Kirchner, B

    2009-06-09

    Different cluster sets containing only 2-fold coordinated water, 2- and 3-fold coordinated water, and 2-fold, 3-fold, and tetrahedrally coordinated water molecules were investigated by applying second-order Møller-Plesset perturbation theory and density functional theory based on generalized gradient approximation functionals in the framework of the quantum cluster equilibrium theory. We found an improvement of the calculated isobars at low temperatures if tetrahedrally coordinated water molecules were included in the set of 2-fold hydrogen-bonded clusters. This was also reflected in a reduced parameter for the intercluster interaction. If all parameters were kept constant and only the electronic structure methods were varied, large basis set dependencies in the liquid state for the density functional theory results were found. The behavior of the intercluster parameter was also examined for the case that cooperative effects were neglected. The values were 3 times as large as in the calculations including the total electronic structure. Furthermore, these effects are more severe in the tetrahedrally coordinated clusters. Different populations were considered, one weighted by the total number of clusters and one depending on the monomers.

  4. Hydrogen production by the decomposition of water

    DOEpatents

    Hollabaugh, Charles M.; Bowman, Melvin G.

    1981-01-01

    How to produce hydrogen from water was a problem addressed by this invention. The solution employs a combined electrolytical-thermochemical sulfuric acid process. Additionally, high purity sulfuric acid can be produced in the process. Water and SO.sub.2 react in electrolyzer (12) so that hydrogen is produced at the cathode and sulfuric acid is produced at the anode. Then the sulfuric acid is reacted with a particular compound M.sub.r X.sub.s so as to form at least one water insoluble sulfate and at least one water insoluble oxide of molybdenum, tungsten, or boron. Water is removed by filtration; and the sulfate is decomposed in the presence of the oxide in sulfate decomposition zone (21), thus forming SO.sub.3 and reforming M.sub.r X.sub.s. The M.sub.r X.sub.s is recycled to sulfate formation zone (16). If desired, the SO.sub.3 can be decomposed to SO.sub.2 and O.sub.2 ; and the SO.sub.2 can be recycled to electrolyzer (12) to provide a cycle for producing hydrogen.

  5. Using permeable membranes to produce hydrogen and oxygen from water

    NASA Technical Reports Server (NTRS)

    Sanders, A. P.; Williams, R. J.; Downs, W. R.; Mcbryar, H.

    1975-01-01

    Concept may make it profitable to obtain hydrogen fuel from water. Laboratory tests have demonstrated that method enables decomposition of water several orders of magnitude beyond equilibrium state where only small amounts of free hydrogen are present.

  6. Photocatalytic generation of hydrogen from water

    NASA Technical Reports Server (NTRS)

    Bottoms, W. R.; Miles, R. B.

    1976-01-01

    A concept designed to overcome the problems encountered when using photodissociation for the generation of hydrogen is discussed. The problems limiting the efficiency of photodissociation of water are the separation of the photolysis products and the high energy photons necessary for the reaction. It is shown that the dissociation energy of a large number of molecules is catalytically reduced when these molecules are in intimate contact with the surface of certain metals. It is proposed to develop a surface which will take advantage of this catalytic shift in dissociation energies to reduce the photon energy required to produce hydrogen. This same catalytic surface can be used to separate the reaction products if it is made so that one of the dissociations products is soluble in the metal and others are not. This condition is met by many metal systems such as platinum group metals which have been used commercially to separate hydrogen from other gases and liquids.

  7. Enzymatic Hydrogen Production from Starch and Water

    SciTech Connect

    Zhang, Y.-H. Percival; Evans, Barbara R; Mielenz, Jonathan R; Hopkins, Robert C.; Adams, Michael W. W.

    2007-01-01

    A novel enzymatic reaction was conducted for producing hydrogen from starch and water at 30oC. The overall reaction comprised of 13 enzymes, 1 cofactor (NADP+), and phosphate was driven by energy stored in carbohydrate starch according to the overall stoichiometry stoichiometric reaction of C6H10O5 (l) + 7 H2O (l) --> 12 H2 (g) + 6 CO2 (g). It is spontaneous and unidirectional because of negative Gibbs free energy and the removal of gaseous products from the aqueous reaction solution. With technology improvement and integration with fuel cells, this technology would be suitable for mobile applications and also solve the challenges associated with hydrogen storage, distribution, and infrastructure in a hydrogen economy.

  8. INTEGRATED HYDROGEN STORAGE SYSTEM MODEL

    SciTech Connect

    Hardy, B

    2007-11-16

    Hydrogen storage is recognized as a key technical hurdle that must be overcome for the realization of hydrogen powered vehicles. Metal hydrides and their doped variants have shown great promise as a storage material and significant advances have been made with this technology. In any practical storage system the rate of H2 uptake will be governed by all processes that affect the rate of mass transport through the bed and into the particles. These coupled processes include heat and mass transfer as well as chemical kinetics and equilibrium. However, with few exceptions, studies of metal hydrides have focused primarily on fundamental properties associated with hydrogen storage capacity and kinetics. A full understanding of the complex interplay of physical processes that occur during the charging and discharging of a practical storage system requires models that integrate the salient phenomena. For example, in the case of sodium alanate, the size of NaAlH4 crystals is on the order of 300nm and the size of polycrystalline particles may be approximately 10 times larger ({approx}3,000nm). For the bed volume to be as small as possible, it is necessary to densely pack the hydride particles. Even so, in packed beds composed of NaAlH{sub 4} particles alone, it has been observed that the void fraction is still approximately 50-60%. Because of the large void fraction and particle to particle thermal contact resistance, the thermal conductivity of the hydride is very low, on the order of 0.2 W/m-{sup o}C, Gross, Majzoub, Thomas and Sandrock [2002]. The chemical reaction for hydrogen loading is exothermic. Based on the data in Gross [2003], on the order of 10{sup 8}J of heat of is released for the uptake of 5 kg of H{sub 2}2 and complete conversion of NaH to NaAlH{sub 4}. Since the hydride reaction transitions from hydrogen loading to discharge at elevated temperatures, it is essential to control the temperature of the bed. However, the low thermal conductivity of the hydride

  9. Molecular simulation and macroscopic modeling of the diffusion of hydrogen, carbon monoxide and water in heavy n-alkane mixtures.

    PubMed

    Makrodimitri, Zoi A; Unruh, Dominik J M; Economou, Ioannis G

    2012-03-28

    The self-diffusion coefficient of hydrogen (H(2)), carbon monoxide (CO) and water (H(2)O) in n-alkanes was studied by molecular dynamics simulation. Diffusion in a few pure n-alkanes (namely n-C(8), n-C(20), n-C(64) and n-C(96)) was examined. In addition, binary n-C(12)-n-C(96) mixtures with various compositions as well as more realistic five- and six-n-alkane component mixtures were simulated. In all cases, the TraPPE united atom force field was used for the n-alkane molecules. The force field for the mixture of n-alkanes was initially validated against experimental density values and was shown to be accurate. Moreover, macroscopic correlations for predicting diffusion coefficient of H(2), CO and H(2)O in n-alkanes and mixtures of n-alkanes were developed. The functional form of the correlation was based on the rough hard sphere theory (RHS). The correlation was applied to simulation data and an absolute average deviation (AAD) of 5.8% for pure n-alkanes and 3.4% for n-alkane mixtures was obtained. Correlation parameters vary in a systematic way with carbon number and so they can be used to provide predictions in the absence of any experimental or molecular simulation data. Finally, in order to reduce the number of adjustable parameters, for the n-alkane mixtures the "pseudo-carbon number" approach was used. This approach resulted in relatively higher deviation from MD simulation data (AAD of 18.2%); however, it provides a convenient and fast method to predict diffusion coefficients. The correlations developed here are expected to be useful for engineering calculations related to the design of the Gas-to-Liquid process.

  10. Hydrogen in drinking water reduces dopaminergic neuronal loss in the 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine mouse model of Parkinson's disease.

    PubMed

    Fujita, Kyota; Seike, Toshihiro; Yutsudo, Noriko; Ohno, Mizuki; Yamada, Hidetaka; Yamaguchi, Hiroo; Sakumi, Kunihiko; Yamakawa, Yukiko; Kido, Mizuho A; Takaki, Atsushi; Katafuchi, Toshihiko; Tanaka, Yoshinori; Nakabeppu, Yusaku; Noda, Mami

    2009-09-30

    It has been shown that molecular hydrogen (H(2)) acts as a therapeutic antioxidant and suppresses brain injury by buffering the effects of oxidative stress. Chronic oxidative stress causes neurodegenerative diseases such as Parkinson's disease (PD). Here, we show that drinking H(2)-containing water significantly reduced the loss of dopaminergic neurons in PD model mice using both acute and chronic administration of 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP). The concentration-dependency of H(2) showed that H(2) as low as 0.08 ppm had almost the same effect as saturated H(2) water (1.5 ppm). MPTP-induced accumulation of cellular 8-oxoguanine (8-oxoG), a marker of DNA damage, and 4-hydroxynonenal (4-HNE), a marker of lipid peroxidation were significantly decreased in the nigro-striatal dopaminergic pathway in mice drinking H(2)-containing water, whereas production of superoxide (O(2)*(-)) detected by intravascular injection of dihydroethidium (DHE) was not reduced significantly. Our results indicated that low concentration of H(2) in drinking water can reduce oxidative stress in the brain. Thus, drinking H(2)-containing water may be useful in daily life to prevent or minimize the risk of life style-related oxidative stress and neurodegeneration.

  11. Pyrene: hydrogenation, hydrogen evolution, and π-band model.

    PubMed

    Rasmussen, Jakob Arendt; Henkelman, Graeme; Hammer, Bjørk

    2011-04-28

    We present a theoretical investigation of the hydrogenation of pyrene and of the subsequent molecular hydrogen evolution. Using density functional theory (DFT) at the GGA-PBE level, the chemical binding of atomic hydrogen to pyrene is found to be exothermic by up to 1.6 eV with a strong site dependence. The edge C atoms are found most reactive. The barrier for the formation of the hydrogen-pyrene bond is small, down to 0.06 eV. A second hydrogen binds barrierless at many sites. The most stable structure of dihydrogenpyrene is more stable by 0.64 eV than pyrene plus a molecular hydrogen molecule and a large barrier of 3.7 eV for the molecular hydrogen evolution is found. Using a simple tight-binding model we demonstrate that the projected density of π-states can be used to predict the most stable binding sites for hydrogen atoms and the model is used to investigate the most favorable binding sites on more hydrogenated pyrene molecules and on coronene. Some of the DFT calculations were complemented with hybrid-DFT (PBE0) showing a general agreement between the DFT and hybrid-DFT results.

  12. Hydrogen production through solar energy water electrolysis

    NASA Astrophysics Data System (ADS)

    Dini, D.

    Water electrolysis systems are seen as the principal means of producing a large amount of hydrogen in the future. Hydrogen energy production from direct solar energy conversion facilities located on the shores of oceans and lakes is discussed. The electrolysis interface is shown to be conveniently adapted to direct solar energy conversion; this, however, will depend on technical and economic feasibility aspects as they emerge from the research phases. The basic requirements for relatively immense solar collection areas for large-scale central conversion facilities, with widely variable electricity charges, are outlined. The operation of electrolysis and photovoltaic array combination is verified at various insolation levels. It is pointed out that solar cell arrays and electrolyzers are producing the expected results with solar energy inputs that are continuously varying.

  13. Counting peptide-water hydrogen bonds in unfolded proteins.

    PubMed

    Gong, Haipeng; Porter, Lauren L; Rose, George D

    2011-02-01

    It is often assumed that the peptide backbone forms a substantial number of additional hydrogen bonds when a protein unfolds. We challenge that assumption in this article. Early surveys of hydrogen bonding in proteins of known structure typically found that most, but not all, backbone polar groups are satisfied, either by intramolecular partners or by water. When the protein is folded, these groups form approximately two hydrogen bonds per peptide unit, one donor or acceptor for each carbonyl oxygen or amide hydrogen, respectively. But when unfolded, the backbone chain is often believed to form three hydrogen bonds per peptide unit, one partner for each oxygen lone pair or amide hydrogen. This assumption is based on the properties of small model compounds, like N-methylacetamide, or simply accepted as self-evident fact. If valid, a chain of N residues would have approximately 2N backbone hydrogen bonds when folded but 3N backbone hydrogen bonds when unfolded, a sufficient difference to overshadow any uncertainties involved in calculating these per-residue averages. Here, we use exhaustive conformational sampling to monitor the number of H-bonds in a statistically adequate population of blocked polyalanyl-six-mers as the solvent quality ranges from good to poor. Solvent quality is represented by a scalar parameter used to Boltzmann-weight the population energy. Recent experimental studies show that a repeating (Gly-Ser) polypeptide undergoes a denaturant-induced expansion accompanied by breaking intramolecular peptide H-bonds. Results from our simulations augment this experimental finding by showing that the number of H-bonds is approximately conserved during such expansion⇋compaction transitions.

  14. Materials for Hydrogen Generation via Water Electrolysis

    SciTech Connect

    Paul A. Lessing

    2007-05-01

    A review is presented of materials that could be utilized as electrolytes (and their associated electrodes and interconnect materials) in solid-state electrolysis cells to convert water (or steam) into hydrogen and oxygen. Electrolytes that function as oxygen ion conductors or proton conductors are considered for various operating temperatures from approximately 80 °C to 1000 °C. The fundamental electrochemical reactions are reviewed with some discussion of special sources of steam and DC electricity (advanced nuclear) to drive the reactions at the higher temperatures.

  15. Hydrogen bonding in water clusters and their ionized counterparts.

    PubMed

    Neela, Y Indra; Mahadevi, A Subha; Sastry, G Narahari

    2010-12-30

    Ab initio and DFT computations were carried out on four distinct hydrogen-bonded arrangements of water clusters (H(2)O)(n), n = 2-20, represented as W1D, W2D, W2DH, and W3D. The variation in the strength of hydrogen bond as a function of the chain length is studied. In all the four cases, there is a substantial cooperative interaction, albeit in different degrees. The effect of basis set superposition error (BSSE) on the complexation energy of water clusters has been analyzed. Atoms in molecules (AIM) analysis performed to evaluate the nature of the hydrogen bonding shows a high correlation between hydrogen bond strength and the trends in complexation energy. Solvated water clusters exhibit lower complexation energies compared to corresponding gas-phase geometries on PCM (polarized continuum model) optimization. The feasibility of stripping an electron or addition of an electron increases dramatically as the cluster size increases. Although W3D caged structures are stable for neutral clusters, the helical W2DH arrangement appeared to be an optimal choice for its ionized counterparts.

  16. Structure and hydrogen bond dynamics of water-dimethyl sulfoxide mixtures by computer simulations

    NASA Astrophysics Data System (ADS)

    Luzar, Alenka; Chandler, David

    1993-05-01

    We have used two different force field models to study concentrated dimethyl sulfoxide (DMSO)-water solutions by molecular dynamics. The results of these simulations are shown to compare well with recent neutron diffraction experiments using H/D isotope substitution [A. K. Soper and A. Luzar, J. Chem. Phys. 97, 1320 (1992)]. Even for the highly concentrated 1 DMSO : 2 H2O solution, the water hydrogen-hydrogen radial distribution function, gHH(r), exhibits the characteristic tetrahedral ordering of water-water hydrogen bonds. Structural information is further obtained from various partial atom-atom distribution functions, not accessible experimentally. The behavior of water radial distribution functions, gOO(r) and gOH(r) indicate that the nearest neighbor correlations among remaining water molecules in the mixture increase with increasing DMSO concentration. No preferential association of methyl groups on DMSO is detected. The pattern of hydrogen bonding and the distribution of hydrogen bond lifetimes in the simulated mixtures is further investigated. Molecular dynamics results show that DMSO typically forms two hydrogen bonds with water molecules. Hydrogen bonds between DMSO and water molecules are longer lived than water-water hydrogen bonds. The hydrogen bond lifetimes determined by reactive flux correlation function approach are about 5 and 3 ps for water-DMSO and water-water pairs, respectively, in 1 DMSO : 2 H2O mixture. In contrast, for pure water, the hydrogen bond lifetime is about 1 ps. We discuss these times in light of experimentally determined rotational relaxation times. The relative values of the hydrogen bond lifetimes are consistent with a statistical (i.e., transition state theory) interpretation.

  17. Hydrogen from the solar photolysis of water

    NASA Technical Reports Server (NTRS)

    Ryason, P. R.

    1978-01-01

    Developments related to the study of photosynthesis are examined and aspects of photosensitization by solids are considered. It is pointed out that solids photosensitization for solar photochemical fuel formation is now an extremely active research area as a consequence of the promising results obtained with semiconductor photoelectrodes. The investigation of water decomposition schemes involving heterogeneous reactions is likely to be a productive area. As is the case for photosynthesis, the known examples of water decomposition by solids photosensitization involve charge separation processes immediately following light absorption. Homogeneous photoredox reactions are also discussed, taking into account thermochemical and photochemical cycles leading to the formation of a photooxidized ion, hydrogen quantum yields in the photo-oxidation aqueous ions, and thermochemical and photochemical cycles leading to the formation of a photoreduced ion.

  18. Modeling of hydrogen diffusion in metals

    SciTech Connect

    Yang, K.; Cao, M.Z.; Wan, X.J.; Shi, C.X.

    1989-02-01

    The study of the diffusion of hydrogen in metals is very important to further understand the hydrogen embrittlement of metals. To describe the diffusion of hydrogen in metals the diffusion equation deduced from Fick's law under an ideal condition has been generally used and the effect of hydrogen trapping in metals has been neglected. In the process of hydrogen diffusion through a metal, hydrogen fills the traps continuously and the fraction of the traps filled by hydrogen, which have only little effect on the diffusion of hydrogen, may be different at different places because the distribution of hydrogen concentration may be different at different places. Thus the hydrogen diffusion coefficient in the metal may also be different at different positions, i.e., the diffusion coefficient should be affected by time in a dynamic process of hydrogen diffusion through a metal. But in the previous analyses, the above fact is not considered and the hydrogen diffusion coefficient is generally taken as a constant. In the present paper a new model of hydrogen diffusion in metals in which the effect of time is taken into account is developed.

  19. Modeling leaks from liquid hydrogen storage systems.

    SciTech Connect

    Winters, William Stanley, Jr.

    2009-01-01

    This report documents a series of models for describing intended and unintended discharges from liquid hydrogen storage systems. Typically these systems store hydrogen in the saturated state at approximately five to ten atmospheres. Some of models discussed here are equilibrium-based models that make use of the NIST thermodynamic models to specify the states of multiphase hydrogen and air-hydrogen mixtures. Two types of discharges are considered: slow leaks where hydrogen enters the ambient at atmospheric pressure and fast leaks where the hydrogen flow is usually choked and expands into the ambient through an underexpanded jet. In order to avoid the complexities of supersonic flow, a single Mach disk model is proposed for fast leaks that are choked. The velocity and state of hydrogen downstream of the Mach disk leads to a more tractable subsonic boundary condition. However, the hydrogen temperature exiting all leaks (fast or slow, from saturated liquid or saturated vapor) is approximately 20.4 K. At these temperatures, any entrained air would likely condense or even freeze leading to an air-hydrogen mixture that cannot be characterized by the REFPROP subroutines. For this reason a plug flow entrainment model is proposed to treat a short zone of initial entrainment and heating. The model predicts the quantity of entrained air required to bring the air-hydrogen mixture to a temperature of approximately 65 K at one atmosphere. At this temperature the mixture can be treated as a mixture of ideal gases and is much more amenable to modeling with Gaussian entrainment models and CFD codes. A Gaussian entrainment model is formulated to predict the trajectory and properties of a cold hydrogen jet leaking into ambient air. The model shows that similarity between two jets depends on the densimetric Froude number, density ratio and initial hydrogen concentration.

  20. Structure and Hydrogen Bonding of Water in Polyacrylate Gels: Effects of Polymer Hydrophilicity and Water Concentration.

    PubMed

    Mani, Sriramvignesh; Khabaz, Fardin; Godbole, Rutvik V; Hedden, Ronald C; Khare, Rajesh

    2015-12-10

    The ability to tune the hydrophilicity of polyacrylate copolymers by altering their composition makes these materials attractive candidates for membranes used to separate alcohol-water mixtures. The separation behavior of these polyacrylate membranes is governed by a complex interplay of factors such as water and alcohol concentrations, water structure in the membrane, polymer hydrophilicity, and temperature. We use molecular dynamics simulations to investigate the effect of polymer hydrophilicity and water concentration on the structure and dynamics of water molecules in the polymer matrix. Samples of poly(n-butyl acrylate) (PBA), poly(2-hydroxyethyl acrylate) (PHEA), and a 50/50 copolymer of BA and HEA were synthesized in laboratory, and their properties were measured. Model structures of these systems were validated by comparing the simulated values of their volumetric properties with the experimental values. Molecular simulations of polyacrylate gels swollen in water and ethanol mixtures showed that water exhibits very different affinities toward the different (carbonyl, alkoxy, and hydroxyl) functional groups of the polymers. Water molecules are well dispersed in the system at low concentrations and predominantly form hydrogen bonds with the polymer. However, water forms large clusters at high concentrations along with the predominant formation of water-water hydrogen bonds and the acceleration of hydrogen bond dynamics.

  1. Process for the production of hydrogen from water

    DOEpatents

    Miller, William E.; Maroni, Victor A.; Willit, James L.

    2010-05-25

    A method and device for the production of hydrogen from water and electricity using an active metal alloy. The active metal alloy reacts with water producing hydrogen and a metal hydroxide. The metal hydroxide is consumed, restoring the active metal alloy, by applying a voltage between the active metal alloy and the metal hydroxide. As the process is sustainable, only water and electricity is required to sustain the reaction generating hydrogen.

  2. Insights into hydrogen bonding via ice interfaces and isolated water

    NASA Astrophysics Data System (ADS)

    Shultz, Mary Jane; Bisson, Patrick; Vu, Tuan Hoang

    2014-11-01

    Water in a confined environment has a combination of fewer available configurations and restricted mobility. Both affect the spectroscopic signature. In this work, the spectroscopic signature of water in confined environments is discussed in the context of competing models for condensed water: (1) as a system of intramolecular coupled molecules or (2) as a network with intermolecular dipole-dipole coupled O-H stretches. Two distinct environments are used: the confined asymmetric environment at the ice surface and the near-isolated environment of water in an infrared transparent matrix. Both the spectroscopy and the environment are described followed by a perspective discussion of implications for the two competing models. Despite being a small molecule, water is relatively complex; perhaps not surprisingly the results support a model that blends inter- and intramolecular coupling. The frequency, and therefore the hydrogen-bond strength, appears to be a function of donor-acceptor interaction and of longer-range dipole-dipole alignment in the hydrogen-bonded network. The O-H dipole direction depends on the local environment and reflects intramolecular O-H stretch coupling.

  3. Insights into hydrogen bonding via ice interfaces and isolated water.

    PubMed

    Shultz, Mary Jane; Bisson, Patrick; Vu, Tuan Hoang

    2014-11-14

    Water in a confined environment has a combination of fewer available configurations and restricted mobility. Both affect the spectroscopic signature. In this work, the spectroscopic signature of water in confined environments is discussed in the context of competing models for condensed water: (1) as a system of intramolecular coupled molecules or (2) as a network with intermolecular dipole-dipole coupled O-H stretches. Two distinct environments are used: the confined asymmetric environment at the ice surface and the near-isolated environment of water in an infrared transparent matrix. Both the spectroscopy and the environment are described followed by a perspective discussion of implications for the two competing models. Despite being a small molecule, water is relatively complex; perhaps not surprisingly the results support a model that blends inter- and intramolecular coupling. The frequency, and therefore the hydrogen-bond strength, appears to be a function of donor-acceptor interaction and of longer-range dipole-dipole alignment in the hydrogen-bonded network. The O-H dipole direction depends on the local environment and reflects intramolecular O-H stretch coupling.

  4. Origin of hydrophobicity and enhanced water hydrogen bond strength near purely hydrophobic solutes

    PubMed Central

    Grdadolnik, Joze; Merzel, Franci; Avbelj, Franc

    2017-01-01

    Hydrophobicity plays an important role in numerous physicochemical processes from the process of dissolution in water to protein folding, but its origin at the fundamental level is still unclear. The classical view of hydrophobic hydration is that, in the presence of a hydrophobic solute, water forms transient microscopic “icebergs” arising from strengthened water hydrogen bonding, but there is no experimental evidence for enhanced hydrogen bonding and/or icebergs in such solutions. Here, we have used the redshifts and line shapes of the isotopically decoupled IR oxygen–deuterium (O-D) stretching mode of HDO water near small purely hydrophobic solutes (methane, ethane, krypton, and xenon) to study hydrophobicity at the most fundamental level. We present unequivocal and model-free experimental proof for the presence of strengthened water hydrogen bonds near four hydrophobic solutes, matching those in ice and clathrates. The water molecules involved in the enhanced hydrogen bonds display extensive structural ordering resembling that in clathrates. The number of ice-like hydrogen bonds is 10–15 per methane molecule. Ab initio molecular dynamics simulations have confirmed that water molecules in the vicinity of methane form stronger, more numerous, and more tetrahedrally oriented hydrogen bonds than those in bulk water and that their mobility is restricted. We show the absence of intercalating water molecules that cause the electrostatic screening (shielding) of hydrogen bonds in bulk water as the critical element for the enhanced hydrogen bonding around a hydrophobic solute. Our results confirm the classical view of hydrophobic hydration. PMID:28028244

  5. Polarizability calculations on water, hydrogen, oxygen, and carbon dioxide

    NASA Technical Reports Server (NTRS)

    Nir, S.; Adams, S.; Rein, R.

    1973-01-01

    A semiclassical model of damped oscillators is used as a basis for the calculation of the dispersion of the refractive index, polarizability, and dielectric permeability in water, hydrogen, and oxygen in liquid and gaseous states, and in gaseous carbon dioxide. The absorption coefficient and the imaginary part of the refractive index are also calculated at corresponding wavelengths. A good agreement is obtained between the observed and calculated values of refractive indices, and between those of absorption coefficients in the region of absorption bands. The calculated values of oscillator strengths and damping factors are also discussed. The value of the polarizability of liquid water was about 2.8 times that of previous calculations.

  6. MODEL OF DIFFUSERS / PERMEATORS FOR HYDROGEN PROCESSING

    SciTech Connect

    Hang, T; William Jacobs, W

    2007-08-27

    Palladium-silver (Pd-Ag) diffusers are mainstays of hydrogen processing. Diffusers separate hydrogen from inert species such as nitrogen, argon or helium. The tubing becomes permeable to hydrogen when heated to more than 250 C and a differential pressure is created across the membrane. The hydrogen diffuses better at higher temperatures. Experimental or experiential results have been the basis for determining or predicting a diffuser's performance. However, the process can be mathematically modeled, and comparison to experimental or other operating data can be utilized to improve the fit of the model. A reliable model-based diffuser system design is the goal which will have impacts on tritium and hydrogen processing. A computer model has been developed to solve the differential equations for diffusion given the operating boundary conditions. The model was compared to operating data for a low pressure diffuser system. The modeling approach and the results are presented in this paper.

  7. Molecular hydrogen solvated in water – A computational study

    SciTech Connect

    Śmiechowski, Maciej

    2015-12-28

    The aqueous hydrogen molecule is studied with molecular dynamics simulations at ambient temperature and pressure conditions, using a newly developed flexible and polarizable H{sub 2} molecule model. The design and implementation of this model, compatible with an existing flexible and polarizable force field for water, is presented in detail. The structure of the hydration layer suggests that first-shell water molecules accommodate the H{sub 2} molecule without major structural distortions and two-dimensional, radial-angular distribution functions indicate that as opposed to strictly tangential, the orientation of these water molecules is such that the solute is solvated with one of the free electron pairs of H{sub 2}O. The calculated self-diffusion coefficient of H{sub 2}(aq) agrees very well with experimental results and the time dependence of mean square displacement suggests the presence of caging on a time scale corresponding to hydrogen bond network vibrations in liquid water. Orientational correlation function of H{sub 2} experiences an extremely short-scale decay, making the H{sub 2}–H{sub 2}O interaction potential essentially isotropic by virtue of rotational averaging. The inclusion of explicit polarizability in the model allows for the calculation of Raman spectra that agree very well with available experimental data on H{sub 2}(aq) under differing pressure conditions, including accurate reproduction of the experimentally noted trends with solute pressure or concentration.

  8. Hydrogen production by the decomposition of water

    DOEpatents

    Hollabaugh, C.M.; Bowman, M.G.

    A process is described for the production of hydrogen from water by a sulfuric acid process employing electrolysis and thermo-chemical decomposition. The water containing SO/sub 2/ is electrolyzed to produce H/sub 2/ at the cathode and to oxidize the SO/sub 2/ to form H/sub 2/SO/sub 4/ at the anode. After the H/sub 2/ has been separated, a compound of the type M/sub r/X/sub s/ is added to produce a water insoluble sulfate of M and a water insoluble oxide of the metal in the radical X. In the compound M/sub r/X/sub s/, M is at least one metal selected from the group consisting of Ba/sup 2 +/, Ca/sup 2 +/, Sr/sup 2 +/, La/sup 2 +/, and Pb/sup 2 +/; X is at least one radical selected from the group consisting of molybdate (MoO/sub 4//sup 2 -/), tungstate (WO/sub 4//sup 2 -/), and metaborate (BO/sub 2//sup 1 -/); and r and s are either 1, 2, or 3 depending upon the valence of M and X. The precipitated mixture is filtered and heated to a temperature sufficiently high to form SO/sub 3/ gas and to reform M/sub r/X/sub s/. The SO/sub 3/ is dissolved in a small amount of H/sub 2/O to produce concentrated H/sub 2/SO/sub 4/, and the M/sub r/X/sub s/ is recycled to the process. Alternatively, the SO/sub 3/ gas can be recycled to the beginning of the process to provide a continuous process for the production of H/sub 2/ in which only water need be added in a substantial amount. (BLM)

  9. Economics of liquid hydrogen from water electrolysis

    NASA Technical Reports Server (NTRS)

    Lin, F. N.; Moore, W. I.; Walker, S. W.

    1985-01-01

    An economical model for preliminary analysis of LH2 cost from water electrolysis is presented. The model is based on data from vendors and open literature, and is suitable for computer analysis of different scenarios for 'directional' purposes. Cost data associated with a production rate of 10,886 kg/day are presented. With minimum modification, the model can also be used to predict LH2 cost from any electrolyzer once the electrolyzer's cost data are available.

  10. Device separates hydrogen from solution in water at ambient temperatures

    NASA Technical Reports Server (NTRS)

    Albright, C. F.

    1969-01-01

    Separator decreases the partial pressure of hydrogen gas dissolved in the water produced by fuel cells containing an alkaline electrolyte. The unit eliminates the hazards associated with the release of hydrogen from water solution when the hydrostatic pressure is rapidly decreased.

  11. The Hydrogen Atom: The Rutherford Model

    NASA Astrophysics Data System (ADS)

    Tilton, Homer Benjamin

    1996-06-01

    Early this century Ernest Rutherford established the nuclear model of the hydrogen atom, presently taught as representing the best visual model after modification by Niels Bohr and Arnold Sommerfeld. It replaced the so-called "plum pudding" model of J. J. Thomson which held sway previously. While the Rutherford model represented a large step forward in our understanding of the hydrogen atom, questions remained, and still do.

  12. Photoelectrochemical hydrogen production from biomass derivatives and water.

    PubMed

    Lu, Xihong; Xie, Shilei; Yang, Hao; Tong, Yexiang; Ji, Hongbing

    2014-11-21

    Hydrogen, a clean energy carrier with high energy capacity, is a very promising candidate as a primary energy source for the future. Photoelectrochemical (PEC) hydrogen production from renewable biomass derivatives and water is one of the most promising approaches to producing green chemical fuel. Compared to water splitting, hydrogen production from renewable biomass derivatives and water through a PEC process is more efficient from the viewpoint of thermodynamics. Additionally, the carbon dioxide formed can be re-transformed into carbohydrates via photosynthesis in plants. In this review, we focus on the development of photoanodes and systems for PEC hydrogen production from water and renewable biomass derivatives, such as methanol, ethanol, glycerol and sugars. We also discuss the future challenges and opportunities for the design of the state-of-the-art photoanodes and PEC systems for hydrogen production from biomass derivatives and water.

  13. Thermochemical water decomposition. [hydrogen separation for energy applications

    NASA Technical Reports Server (NTRS)

    Funk, J. E.

    1977-01-01

    At present, nearly all of the hydrogen consumed in the world is produced by reacting hydrocarbons with water. As the supply of hydrocarbons diminishes, the problem of producing hydrogen from water alone will become increasingly important. Furthermore, producing hydrogen from water is a means of energy conversion by which thermal energy from a primary source, such as solar or nuclear fusion of fission, can be changed into an easily transportable and ecologically acceptable fuel. The attraction of thermochemical processes is that they offer the potential for converting thermal energy to hydrogen more efficiently than by water electrolysis. A thermochemical hydrogen-production process is one which requires only water as material input and mainly thermal energy, or heat, as an energy input. Attention is given to a definition of process thermal efficiency, the thermodynamics of the overall process, the single-stage process, the two-stage process, multistage processes, the work of separation and a process evaluation.

  14. Fuel from water: the photochemical generation of hydrogen from water.

    PubMed

    Han, Zhiji; Eisenberg, Richard

    2014-08-19

    Hydrogen has been labeled the fuel of the future since it contains no carbon, has the highest specific enthalpy of combustion of any chemical fuel, yields only water upon complete oxidation, and is not limited by Carnot considerations in the amount of work obtained when used in a fuel cell. To be used on the scale needed for sustainable growth on a global scale, hydrogen must be produced by the light-driven splitting of water into its elements, as opposed to reforming of methane, as is currently done. The photochemical generation of H2, which is the reductive side of the water splitting reaction, is the focus of this Account, particularly with regard to work done in the senior author's laboratory over the last 5 years. Despite seminal work done more than 30 years ago and the extensive research conducted since then on all aspects of the process, no viable system has been developed for the efficient and robust photogeneration of H2 from water using only earth abundant elements. For the photogeneration of H2 from water, a system must contain a light absorber, a catalyst, and a source of electrons. In this Account, the discovery and study of new Co and Ni catalysts are described that suggest H2 forms via a heterocoupling mechanism from a metal-hydride and a ligand-bound proton. Several complexes with redox active dithiolene ligands are newly recognized to be effective in promoting the reaction. A major new development in the work described is the use of water-soluble CdSe quantum dots (QDs) as light absorbers for H2 generation in water. Both activity and robustness of the most successful systems are impressive with turnover numbers (TONs) approaching 10(6), activity maintained over 15 days, and a quantum yield for H2 of 36% with 520 nm light. The water solubilizing capping agent for the first system examined was dihydrolipoic acid (DHLA) anion, and the catalyst was determined to be a DHLA complex of Ni(II) formed in situ. Dissociation of DHLA from the QD surface proved

  15. The water intensity of the transitional hydrogen economy

    NASA Astrophysics Data System (ADS)

    Webber, Michael E.

    2007-09-01

    The water intensity of the transitional hydrogen economy is analyzed by quantifying the direct and indirect water requirements to annually manufacture 60 billion kg of hydrogen partly by thermoelectrically powered electrolysis. It is determined that up to 143 billion gallons of water would be directly consumed as a feedstock, with a total consumption including evaporation of cooling water at power plants of 0.5 1.7 trillion gallons annually. Total water withdrawals for thermoelectric cooling (most of which is not consumed) are expected to increase by 27 97% from 195 000 million gallons/day today, depending primarily on the aggregate efficiency of electrolyzers that will be in place and the portion of hydrogen that is produced by thermoelectrically powered electrolysis. On a per unit basis, thermoelectric power generation for electrolysis will on average withdraw approximately 1100 gallons of cooling water and will consume 27 gallons of water as a feedstock and coolant for every kilogram of hydrogen that is produced using an electrolyzer that has an efficiency of 75%. Given that water withdrawals have remained steady for decades, this increase in water use represents a significant potential impact of the hydrogen economy on a critical resource, and is consequently relevant to water resource planners. Thus, if minimizing the impact of water resources is a priority and electrolysis becomes a widespread method of hydrogen production, hydrogen production would need to be from hydrogen production pathways that do not use much water (such as wind or solar), or effective water-free cooling methods (e.g. air cooling) will need to be developed and widely deployed.

  16. Inhalation of water electrolysis-derived hydrogen ameliorates cerebral ischemia-reperfusion injury in rats - A possible new hydrogen resource for clinical use.

    PubMed

    Cui, Jin; Chen, Xiao; Zhai, Xiao; Shi, Dongchen; Zhang, Rongjia; Zhi, Xin; Li, Xiaoqun; Gu, Zhengrong; Cao, Liehu; Weng, Weizong; Zhang, Jun; Wang, Liping; Sun, Xuejun; Ji, Fang; Hou, Jiong; Su, Jiacan

    2016-10-29

    Hydrogen is a kind of noble gas with the character to selectively neutralize reactive oxygen species. Former researches proved that low-concentration of hydrogen can be used to ameliorating cerebral ischemia/reperfusion injury. Hydrogen electrolyzed from water has a hydrogen concentration of 66.7%, which is much higher than that used in previous studies. And water electrolysis is a potential new hydrogen resource for regular clinical use. This study was designed and carried out for the determination of safety and neuroprotective effects of water electrolysis-derived hydrogen. Sprague-Dawley rats were used as experimental animals, and middle cerebral artery occlusion was used to make cerebral ischemia/reperfusion model. Pathologically, tissues from rats in hydrogen inhalation group showed no significant difference compared with the control group in HE staining pictures. The blood biochemical findings matched the HE staining result. TTC, Nissl, and TUNEL staining showed the significant improvement of infarction volume, neuron morphology, and neuron apoptosis in rat with hydrogen treatment. Biochemically, hydrogen inhalation decreased brain caspase-3, 3-nitrotyrosine and 8-hydroxy-2-deoxyguanosine-positive cells and inflammation factors concentration. Water electrolysis-derived hydrogen inhalation had neuroprotective effects on cerebral ischemia/reperfusion injury in rats with the effect of suppressing oxidative stress and inflammation, and it is a possible new hydrogen resource to electrolyze water at the bedside clinically.

  17. Effects of chlorine and hydrogen peroxide sanitation in low bacterial content water on biofilm formation model of poultry brooding house waterlines.

    PubMed

    Maharjan, P; Huff, G; Zhang, W; Watkins, S

    2017-02-22

    An in vitro experiment was performed to determine if biofilm would develop when polyvinylchloride (PVC) test coupons (material used for poultry waterlines) were exposed to low bacterial content warm water (≤1000 cfu/mL, test water) and also to determine if biofilm development would be influenced by adding a sanitizer. PVC sections 2.54 cm long and internal diameter of 1. 90 cm were used as test coupons to grow biofilm. Two coupons were immersed in 600 mL test water in a beaker. Nine beakers were utilized similarly with a total of 18 coupons. Three beakers (T1) were treated with a chlorine (Cl) based product (targeted to produce 2 to 4 ppm residual) and the other 3 (T2) with hydrogen peroxide a (HP) based product (targeted to produce 25 to 50 ppm residual). Three untreated beakers served as controls (T3). All beakers and coupons were placed into a water bath shaker under warm and moving water conditions mimicking poultry brooding conditions. Coupons and test water were sampled for treatments for aerobic plate count (APC). Trial 1 used test water with zero cfu bacteria/mL initial APC, whereas the Trial 2 test water initial APC was 3 log10 cfu/mL. Test water samples and coupons had no bacterial growth for all treatments on sampling occasions for Trial 1. In Trial 2, T3 (control) and T2 (HP treated) had APC growth in both test water (2.5 to 3.0 log10 cfu/mL) and on coupons (2 to 2.5 log10 cfu/cm2) on sampling d with no difference (P > 0.05) between these treatments. Whereas, T1 (Cl treated) eliminated bacteria (zero cfu/mL) in test water and inhibited biofilm growth on test coupons (≤0.2 log10 cfu/cm2) during sampling d (P < 0.05). This experiment showed that biofilm can develop in minimally contaminated water even in the presence of sanitizers, yet chlorine was more effective than hydrogen peroxide in limiting this development.

  18. [Determination of the redox potential of water saturated with hydrogen].

    PubMed

    Piskarev, I M; Ushkanov, V A; Aristova, N A; Likhachev, P P; Myslivets, T C

    2010-01-01

    It has been shown that the redox potential of water saturated with hydrogen is -500--700 mV. The time of the establishment of the potential is 24 h. The potential somewhat increases with increasing volume of hydrogen introduced to a reservoir with water and practically does not depend on the presence of additions in water, provided these additions are not reduced by hydrogen. The pH value of water does not change after the addition of water. In a glass vessel with a metallic cover resting on the side, no decrease in potential during the 2.5-month storage was observed. In plastic bottles, the content of hydrogen decreased; on storage for more than two weeks, it disappeared almost completely, and as a result, the potential increased after storage for three to four weeks to a level near zero. In an open vessel, the potential remained negative for two days.

  19. Reaction of Aluminum with Water to Produce Hydrogen - 2010 Update

    SciTech Connect

    Petrovic, John; Thomas, George

    2011-06-01

    A Study of Issues Related to the Use of Aluminum for On-Board Vehicular Hydrogen Storage The purpose of this White Paper is to describe and evaluate the potential of aluminum-water reactions for the production of hydrogen for on-board hydrogen-powered vehicle applications. Although the concept of reacting aluminum metal with water to produce hydrogen is not new, there have been a number of recent claims that such aluminum-water reactions might be employed to power fuel cell devices for portable applications such as emergency generators and laptop computers, and might even be considered for possible use as the hydrogen source for fuel cell-powered vehicles.

  20. Hydrogen bonding definitions and dynamics in liquid water.

    PubMed

    Kumar, R; Schmidt, J R; Skinner, J L

    2007-05-28

    X-ray and neutron diffractions, vibrational spectroscopy, and x-ray Raman scattering and absorption experiments on water are often interpreted in terms of hydrogen bonding. To this end a number of geometric definitions of hydrogen bonding in water have been developed. While all definitions of hydrogen bonding are to some extent arbitrary, those involving one distance and one angle for a given water dimer are unnecessarily so. In this paper the authors develop a systematic procedure based on two-dimensional potentials of mean force for defining cutoffs for a given pair of distance and angular coordinates. They also develop an electronic structure-based definition of hydrogen bonding in liquid water, related to the electronic occupancy of the antibonding OH orbitals. This definition turns out to be reasonably compatible with one of the distance-angle geometric definitions. These two definitions lead to an estimate of the number of hydrogen bonds per molecule in liquid simple point charge/extended (SPC/E) water of between 3.2 and 3.4. They also used these and other hydrogen-bond definitions to examine the dynamics of local hydrogen-bond number fluctuations, finding an approximate long-time decay constant for SPC/E water of between 0.8 and 0.9 ps, which corresponds to the time scale for local structural relaxation.

  1. Selective electrochemical generation of hydrogen peroxide from water oxidation

    SciTech Connect

    Viswanathan, Venkatasubramanian; Hansen, Heine A.; Norskov, Jens K.

    2015-10-08

    Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, we show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e– water oxidation to H2O2 and the 4e– oxidation to O2. We show that materials which bind oxygen intermediates sufficiently weakly, such as SnO2, can activate hydrogen peroxide evolution. Furthermore, we present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H2O2 evolution selectively.

  2. Selective electrochemical generation of hydrogen peroxide from water oxidation

    DOE PAGES

    Viswanathan, Venkatasubramanian; Hansen, Heine A.; Norskov, Jens K.

    2015-10-08

    Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, wemore » show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e– water oxidation to H2O2 and the 4e– oxidation to O2. We show that materials which bind oxygen intermediates sufficiently weakly, such as SnO2, can activate hydrogen peroxide evolution. Furthermore, we present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H2O2 evolution selectively.« less

  3. Process for hydrogen isotope concentration between liquid water and hydrogen gas

    DOEpatents

    Stevens, William H.

    1976-09-21

    A process for hydrogen isotope exchange and concentration between liquid water and hydrogen gas, wherein liquid water and hydrogen gas are contacted, in an exchange section, with one another and with at least one catalyst body comprising at least one metal selected from Group VIII of the Periodic Table and preferably a support therefor, the catalyst body has a liquid-water-repellent, gas permeable polymer or organic resin coating, preferably a fluorinated olefin polymer or silicone coating, so that the isotope concentration takes place by two simultaneously occurring steps, namely, ##EQU1## WHILE THE HYDROGEN GAS FED TO THE EXCHANGE SECTION IS DERIVED IN A REACTOR VESSEL FROM LIQUID WATER THAT HAS PASSED THROUGH THE EXCHANGE SECTION.

  4. Generating Hydrogen through Water Electrolysis using Concentrator Photovoltaics

    SciTech Connect

    McConnell, R.; Thompson, J.

    2005-01-01

    Hydrogen can be an important element in reducing global climate change if the feedstock and process to produce the hydrogen are carbon free. Using nuclear energy to power a high temperature water electrolysis process meets these constraints while another uses heat and electricity from solar electric concentrators. Nuclear researchers have estimated the cost of hydrogen generated in this fashion and we will compare their estimates with those we have made for generating hydrogen using electricity and waste heat from a dish concentrator photovoltaic system. The conclusion is that the costs are comparable and low enough to compete with gasoline costs in the not too distant future.

  5. Comparison of Modeled and Observed Environmental Influences on the Stable Oxygen and Hydrogen Isotope Composition of Leaf Water in Phaseolus vulgaris L. 1

    PubMed Central

    Flanagan, Lawrence B.; Comstock, Jonathan P.; Ehleringer, James R.

    1991-01-01

    In this paper we describe how a model of stable isotope fractionation processes, originally developed by H. Craig and L. I. Gordon ([1965] in E Tongiorgi, ed, Proceedings of a Conference on Stable Isotopes in Oceanographic Studies and Paleotemperature, Spoleto, Italy, pp 9-130) for evaporation of water from the ocean, can be applied to leaf transpiration. The original model was modified to account for turbulent conditions in the leaf boundary layer. Experiments were conducted to test the factors influencing the stable isotopic composition of leaf water under controlled environment conditions. At steady state, the observed leaf water isotopic composition was enriched above that of stem water with the extent of the enrichment dependent on the leaf-air vapor pressure difference (VPD) and the isotopic composition of atmospheric water vapor (AWV). The higher the VPD, the larger was the observed heavy isotope content of leaf water. At a constant VPD, leaf water was relatively depleted in heavy isotopes when exposed to AWV with a low heavy isotope composition, and leaf water was relatively enriched in heavy isotopes when exposed to AWV with a large heavy isotope composition. However, the observed heavy isotope composition of leaf water was always less than that predicted by the model. The extent of the discrepancy between the modeled and observed leaf water isotopic composition was a strong linear function of the leaf transpiration rate. PMID:16668226

  6. Sea water for hydrogen and for municipal use

    NASA Astrophysics Data System (ADS)

    Lodhi, M. A. K.

    The production of hydrogen from sea water using solar energy is discussed, and a set of parameters for the project is worked out. The energy produced by electrolysis is directly proportional to the rate of evaporation. If the water is collected in a sink reservoir from the sea and solar energy is used directly to produce hydrogen, the evaporation rate will increase and more hydraulic energy will be available. The end-product of hydrogen electrolysis is fresh water, which can be used for domestic, industrial, or agricultural purposes. Letting this water evaporate into the atmosphere might increase the humidity and lead to some environmental hazards. The cost of hydrogen production is currently greater than that of other conventional energies, despite its low transportation and distribution costs.

  7. Ionic model for highly compressed solid hydrogen

    NASA Astrophysics Data System (ADS)

    Yakub, E. S.

    2013-05-01

    We propose a simple ionic model for high-pressure conducting phase IV of solid hydrogen observed recently at room temperature. It is based on an assumption of dissociative ionization of hydrogen molecules 3H2=2H2(+)+2H(-) induced by high compression. The proposed model predicts the first order transition of molecular hydrogen solid into partly ionic conducting phase at megabar pressures and describes the temperature dependence of resistivity at room temperature. Its predictions are consistent with high temperature shock-compression experiments which exhibit conductivity of multiply shocked hydrogen. The location of phase transition line, the volume change, and the ionization degree in solid phase IV are estimated.

  8. Hydrogen generation from water using Si nanopowder fabricated from swarf

    NASA Astrophysics Data System (ADS)

    Imamura, Kentaro; Kimura, Katsuya; Fujie, Shunta; Kobayashi, Hikaru

    2016-05-01

    Si nanopowder is fabricated from Si swarf by the simple beads milling method. Si nanopowder possesses the maximum crystallite size distribution at 7 nm and the average diameter of 12 nm. Fabricated Si nanopowder easily reacts with water, resulting in generation of hydrogen. The hydrogen generation rate strongly depends on pH value of the solutions and the temperature. When the pH value and the reaction temperature are set at 13.0 and 50 °C, respectively, the hydrogen evolution rate in the initial 1 min reaches to ˜580 mL/min g, i.e., more than 1000 mL hydrogen is generated from 1 g Si nanopowder in 2 min. Hydrogen generation stops when a thick SiO2 layer is formed on the surface of Si nanopowder. Analysis of evolved hydrogen volume versus the reaction time shows that in the initial reaction period, dissolution of Si by OH- ions to form soluble H2SiO4 2- ions and hydrogen molecules is the dominant reaction, while in the subsequent period, the reaction of Si nanopowder with OH- ions forms SiO2, leading to generation of hydrogen molecules and electrons in the SiO2 conduction band. Generated electrons are accepted by water molecules, resulting in formation of hydrogen and OH- ions.

  9. Correlation of structural order, anomalous density, and hydrogen bonding network of liquid water.

    PubMed

    Bandyopadhyay, Dibyendu; Mohan, S; Ghosh, S K; Choudhury, Niharendu

    2013-07-25

    We use extensive molecular dynamics simulations employing different state-of-the-art force fields to find a common framework for comparing structural orders and density anomalies as obtained from different water models. It is found that the average number of hydrogen bonds correlates well with various order parameters as well as the temperature of maximum densities across the different models, unifying apparently disparate results from different models and emphasizing the importance of hydrogen bonding in determining anomalous properties and the structure of water. A deeper insight into the hydrogen bond network of water reveals that the solvation shell of a water molecule can be defined by considering only those neighbors that are hydrogen-bonded to it. On the basis of this view, the origin of the appearance of a non-tetrahedral peak at a higher temperature in the distribution of tetrahedral order parameters has been explained. It is found that a neighbor that is hydrogen-bonded to the central molecule is tetrahedrally coordinated even at higher temperatures. The non-tetrahedral peak at a higher temperature arises due to the strained orientation of the neighbors that are non-hydrogen-bonded to the central molecule. With the new definition of the solvation shell, liquid water can be viewed as an instantaneously changing random hydrogen-bonded network consisting of differently coordinated hydrogen-bonded molecules with their distinct solvation shells. The variation of the composition of these hydrogen-bonded molecules against temperature accounts for the density anomaly without introducing the concept of large-scale structural polyamorphism in water.

  10. Hydrogen Bonding Characteristics of Crystalline Water in Inorganic Crystals

    NASA Astrophysics Data System (ADS)

    Zhang, Fangfang; Li, Keyan; Xue, Dongfeng

    From the chemical bond viewpoint, the microscopic characterstatics of hydrogen bonds in Mi—OH2⋯O (M is the metal cation coordinated to water molecule and i is the number of M) systems were comprehensively studied. It is shown that the original O—OH and H⋯O bond lengths of each hydrogen bonding system are evidently influenced by the crystalline environment and strongly dependent on the corresponding average bond lengths of each system, bar d{O - {H}} and bar d{H ... {O}}. Furthermore, the hydrogen bonding capability of water molecules coordinated to various metal cations was properly estimated and found to be related to the ionic electronegativities of these metal cations. The current work provides a useful route to calculating hydrogen bond valences within reasonable accuracy and sheds light on the rational utilization of hydrogen bonds in crystal design.

  11. Comparison of modeled and observed environmental influences on the stable oxygen and hydrogen isotope composition of leaf water in Phaseolus vulgaris L

    SciTech Connect

    Flanagan, L.B.; Comstock, J.P.; Ehleringer, J.R. )

    1991-06-01

    In this paper the authors describe how a model of stable isotope fractionation processes, originally developed by H. Craig and L.I. Gordon for evaporation of water from the ocean, can be applied to leaf transpiration. The original model was modified to account for turbulent conditions in the leaf boundary layer. Experiments were conducted to test the factors influencing the stable isotopic composition of leaf water under controlled environment conditions. At steady state, the observed leaf water isotopic composition was enriched above that of stem water with the extent of the enrichment dependent on the leaf-air vapor pressure difference (VPD) and the isotopic composition of atmospheric water vapor (AMV). The higher the VPD, the larger was the observed heavy isotope content of leaf water. At a constant VPD, leaf water was relatively enriched in heavy isotopes when exposed to AWV with a large heavy isotope composition. However, the observed heavy isotope composition of leaf water was always less than that predicted by the model. The extent of the discrepancy between the modeled and observed leaf water isotopic composition was a strong linear function of the leaf transpiration rate.

  12. Noble metal-free hydrogen evolution catalysts for water splitting.

    PubMed

    Zou, Xiaoxin; Zhang, Yu

    2015-08-07

    Sustainable hydrogen production is an essential prerequisite of a future hydrogen economy. Water electrolysis driven by renewable resource-derived electricity and direct solar-to-hydrogen conversion based on photochemical and photoelectrochemical water splitting are promising pathways for sustainable hydrogen production. All these techniques require, among many things, highly active noble metal-free hydrogen evolution catalysts to make the water splitting process more energy-efficient and economical. In this review, we highlight the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER). We review several important kinds of heterogeneous non-precious metal electrocatalysts, including metal sulfides, metal selenides, metal carbides, metal nitrides, metal phosphides, and heteroatom-doped nanocarbons. In the discussion, emphasis is given to the synthetic methods of these HER electrocatalysts, the strategies of performance improvement, and the structure/composition-catalytic activity relationship. We also summarize some important examples showing that non-Pt HER electrocatalysts could serve as efficient cocatalysts for promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water splitting systems, when combined with suitable semiconductor photocatalysts.

  13. Hydrogen Generation from the Dissociation of Water Using Microwave Plasmas

    NASA Astrophysics Data System (ADS)

    Yong, Ho Jung; Soo Ouk, Jang; Hyun Jong, You

    2013-06-01

    Hydrogen is produced by direct dissociation of water vapor, i.e., splitting water molecules by the electrons in water plasma at low pressure (<10-50 Torr) using microwave plasma discharge. This condition generates a high electron temperature, which facilitates the direct dissociation of water molecules. A microwave plasma source is developed, utilizing the magnetron of a microwave oven and a TE10 rectangular waveguide. The quantity of the generated hydrogen is measured using a residual gas analyzer. The electron density and temperature are measured by a Langmuir probe, and the neutral temperature is calculated from the OH line intensity.

  14. Molecular cobalt pentapyridine catalysts for generating hydrogen from water

    DOEpatents

    Long, Jeffrey R; Chang, Christopher J; Sun, Yujie

    2013-11-05

    A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition including the moiety of the general formula. [(PY5Me.sub.2)CoL].sup.2+, where L can be H.sub.2O, OH.sup.-, a halide, alcohol, ether, amine, and the like. In embodiments of the invention, water, such as tap water or sea water can be subject to low electric potentials, with the result being, among other things, the generation of hydrogen.

  15. Effects of hydrogen-rich water on depressive-like behavior in mice.

    PubMed

    Zhang, Yi; Su, Wen-Jun; Chen, Ying; Wu, Teng-Yun; Gong, Hong; Shen, Xiao-Liang; Wang, Yun-Xia; Sun, Xue-Jun; Jiang, Chun-Lei

    2016-03-30

    Emerging evidence suggests that neuroinflammation and oxidative stress may be major contributors to major depressive disorder (MDD). Patients or animal models of depression show significant increase of proinflammatory cytokine interleukin-1β (IL-1β) and oxidative stress biomarkers in the periphery or central nervous system (CNS). Recent studies show that hydrogen selectively reduces cytotoxic oxygen radicals, and hydrogen-rich saline potentially suppresses the production of several proinflammatory mediators. Since current depression medications are accompanied by a wide spectrum of side effects, novel preventative or therapeutic measures with fewer side effects might have a promising future. We investigated the effects of drinking hydrogen-rich water on the depressive-like behavior in mice and its underlying mechanisms. Our study show that hydrogen-rich water treatment prevents chronic unpredictable mild stress (CUMS) induced depressive-like behavior. CUMS induced elevation in IL-1β protein levels in the hippocampus, and the cortex was significantly attenuated after 4 weeks of feeding the mice hydrogen-rich water. Over-expression of caspase-1 (the IL-1β converting enzyme) and excessive reactive oxygen species (ROS) production in the hippocampus and prefrontal cortex (PFC) was successfully suppressed by hydrogen-rich water treatment. Our data suggest that the beneficial effects of hydrogen-rich water on depressive-like behavior may be mediated by suppression of the inflammasome activation resulting in attenuated protein IL-1β and ROS production.

  16. Modeling of a Hydrogenic Pellet Production System

    NASA Astrophysics Data System (ADS)

    Leachman, J. W.; Pfotenhauer, J. M.; Nellis, G. F.

    2010-04-01

    Solid hydrogenic pellets are used as fuel for fusion energy machines like the ITER device. This paper discusses the numerical modeling of a Pellet Production System (PPS) that is used to generate these pellets. The PPS utilizes a source of supercritical helium to provide the cooling that is necessary to precool, liquefy, and solidify hydrogenic material that is ultimately extruded and cut into fuel pellets. The specific components within the PPS include a pre-cooling heat exchanger, a liquefier, and a twin-screw solidifying extruder. This paper presents numerical models of each component. These numerical models are used as design tools to predict the performance of the respective devices. The performance of the PPS is dominated by the heat transfer coefficient and viscous dissipation associated with the solidifying hydrogenic fluid in the twin-screw extruder. This observation motivates experimental efforts aimed at precise measurement of these quantities.

  17. Zeolite Membrane Reactor for Water Gas Shift Reaction for Hydrogen Production

    SciTech Connect

    Lin, Jerry Y.S.

    2013-01-29

    Gasification of biomass or heavy feedstock to produce hydrogen fuel gas using current technology is costly and energy-intensive. The technology includes water gas shift reaction in two or more reactor stages with inter-cooling to maximize conversion for a given catalyst volume. This project is focused on developing a membrane reactor for efficient conversion of water gas shift reaction to produce a hydrogen stream as a fuel and a carbon dioxide stream suitable for sequestration. The project was focused on synthesizing stable, hydrogen perm-selective MFI zeolite membranes for high temperature hydrogen separation; fabricating tubular MFI zeolite membrane reactor and stable water gas shift catalyst for membrane reactor applications, and identifying experimental conditions for water gas shift reaction in the zeolite membrane reactor that will produce a high purity hydrogen stream. The project has improved understanding of zeolite membrane synthesis, high temperature gas diffusion and separation mechanisms for zeolite membranes, synthesis and properties of sulfur resistant catalysts, fabrication and structure optimization of membrane supports, and fundamentals of coupling reaction with separation in zeolite membrane reactor for water gas shift reaction. Through the fundamental study, the research teams have developed MFI zeolite membranes with good perm-selectivity for hydrogen over carbon dioxide, carbon monoxide and water vapor, and high stability for operation in syngas mixture containing 500 part per million hydrogen sulfide at high temperatures around 500°C. The research teams also developed a sulfur resistant catalyst for water gas shift reaction. Modeling and experimental studies on the zeolite membrane reactor for water gas shift reaction have demonstrated the effective use of the zeolite membrane reactor for production of high purity hydrogen stream.

  18. Thermochemical generation of hydrogen and oxygen from water

    DOEpatents

    Robinson, Paul R.; Bamberger, Carlos E.

    1981-01-01

    A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO.sub.2) and titanium dioxide (TiO.sub.2) to form sodium titanate (Na.sub.2 TiO.sub.3), manganese (II) titanate (MnTiO.sub.3) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

  19. Thermochemical generation of hydrogen and oxygen from water

    DOEpatents

    Robinson, Paul R.; Bamberger, Carlos E.

    1982-01-01

    A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO.sub.2) and titanium dioxide (TiO.sub.2) to form sodium titanate (Na.sub.2 TiO.sub.3), manganese (II) titanate (MnTiO.sub.3) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

  20. Nuclear driven water decomposition plant for hydrogen production

    NASA Technical Reports Server (NTRS)

    Parker, G. H.; Brecher, L. E.; Farbman, G. H.

    1976-01-01

    The conceptual design of a hydrogen production plant using a very-high-temperature nuclear reactor (VHTR) to energize a hybrid electrolytic-thermochemical system for water decomposition has been prepared. A graphite-moderated helium-cooled VHTR is used to produce 1850 F gas for electric power generation and 1600 F process heat for the water-decomposition process which uses sulfur compounds and promises performance superior to normal water electrolysis or other published thermochemical processes. The combined cycle operates at an overall thermal efficiency in excess of 45%, and the overall economics of hydrogen production by this plant have been evaluated predicated on a consistent set of economic ground rules. The conceptual design and evaluation efforts have indicated that development of this type of nuclear-driven water-decomposition plant will permit large-scale economic generation of hydrogen in the 1990s.

  1. Hydrogen bonding in protic ionic liquids: reminiscent of water.

    PubMed

    Fumino, Koichi; Wulf, Alexander; Ludwig, Ralf

    2009-01-01

    Similarities and differences: Far-infrared spectra of protic ionic liquids could be assigned to intermolecular bending and stretching modes of hydrogen bonds. The characteristics of the low-frequency spectra resemble those of water. Both liquids form three-dimensional network structures, but only water is capable of building tetrahedral configurations. EAN: ethylammonium nitrate, PAN: propylammonium nitrate, DMAN: dimethylammonium nitrate.

  2. Method and apparatus for hydrogen production from water

    NASA Technical Reports Server (NTRS)

    Muradov, Nazim Z. (Inventor)

    2012-01-01

    A method, apparatuses and chemical compositions are provided for producing high purity hydrogen from water. Metals or alloys capable of reacting with water and producing hydrogen in aqueous solutions at ambient conditions are reacted with one or more inorganic hydrides capable of releasing hydrogen in aqueous solutions at ambient conditions, one or more transition metal compounds are used to catalyze the reaction and, optionally, one or more alkali metal-based compounds. The metal or alloy is preferably aluminum. The inorganic hydride is from a family of complex inorganic hydrides; most preferably, NaBH.sub.4. The transition metal catalyst is from the groups VIII and IB; preferably, Cu and Fe. The alkali metal-based compounds are preferably NaOH, KOH, and the like. Hydrogen generated has a purity of at least 99.99 vol. % (dry basis), and is used without further purification in all types of fuel cells, including the polymer electrolyte membrane (PEM) fuel cell.

  3. Direct synthesis of hydrogen peroxide in water at ambient temperature.

    PubMed

    Crole, David A; Freakley, Simon J; Edwards, Jennifer K; Hutchings, Graham J

    2016-06-01

    The direct synthesis of hydrogen peroxide (H2O2) from hydrogen and oxygen has been studied using an Au-Pd/TiO2 catalyst. The aim of this study is to understand the balance of synthesis and sequential degradation reactions using an aqueous, stabilizer-free solvent at ambient temperature. The effects of the reaction conditions on the productivity of H2O2 formation and the undesirable hydrogenation and decomposition reactions are investigated. Reaction temperature, solvent composition and reaction time have been studied and indicate that when using water as the solvent the H2O2 decomposition reaction is the predominant degradation pathway, which provides new challenges for catalyst design, which has previously focused on minimizing the subsequent hydrogenation reaction. This is of importance for the application of this catalytic approach for water purification.

  4. DOE Annual Progress Report: Water Needs and Constraints for Hydrogen Pathways

    SciTech Connect

    Simon, A; Daily, W

    2009-07-02

    Water is a critical feedstock in the production of hydrogen. In fact, water and many of the energy transformations upon which society depends are inextricably linked. Approximately 39% of freshwater withdrawals are used for cooling of power plants, and another 8% are used in industry and mining (including oil and gas extraction and refining). Major changes in the energy infrastructure (as envisioned in a transformation to a hydrogen economy) will necessarily result in changes to the water infrastructure. Depending on the manner in which a hydrogen economy evolves, these changes could be large or small, detrimental or benign. Water is used as a chemical feedstock for hydrogen production and as a coolant for the production process. Process and cooling water must meet minimum quality specifications (limits on mineral and organic contaminants) at both the inlet to the process and at the point of discharge. If these specifications are not met, then the water must be treated, which involves extra expenditure on equipment and energy. There are multiple options for water treatment and cooling systems, each of which has a different profile of equipment cost and operational requirements. The engineering decisions that are made when building out the hydrogen infrastructure will play an important role in the cost of producing hydrogen, and those decisions will be influenced by the regional and national policies that help to manage water resources. In order to evaluate the impacts of water on hydrogen production and of a hydrogen economy on water resources, this project takes a narrowly-scoped lifecycle analysis approach. We begin with a process model of hydrogen production and calculate the process water, cooling, electricity and energy feedstock demands. We expand beyond the production process itself by analyzing the details of the cooling system and water treatment system. At a regional scale, we also consider the water use associated with the electricity and fuel that feed

  5. Hydrogen evolution in nickel-water heat pipes.

    NASA Technical Reports Server (NTRS)

    Anderson, W. T.

    1973-01-01

    A study was made of the evolution of hydrogen gas in nickel-water heat pipes for the purpose of investigating methods of accelerated life testing. The data were analyzed in terms of a phenomenological corrosion model of heat pipe degradation which incorporates corrosion and oxidation theory and contains parameters which can be determined by experiment. The gas was evolved with a linear time dependence and an exponential temperature dependence with an activation energy of 1.03 x 10 to the minus 19th joules. A flow-rate dependence of the gas evolution was found in the form of a threshold. The results were used to predict usable lifetimes of heat pipes operated at normal operating conditions from results taken under accelerated operating conditions.

  6. Quantum theory of atoms in molecules/charge-charge flux-dipole flux models for fundamental vibrational intensity changes on H-bond formation of water and hydrogen fluoride

    SciTech Connect

    Silva, Arnaldo F.; Richter, Wagner E.; Bruns, Roy E.; Terrabuio, Luiz A.; Haiduke, Roberto L. A.

    2014-02-28

    The Quantum Theory of Atoms In Molecules/Charge-Charge Flux-Dipole Flux (QTAIM/CCFDF) model has been used to investigate the electronic structure variations associated with intensity changes on dimerization for the vibrations of the water and hydrogen fluoride dimers as well as in the water-hydrogen fluoride complex. QCISD/cc-pVTZ wave functions applied in the QTAIM/CCFDF model accurately provide the fundamental band intensities of water and its dimer predicting symmetric and antisymmetric stretching intensity increases for the donor unit of 159 and 47 km mol{sup −1} on H-bond formation compared with the experimental values of 141 and 53 km mol{sup −1}. The symmetric stretching of the proton donor water in the dimer has intensity contributions parallel and perpendicular to its C{sub 2v} axis. The largest calculated increase of 107 km mol{sup −1} is perpendicular to this axis and owes to equilibrium atomic charge displacements on vibration. Charge flux decreases occurring parallel and perpendicular to this axis result in 42 and 40 km mol{sup −1} total intensity increases for the symmetric and antisymmetric stretches, respectively. These decreases in charge flux result in intensity enhancements because of the interaction contributions to the intensities between charge flux and the other quantities. Even though dipole flux contributions are much smaller than the charge and charge flux ones in both monomer and dimer water they are important for calculating the total intensity values for their stretching vibrations since the charge-charge flux interaction term cancels the charge and charge flux contributions. The QTAIM/CCFDF hydrogen-bonded stretching intensity strengthening of 321 km mol{sup −1} on HF dimerization and 592 km mol{sup −1} on HF:H{sub 2}O complexation can essentially be explained by charge, charge flux and their interaction cross term. Atomic contributions to the intensities are also calculated. The bridge hydrogen atomic contributions alone

  7. Dynamical Crossover in Hot Dense Water: The Hydrogen Bond Role.

    PubMed

    Ranieri, Umbertoluca; Giura, Paola; Gorelli, Federico A; Santoro, Mario; Klotz, Stefan; Gillet, Philippe; Paolasini, Luigi; Koza, Michael Marek; Bove, Livia E

    2016-09-01

    We investigate the terahertz dynamics of liquid H2O as a function of pressure along the 450 K isotherm, by coupled quasielastic neutron scattering and inelastic X-ray scattering experiments. The pressure dependence of the single-molecule dynamics is anomalous in terms of both microscopic translation and rotation. In particular, the Stokes-Einstein-Debye equations are shown to be violated in hot water compressed to the GPa regime. The dynamics of the hydrogen bond network is only weakly affected by the pressure variation. The time scale of the structural relaxation driving the collective dynamics increases by a mere factor of 2 along the investigated isotherm, and the structural relaxation strength turns out to be almost pressure independent. Our results point at the persistence of the hydrogen bond network in hot dense water up to ice VII crystallization, thus questioning the long-standing perception that hydrogen bonds are broken in liquid water under the effect of compression.

  8. Screening parameters for the relativistic hydrogenic model

    NASA Astrophysics Data System (ADS)

    Lanzini, Fernando; Di Rocco, Héctor O.

    2015-12-01

    We present a Relativistic Screened Hydrogenic Model (RSHM) where the screening parameters depend on the variables (n , l , j) and the parameters (Z , N) . These screening parameters were derived theoretically in a neat form with no use of experimental values nor numerical values from self-consistent codes. The results of the model compare favorably with those obtained by using more sophisticated approaches. For the interested reader, a copy of our code can be requested from the corresponding author.

  9. MISCIBILITY CALCULATIONS FOR WATER AND HYDROGEN IN GIANT PLANETS

    SciTech Connect

    Soubiran, François; Militzer, Burkhard

    2015-06-20

    We present results from ab initio simulations of liquid water–hydrogen mixtures in the range from 2 to 70 GPa and from 1000 to 6000 K, covering conditions in the interiors of ice giant planets and parts of the outer envelope of gas giant planets. In addition to computing the pressure and the internal energy, we derive the Gibbs free energy by performing a thermodynamic integration. For all conditions under consideration, our simulations predict hydrogen and water to mix in all proportions. The thermodynamic behavior of the mixture can be well described with an ideal mixing approximation. We suggest that a substantial fraction of water and hydrogen in giant planets may occur in homogeneously mixed form rather than in separate layers. The extent of mixing depends on the planet’s interior dynamics and its conditions of formation, in particular on how much hydrogen was present when icy planetesimals were delivered. Based on our results, we do not predict water–hydrogen mixtures to phase separate during any stage of the evolution of giant planets. We also show that the hydrogen content of an exoplanet is much higher if the mixed interior is assumed.

  10. Electrokinetic Hydrogen Generation from Liquid WaterMicrojets

    SciTech Connect

    Duffin, Andrew M.; Saykally, Richard J.

    2007-05-31

    We describe a method for generating molecular hydrogen directly from the charge separation effected via rapid flow of liquid water through a metal orifice, wherein the input energy is the hydrostatic pressure times the volume flow rate. Both electrokinetic currents and hydrogen production rates are shown to follow simple equations derived from the overlap of the fluid velocity gradient and the anisotropic charge distribution resulting from selective adsorption of hydroxide ions to the nozzle surface. Pressure-driven fluid flow shears away the charge balancing hydronium ions from the diffuse double layer and carries them out of the aperture. Downstream neutralization of the excess protons at a grounded target electrode produces gaseous hydrogen molecules. The hydrogen production efficiency is currently very low (ca. 10-6) for a single cylindrical jet, but can be improved with design changes.

  11. Hydrogen isotopes in individual amino acids reflect differentiated pools of hydrogen from food and water in Escherichia coli

    PubMed Central

    Fogel, Marilyn L.; Griffin, Patrick L.; Newsome, Seth D.

    2016-01-01

    Hydrogen isotope (δ2H) analysis is widely used in animal ecology to study continental-scale movement because δ2H can trace precipitation and climate. To understand the biochemical underpinnings of how hydrogen is incorporated into biomolecules, we measured the δ2H of individual amino acids (AAs) in Escherichia coli cultured in glucose-based or complex tryptone-based media in waters with δ2H values ranging from −55‰ to +1,070‰. The δ2H values of AAs in tryptone spanned a range of ∼250‰. In E. coli grown on glucose, the range of δ2H among AAs was nearly 200‰. The relative distributions of δ2H of AAs were upheld in cultures grown in enriched waters. In E. coli grown on tryptone, the δ2H of nonessential AAs varied linearly with the δ2H of media water, whereas δ2H of essential AAs was nearly identical to δ2H in diet. Model calculations determined that as much as 46% of hydrogen in some nonessential AAs originated from water, whereas no more than 12% of hydrogen in essential AAs originated from water. These findings demonstrate that δ2H can route directly at the molecular level. We conclude that the patterns and distributions in δ2H of AAs are determined through biosynthetic reactions, suggesting that δ2H could become a new biosignature for studying novel microbial pathways. Our results also show that δ2H of AAs in an organism’s tissues provides a dual tracer for food and environmental (e.g., drinking) water. PMID:27444017

  12. Innovative Strategy on Hydrogen Evolution Reaction Utilizing Activated Liquid Water

    PubMed Central

    Hwang, Bing-Joe; Chen, Hsiao-Chien; Mai, Fu-Der; Tsai, Hui-Yen; Yang, Chih-Ping; Rick, John; Liu, Yu-Chuan

    2015-01-01

    Splitting water for hydrogen production using light, or electrical energy, is the most developed ‘green technique’. For increasing efficiency in hydrogen production, currently, the most exciting and thriving strategies are focused on efficient and inexpensive catalysts. Here, we report an innovative idea for efficient hydrogen evolution reaction (HER) utilizing plasmon-activated liquid water with reduced hydrogen-bonded structure by hot electron transfer. This strategy is effective for all HERs in acidic, basic and neutral systems, photocatalytic system with a g-C3N4 (graphite carbon nitride) electrode, as well as in an inert system with an ITO (indium tin oxide) electrode. Compared to deionized water, the efficiency of HER increases by 48% based on activated water ex situ on a Pt electrode. Increase in energy efficiency from activated water is 18% at a specific current yield of −20 mA in situ on a nanoscale-granulated Au electrode. Moreover, the onset potential of −0.023 V vs RHE was very close to the thermodynamic potential of the HER (0 V). The measured current density at the corresponding overpotential for HER in an acidic system was higher than any data previously reported in the literature. This approach establishes a new vista in clean green energy production. PMID:26541371

  13. Effect of water on hydrogen permeability. [Stirling engines

    NASA Technical Reports Server (NTRS)

    Hulligan, D. D.; Tomazic, W. A.

    1984-01-01

    Doping of hydrogen with CO or CO2 was developed to reduce hydrogen permeation in Stirling engines by forming low permeability oxide coatings in the heater tubes. An end product of this process is water - which can condense in the cold parts of the engine system. If the water vapor is reduced to a low enough level, the hydrogen can reduce the oxide coating resulting in increased permeability. The equilibrium level of water (oxygen bearing gas) required to avoid reduction of the oxide coating was investigated. Results at 720 C and 13.8 MPa have shown that: (1) pure hydrogen will reduce the coating; (2) 500 ppm CO (500 ppm water equivalent) does not prevent the reduction; and (3) 500 ppm CO2 (1000 ppm water) appears to be close to the equilibrium level. Further tests are planned to define the equilibrium level more precisely and to extend the data to 820 C and 3.4, 6.9, and 13.8 MPa.

  14. Innovative Strategy on Hydrogen Evolution Reaction Utilizing Activated Liquid Water

    NASA Astrophysics Data System (ADS)

    Hwang, Bing-Joe; Chen, Hsiao-Chien; Mai, Fu-Der; Tsai, Hui-Yen; Yang, Chih-Ping; Rick, John; Liu, Yu-Chuan

    2015-11-01

    Splitting water for hydrogen production using light, or electrical energy, is the most developed ‘green technique’. For increasing efficiency in hydrogen production, currently, the most exciting and thriving strategies are focused on efficient and inexpensive catalysts. Here, we report an innovative idea for efficient hydrogen evolution reaction (HER) utilizing plasmon-activated liquid water with reduced hydrogen-bonded structure by hot electron transfer. This strategy is effective for all HERs in acidic, basic and neutral systems, photocatalytic system with a g-C3N4 (graphite carbon nitride) electrode, as well as in an inert system with an ITO (indium tin oxide) electrode. Compared to deionized water, the efficiency of HER increases by 48% based on activated water ex situ on a Pt electrode. Increase in energy efficiency from activated water is 18% at a specific current yield of -20 mA in situ on a nanoscale-granulated Au electrode. Moreover, the onset potential of -0.023 V vs RHE was very close to the thermodynamic potential of the HER (0 V). The measured current density at the corresponding overpotential for HER in an acidic system was higher than any data previously reported in the literature. This approach establishes a new vista in clean green energy production.

  15. How strongly do hydrogen and water molecules stick to carbon nanomaterials?

    NASA Astrophysics Data System (ADS)

    Al-Hamdani, Yasmine S.; Alfè, Dario; Michaelides, Angelos

    2017-03-01

    The interaction strength of molecular hydrogen and water to carbon nanomaterials is relevant to, among many applications, hydrogen storage, water treatment, and water flow. However, accurate interaction energies for hydrogen and water with carbon nanotubes (CNTs) remain scarce despite the importance of having reliable benchmark data to inform experiments and to validate computational models. Here, benchmark fixed-node diffusion Monte Carlo (DMC) interaction energies are provided for hydrogen and water monomers inside and outside a typical zigzag CNT. The DMC interaction energies provide valuable insight into molecular interactions with CNTs in general and are also expected to be particularly relevant to gas uptake studies on CNTs. In addition, a selection of density functional theory (DFT) exchange-correlation (xc) functionals and force field potentials that ought to be suitable for these systems is compared. An unexpected variation is found in the performance of DFT van der Waals (vdW) models in particular. An analysis of the peculiar discrepancy between different vdW models indicates that medium-range correlation (at circa 3 to 5 Å) plays a key role inside CNTs and is poorly predicted by some vdW models. Using accurate reference information, this work reveals which xc functionals and force fields perform well for molecules interacting with CNTs. The findings will be valuable to future work on these and related systems that involve molecules interacting with low-dimensional systems.

  16. Solvated water molecules and hydrogen-bridged networks in liquid water

    NASA Astrophysics Data System (ADS)

    Corongiu, Giorgina; Clementi, Enrico

    1993-02-01

    We have analyzed the molecular-dynamics (MD) trajectories for the oxygen and hydrogen atoms of liquid water, at six temperatures (from hot, T=361 K, to supercooled water, T=242 K); in the MD simulations the Nieser-Corongiu-Clementi ab initio potential has been used, since it yields reliable x-ray and neutron-diffraction data as well as infrared, Raman, and neutron-scattering spectra. Our analysis leads to two complementary models where we can consider each water as a solvated molecule (placed at the center of a solvation shell) or as a component of a cyclic polymer, a substructure of the hydrogen-bonded network. In the first solvation shell all water molecules are solvated with coordination values in the range 2-8. The most probable solvation number is four, at low temperature, and five at high temperature considering oxygen-oxygen pairs; however, the coordination number is four at all the temperatures if we consider oxygen-hydrogen pairs. The lifetime of the tetra coordinated complexes is the largest one and increases as temperature decreases. The computed population of cyclic polymers is highest for the pentameters in the studied temperature range, the second most probable cyclic structure is for hexamers. The average O-O distances in the liquid are temperature dependent and shorter than those in the gas phase, approaching ice values at low temperature (except for cyclic trimers, for which the O-O distance is nearly temperature independent). As a preliminary result, the lifetime of the polygons is estimated to be around 0.01 ps.

  17. Nuclear quantum effects and hydrogen bond fluctuations in water.

    PubMed

    Ceriotti, Michele; Cuny, Jérôme; Parrinello, Michele; Manolopoulos, David E

    2013-09-24

    The hydrogen bond (HB) is central to our understanding of the properties of water. However, despite intense theoretical and experimental study, it continues to hold some surprises. Here, we show from an analysis of ab initio simulations that take proper account of nuclear quantum effects that the hydrogen-bonded protons in liquid water experience significant excursions in the direction of the acceptor oxygen atoms. This generates a small but nonnegligible fraction of transient autoprotolysis events that are not seen in simulations with classical nuclei. These events are associated with major rearrangements of the electronic density, as revealed by an analysis of the computed Wannier centers and (1)H chemical shifts. We also show that the quantum fluctuations exhibit significant correlations across neighboring HBs, consistent with an ephemeral shuttling of protons along water wires. We end by suggesting possible implications for our understanding of how perturbations (solvated ions, interfaces, and confinement) might affect the HB network in water.

  18. HYDROGEN ISOTOPE RECOVERY USING PROTON EXCHANGE MEMBRANE ELECTROLYSIS OF WATER

    SciTech Connect

    Fox, E; Scott Greenway, S; Amy Ekechukwu, A

    2007-08-27

    A critical component of tritium glovebox operations is the recovery of high value tritium from the water vapor in the glove box atmosphere. One proposed method to improve existing tritium recovery systems is to replace the disposable hot magnesium beds used to separate the hydrogen and oxygen in water with continuous use Proton Exchange Membrane Electrolyzers (PEMEs). This study examines radiation exposure to the membrane of a PEME and examines the sizing difference that would be needed if the electrolyzer were operated with a cathode water vapor feed instead of an anode liquid water feed.

  19. Hydrogen generation through static-feed water electrolysis

    NASA Technical Reports Server (NTRS)

    Jensen, F. C.; Schubert, F. H.

    1975-01-01

    A static-feed water electrolysis system (SFWES), developed under NASA sponsorship, is presented for potential applicability to terrestrial hydrogen production. The SFWES concept uses (1) an alkaline electrolyte to minimize power requirements and materials-compatibility problems, (2) a method where the electrolyte is retained in a thin porous matrix eliminating bulk electrolyte, and (3) a static water-feed mechanism to prevent electrode and electrolyte contamination and to promote system simplicity.

  20. The role of molecular hydrogen and methane oxidation in the water vapour budget of the stratosphere

    NASA Technical Reports Server (NTRS)

    Le Texier, H.; Solomon, S.; Garcia, R. R.

    1988-01-01

    The detailed photochemistry of methane oxidation has been studied in a coupled chemical/dynamical model of the middle atmosphere. The photochemistry of formaldehyde plays an important role in determining the production of water vapor from methane oxidation. At high latitudes, the production and transport of molecular hydrogen is particularly important in determining the water vapor distribution. It is shown that the ratio of the methane vertical gradient to the water vapor vertical gradient at any particular latitude should not be expected to be precisely 2, due both to photochemical and dynamical effects. Modeled H2O profiles are compared with measurements from the Limb Infrared Monitor of the Stratosphere (LIMS) experiment at various latitudes. Molecular hydrogen is shown to be responsible for the formation of a secondary maximum displayed by the model water vapor profiles in high latitude summer, a feature also found in the LIMS data.

  1. Thermochemical hydrogen production via a cycle using barium and sulfur - Reaction between barium sulfide and water

    NASA Technical Reports Server (NTRS)

    Ota, K.; Conger, W. L.

    1977-01-01

    The reaction between barium sulfide and water, a reaction found in several sulfur based thermochemical cycles, was investigated kinetically at 653-866 C. Gaseous products were hydrogen and hydrogen sulfide. The rate determining step for hydrogen formation was a surface reaction between barium sulfide and water. An expression was derived for the rate of hydrogen formation.

  2. The origin of proteins: Heteropolypeptides from hydrogen cyanide and water.

    PubMed

    Matthews, C N

    1975-01-01

    Evidence from laboratory and extraterrestrial chemistry is presented consistent with the hypothesis that the original heteropolypeptides on Earth were synthesized spontaneously from hydrogen cyanide and water without the intervening formation of chi-amino acids, a key step being the direct polymerization of atmospheric hydrogen cyanide to polyaminomalononitrile (IV) via dimeric HCN. Molecular orbital calculations (INDO) show that the most probable structure for (HCN)2 is azacyclopropenylidenimine. Successive reactions of hydrogen cyanide with the reactive nitrile side chains of IV then yield heteropolyamidines which are converted by water to heteropolypeptides. To study this postulated modification of a homopolymer to a heteropolymer, poly-chi-cyanoglycine (IX) was prepared from the N-carboxyanhydride of chi-cyanoglycine. Hydrolysis of IX, a polyamide analog of the polyamidine IV, yielded glycine. However, when IX was hydrolysed after being treated with hydrogen cyanide, other chi-amino acids were also obtained including alanine, serine, aspartic acid and glutamic acid, suggesting that the nitrile groups of IX (and therfore of IV) are indeed readily attacked by hydrogen cyanide as predicted. Further theoretical and experimental studies support the view that hydrogen cyanide polymerization along these lines is a universal process that accounts not only for the past formation of primitive proteins on Earth, but also for the yellow-brown-orange colors of Jupiter today and for the presence of water-soluble compounds hydrolyzable to chi-amino acids in materials obtained from environments as diverse as the moon, carbonaceous chondrites and the reaction chambers used to simulate organic synthesis in planetary atmospheres.

  3. Ceria-based model catalysts: fundamental studies on the importance of the metal-ceria interface in CO oxidation, the water-gas shift, CO2 hydrogenation, and methane and alcohol reforming.

    PubMed

    Rodriguez, José A; Grinter, David C; Liu, Zongyuan; Palomino, Robert M; Senanayake, Sanjaya D

    2017-04-03

    Model metal/ceria and ceria/metal catalysts have been shown to be excellent systems for studying fundamental phenomena linked to the operation of technical catalysts. In the last fifteen years, many combinations of well-defined systems involving different kinds of metals and ceria have been prepared and characterized using the modern techniques of surface science. So far most of the catalytic studies have been centered on a few reactions: CO oxidation, the hydrogenation of CO2, and the production of hydrogen through the water-gas shift reaction and the reforming of methane or alcohols. Using model catalysts it has been possible to examine in detail correlations between the structural, electronic and catalytic properties of ceria-metal interfaces. In situ techniques (X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, infrared spectroscopy, scanning tunneling microscopy) have been combined to study the morphological changes under reaction conditions and investigate the evolution of active phases involved in the cleavage of C-O, C-H and C-C bonds. Several studies with model ceria catalysts have shown the importance of strong metal-support interactions. In general, a substantial body of knowledge has been acquired and concepts have been developed for a more rational approach to the design of novel technical catalysts containing ceria.

  4. Determination of Hydrogen Bond Structure in Water versus Aprotic Environments To Test the Relationship Between Length and Stability

    SciTech Connect

    Sigala, Paul A.; Ruben, Eliza A.; Liu, Corey W.; Piccoli, Paula M. B.; Hohenstein, Edward G.; Martinez, Todd J.; Schultz, Arthur J.; Herschiag, Daniel

    2015-05-06

    Hydrogen bonds profoundly influence the architecture and activity of biological macromolecules. Deep appreciation of hydrogen bond contributions to biomolecular function thus requires a detailed understanding of hydrogen bond structure and energetics and the relationship between these properties. Hydrogen bond formation energies (Delta G(f)) are enormously more favorable in aprotic solvents than in water, and two classes of contributing factors have been proposed to explain this energetic difference, focusing respectively on the isolated and hydrogen-bonded species: (I) water stabilizes the dissociated donor and acceptor groups much better than aprotic solvents, thereby reducing the driving force for hydrogen bond formation; and (II) water lengthens hydrogen bonds compared to aprotic environments, thereby decreasing the potential energy within the hydrogen bond. Each model has been proposed to provide a dominant contribution to Delta G(f), but incisive tests that distinguish the importance of these contributions are lacking. Here we directly test the structural basis of model II. Neutron crystallography, NMR spectroscopy, and quantum mechanical calculations demonstrate that O-H center dot center dot center dot O hydrogen bonds in crystals, chloroform, acetone, and water have nearly identical lengths and very similar potential energy surfaces despite Delta G(f) differences >8 kcal/mol across these solvents. These results rule out a substantial contribution from solvent-dependent differences in hydrogen bond structure and potential energy after association (model II) and thus support the conclusion that differences in hydrogen bond Delta G(f) are predominantly determined by solvent interactions with the dissociated groups (model I). These findings advance our understanding of universal hydrogen-bonding interactions and have important implications for biology and engineering.

  5. Hydrogen bonding at the water surface revealed by isotopic dilution spectroscopy.

    PubMed

    Stiopkin, Igor V; Weeraman, Champika; Pieniazek, Piotr A; Shalhout, Fadel Y; Skinner, James L; Benderskii, Alexander V

    2011-06-08

    The air-water interface is perhaps the most common liquid interface. It covers more than 70 per cent of the Earth's surface and strongly affects atmospheric, aerosol and environmental chemistry. The air-water interface has also attracted much interest as a model system that allows rigorous tests of theory, with one fundamental question being just how thin it is. Theoretical studies have suggested a surprisingly short 'healing length' of about 3 ångströms (1 Å = 0.1 nm), with the bulk-phase properties of water recovered within the top few monolayers. However, direct experimental evidence has been elusive owing to the difficulty of depth-profiling the liquid surface on the ångström scale. Most physical, chemical and biological properties of water, such as viscosity, solvation, wetting and the hydrophobic effect, are determined by its hydrogen-bond network. This can be probed by observing the lineshape of the OH-stretch mode, the frequency shift of which is related to the hydrogen-bond strength. Here we report a combined experimental and theoretical study of the air-water interface using surface-selective heterodyne-detected vibrational sum frequency spectroscopy to focus on the 'free OD' transition found only in the topmost water layer. By using deuterated water and isotopic dilution to reveal the vibrational coupling mechanism, we find that the free OD stretch is affected only by intramolecular coupling to the stretching of the other OD group on the same molecule. The other OD stretch frequency indicates the strength of one of the first hydrogen bonds encountered at the surface; this is the donor hydrogen bond of the water molecule straddling the interface, which we find to be only slightly weaker than bulk-phase water hydrogen bonds. We infer from this observation a remarkably fast onset of bulk-phase behaviour on crossing from the air into the water phase.

  6. Hydrogen production in a radio-frequency plasma source operating on water vapor

    NASA Astrophysics Data System (ADS)

    Nguyen, Son-Ca Viet Thi

    The global energy and climate challenges have motivated development of innovative techniques to satisfy energy demand while minimizing emissions. To this end, hydrogen as an alternative energy carrier in the transportation sector is an attractive option. In addition, there is already a great need for hydrogen gas in several industrial processes such as hydro-cracking of crude oil to produce gasoline and production of ammonia and methanol. The current dominant methods of hydrogen production from fossil fuels are well-developed and have reached relatively high energy efficiencies (up to 85%), but these methods rely on non-renewable natural resources and produce carbon dioxide emissions. This work investigates the feasibility of hydrogen production by dissociating water molecules in a radio-frequency (RF) plasma discharge. In addition to the widespread usage of hydrogen gas, applications of water plasma have permeated in many areas of research, and information on basic behaviors of a water plasma discharge will provide fruitful insights for other researchers. An RF plasma source equipped with a double-helix antenna (m = 1 mode) and an applied axial magnetic field is designed to operate on water vapor. It is shown that water molecules are being dissociated in the discharge. Experimental results show that the rate of hydrogen production increases linearly with RF power in the absence of the applied axial magnetic field. With the magnetic field, the rate of hydrogen production increases from 250 to 500 W, and begins to saturate with RF power. Despite this saturation, it is shown that hydrogen increases with magnetic field strength at a fixed RF power. Further, the rate of hydrogen production increases with water input flow rate up to 100 sccm for a fixed RF power level, and begins to decrease at 125 sccm. This dissertation characterizes the rate of hydrogen production and plasma properties as a function of RF power, applied B-field strength, and water input flow rate. A

  7. Hydrogen Bonds and Vibrations of Water on (110) Rutile

    SciTech Connect

    Kumar, Nitin; Neogi, Sanghamitra; Kent, Paul R; Bandura, Andrei V.; Wesolowski, David J; Cole, David R; Sofo, Jorge O.

    2009-01-01

    We study the relation between hydrogen bonding and the vibrational frequency spectra of water on the (110) surface of rutile (α-TiO2) with three structural layers of adsorbed water. Using ab-initio molecular dynamics simulations at 280, 300 and 320K, we find strong, crystallographically-controlled adsorption sites, in general agreement with synchrotron X-ray and classical MD simulations. We demonstrate that these sites are produced by strong hydrogen bonds formed between the surface oxygen atoms and sorbed water molecules. The strength of these bonds is manifested by substantial broadening of the stretching mode vibrational band. The overall vibrational spectrum obtained from our simulations is in good agreement with inelastic neutron scattering experiments. We correlate the vibrational spectrum with different bonds at the surface in order to transform these vibrational measurements into a spectroscopy of surface interactions.

  8. Confinement dependence of electro-catalysts for hydrogen evolution from water splitting

    PubMed Central

    Panas, Itai

    2014-01-01

    Summary Density functional theory is utilized to articulate a particular generic deconstruction of the electrode/electro-catalyst assembly for the cathode process during water splitting. A computational model was designed to determine how alloying elements control the fraction of H2 released during zirconium oxidation by water relative to the amount of hydrogen picked up by the corroding alloy. This model is utilized to determine the efficiencies of transition metals decorated with hydroxide interfaces in facilitating the electro-catalytic hydrogen evolution reaction. A computational strategy is developed to select an electro-catalyst for hydrogen evolution (HE), where the choice of a transition metal catalyst is guided by the confining environment. The latter may be recast into a nominal pressure experienced by the evolving H2 molecule. We arrived at a novel perspective on the uniqueness of oxide supported atomic Pt as a HE catalyst under ambient conditions. PMID:24605286

  9. Confinement dependence of electro-catalysts for hydrogen evolution from water splitting.

    PubMed

    Lindgren, Mikaela; Panas, Itai

    2014-01-01

    Density functional theory is utilized to articulate a particular generic deconstruction of the electrode/electro-catalyst assembly for the cathode process during water splitting. A computational model was designed to determine how alloying elements control the fraction of H2 released during zirconium oxidation by water relative to the amount of hydrogen picked up by the corroding alloy. This model is utilized to determine the efficiencies of transition metals decorated with hydroxide interfaces in facilitating the electro-catalytic hydrogen evolution reaction. A computational strategy is developed to select an electro-catalyst for hydrogen evolution (HE), where the choice of a transition metal catalyst is guided by the confining environment. The latter may be recast into a nominal pressure experienced by the evolving H2 molecule. We arrived at a novel perspective on the uniqueness of oxide supported atomic Pt as a HE catalyst under ambient conditions.

  10. Hydrogen evolution from water through metal sulfide reactions

    NASA Astrophysics Data System (ADS)

    Saha, Arjun; Raghavachari, Krishnan

    2013-11-01

    Transition metal sulfides play an important catalytic role in many chemical reactions. In this work, we have conducted a careful computational study of the structures, electronic states, and reactivity of metal sulfide cluster anions M2SX- (M = Mo and W, X = 4-6) using density functional theory. Detailed structural analysis shows that these metal sulfide anions have ground state isomers with two bridging sulfide bonds, notably different in some cases from the corresponding oxides with the same stoichiometry. The chemical reactivity of these metal sulfide anions with water has also been carried out. After a thorough search on the reactive potential energy surface, we propose several competitive, energetically favorable, reaction pathways that lead to the evolution of hydrogen. Selectivity in the initial water addition and subsequent hydrogen migration are found to be the key steps in all the proposed reaction channels. Initial adsorption of water is most favored involving a terminal metal sulfur bond in Mo2S4- isomers whereas the most preferred orientation for water addition involves a bridging metal sulfur bond in the case of W2S4- and M2S5- isomers. In all the lowest energy H2 elimination steps, the interacting hydrogen atoms involve a metal hydride and a metal hydroxide (or thiol) group. We have also observed a higher energy reaction channel where the interacting hydrogen atoms in the H2 elimination step involve a thiol (-SH) and a hydroxyl (-OH) group. For all the reaction pathways, the Mo sulfide reactions involve a higher barrier than the corresponding W analogues. We observe for both metals that reactions of M2S4- and M2S5- clusters with water to liberate H2 are exothermic and involve modest free energy barriers. However, the reaction of water with M2S6- is highly endothermic with a considerable barrier due to saturation of the local bonding environment.

  11. Solar hydrogen production on some water splitting photocatalysts

    NASA Astrophysics Data System (ADS)

    Takata, Tsuyoshi; Hisatomi, Takashi; Domen, Kazunari

    2016-09-01

    Photocatalytic overall water splitting into H2 and O2 is expected to be a promising method for the efficient utilization of solar energy. The design of optimal photocatalyst structures is a key to efficient overall water splitting, and the development of photocatalysts which can efficiently convert large portion of visible light spectrum has been required. Recently, a series of complex perovskite type transition metal oxynitrides, LaMgxT 1-xO1+3xN2-3x, was developed as photocatalysts for direct water splitting operable at wide wavelength of visible light. In addition two-step excitation water splitting via a novel photocatalytic device termed as photocatalyst sheet was developed. This consists of two types of semiconductors (hydrogen evolution photocatalyst and oxygen evolution photocatalyst) particles embedded in a conductive layer, and showed high efficiency for overall water splitting. These recent advances in photocatalytic water splitting were introduced.

  12. Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Lam, Royce K.; Smith, Jacob W.; Saykally, Richard J.

    2016-05-01

    While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering. We have investigated mixtures of methanol, ethanol, and isopropanol with water by liquid microjet X-ray absorption spectroscopy on the oxygen K-edge, an atom-specific probe providing details of both inter- and intra-molecular structure. The measured spectra evidence a significant enhancement of hydrogen bonding originating from the methanol and ethanol hydroxyl groups upon the addition of water. These additional hydrogen bonding interactions would strengthen the liquid-liquid interactions, resulting in additional ordering in the liquid structures and leading to a reduction in entropy and a negative enthalpy of mixing, consistent with existing thermodynamic data. In contrast, the spectra of the isopropanol-water mixtures exhibit an increase in the number of broken alcohol hydrogen bonds for mixtures containing up to 0.5 water mole fraction, an observation consistent with existing enthalpy of mixing data, suggesting that the measured negative excess entropy is a result of clustering or micro-immiscibility.

  13. Cooperative enhancement of water binding to crownophane by multiple hydrogen bonds: analysis by high level ab initio calculations.

    PubMed

    Tsuzuki, S; Houjou, H; Nagawa, Y; Goto, M; Hiratani, K

    2001-05-09

    The intermolecular interaction energy of the model system of the water-crownophane complex was analyzed. The water molecule has four hydrogen bonds, with the two hydrogen-donating phenolic hydroxy groups and two hydrogen-accepting oxygen atoms of the poly-oxyethylene chain of the crownophane in the complex. The MP2/6-311G(2d,2p) level calculations of the model system of the complex (hydrogen donating unit + hydrogen accepting unit + water) indicate that the binding energy of the water is 21.85 kcal/mol and that the hydrogen bond cooperativity increases the binding energy as much as 3.67 kcal/mol. The calculated interaction energies depend on the basis set, while the basis set dependence of the cooperative increment is negligible. Most of the cooperative increment is covered by the HF level calculation, which suggests that the major source of the hydrogen bond cooperativity in this system has its origin in induction. The BLYP/6-311G** and PW91/6-311G** level interaction energies of the model system are close to the MP2/6-311G** interaction energies, which suggests that the DFT calculations with these functionals are useful methods to evaluated the interactions of hydrogen bonded systems.

  14. Clean hydrogen and power from impure water

    NASA Astrophysics Data System (ADS)

    Acar, Canan; Dincer, Ibrahim; Naterer, Greg F.

    2016-11-01

    This paper presents a new photoelectrochemical (PEC) H2 production system which is capable of providing clean energy and water, and multi-generation of H2, electricity, heat and industrial chemicals from a single clean, abundant and renewable source: sun. This novel system maximizes solar spectrum utilization and increases system efficiencies by generating more outputs from solar energy alone. The hybrid PEC-chloralkali system, coupled with PV/T (Photovoltaic Thermal), is capable of producing H2, Cl2, electricity, and heat simultaneously. Incoming solar light is split into high-energy photons (with wavelengths lower than 400 nm) and low-energy photons. The high-energy portion is used to generate photocurrent in the reactor, and the remaining part is sent to the PV/T. This PV/T supports the electricity needs of the system and also provides electricity output for the end user. Moreover, the heat recovered from PV/T is a system output. The findings suggest that this system is capable of producing H2 and Cl2 as well as heat and electricity with higher efficiencies than the reported PV electrolysis and PEC-based H2 production efficiencies in the literature.

  15. Molecular metal-Oxo catalysts for generating hydrogen from water

    DOEpatents

    Long, Jeffrey R; Chang, Christopher J; Karunadasa, Hemamala I

    2015-02-24

    A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition having the general formula [(PY5W.sub.2)MO].sup.2+, wherein PY5W.sub.2 is (NC.sub.5XYZ)(NC.sub.5H.sub.4).sub.4C.sub.2W.sub.2, M is a transition metal, and W, X, Y, and Z can be H, R, a halide, CF.sub.3, or SiR.sub.3, where R can be an alkyl or aryl group. The two accompanying counter anions, in one embodiment, can be selected from the following Cl.sup.-, I.sup.-, PF.sub.6.sup.-, and CF.sub.3SO.sub.3.sup.-. In embodiments of the invention, water, such as tap water containing electrolyte or straight sea water can be subject to an electric potential of between 1.0 V and 1.4 V relative to the standard hydrogen electrode, which at pH 7 corresponds to an overpotential of 0.6 to 1.0 V, with the result being, among other things, the generation of hydrogen with an optimal turnover frequency of ca. 1.5 million mol H.sub.2/mol catalyst per h.

  16. Method of generating hydrogen by catalytic decomposition of water

    DOEpatents

    Balachandran, Uthamalingam; Dorris, Stephen E.; Bose, Arun C.; Stiegel, Gary J.; Lee, Tae-Hyun

    2002-01-01

    A method for producing hydrogen includes providing a feed stream comprising water; contacting at least one proton conducting membrane adapted to interact with the feed stream; splitting the water into hydrogen and oxygen at a predetermined temperature; and separating the hydrogen from the oxygen. Preferably the proton conducting membrane comprises a proton conductor and a second phase material. Preferable proton conductors suitable for use in a proton conducting membrane include a lanthanide element, a Group VIA element and a Group IA or Group IIA element such as barium, strontium, or combinations of these elements. More preferred proton conductors include yttrium. Preferable second phase materials include platinum, palladium, nickel, cobalt, chromium, manganese, vanadium, silver, gold, copper, rhodium, ruthenium, niobium, zirconium, tantalum, and combinations of these. More preferably second phase materials suitable for use in a proton conducting membrane include nickel, palladium, and combinations of these. The method for generating hydrogen is preferably preformed in the range between about 600.degree. C. and 1,700.degree. C.

  17. Gamma radiation induces hydrogen absorption by copper in water

    PubMed Central

    Lousada, Cláudio M.; Soroka, Inna L.; Yagodzinskyy, Yuriy; Tarakina, Nadezda V.; Todoshchenko, Olga; Hänninen, Hannu; Korzhavyi, Pavel A.; Jonsson, Mats

    2016-01-01

    One of the most intricate issues of nuclear power is the long-term safety of repositories for radioactive waste. These repositories can have an impact on future generations for a period of time orders of magnitude longer than any known civilization. Several countries have considered copper as an outer corrosion barrier for canisters containing spent nuclear fuel. Among the many processes that must be considered in the safety assessments, radiation induced processes constitute a key-component. Here we show that copper metal immersed in water uptakes considerable amounts of hydrogen when exposed to γ-radiation. Additionally we show that the amount of hydrogen absorbed by copper depends on the total dose of radiation. At a dose of 69 kGy the uptake of hydrogen by metallic copper is 7 orders of magnitude higher than when the absorption is driven by H2(g) at a pressure of 1 atm in a non-irradiated dry system. Moreover, irradiation of copper in water causes corrosion of the metal and the formation of a variety of surface cavities, nanoparticle deposits, and islands of needle-shaped crystals. Hence, radiation enhanced uptake of hydrogen by spent nuclear fuel encapsulating materials should be taken into account in the safety assessments of nuclear waste repositories. PMID:27086752

  18. Gamma radiation induces hydrogen absorption by copper in water.

    PubMed

    Lousada, Cláudio M; Soroka, Inna L; Yagodzinskyy, Yuriy; Tarakina, Nadezda V; Todoshchenko, Olga; Hänninen, Hannu; Korzhavyi, Pavel A; Jonsson, Mats

    2016-04-18

    One of the most intricate issues of nuclear power is the long-term safety of repositories for radioactive waste. These repositories can have an impact on future generations for a period of time orders of magnitude longer than any known civilization. Several countries have considered copper as an outer corrosion barrier for canisters containing spent nuclear fuel. Among the many processes that must be considered in the safety assessments, radiation induced processes constitute a key-component. Here we show that copper metal immersed in water uptakes considerable amounts of hydrogen when exposed to γ-radiation. Additionally we show that the amount of hydrogen absorbed by copper depends on the total dose of radiation. At a dose of 69 kGy the uptake of hydrogen by metallic copper is 7 orders of magnitude higher than when the absorption is driven by H2(g) at a pressure of 1 atm in a non-irradiated dry system. Moreover, irradiation of copper in water causes corrosion of the metal and the formation of a variety of surface cavities, nanoparticle deposits, and islands of needle-shaped crystals. Hence, radiation enhanced uptake of hydrogen by spent nuclear fuel encapsulating materials should be taken into account in the safety assessments of nuclear waste repositories.

  19. VOC destruction by water diluted hydrogen mild combustion.

    PubMed

    Sabia, P; Romeo, F; de Joannon, M; Cavaliere, A

    2007-06-01

    This study represents a preliminary numerical evaluation of the effect of steam dilution and hydrogen addition on the oxidation of formaldehyde and benzene, chosen as representative of the volatile organic compounds (VOC), in mild condition by evaluating the autoignition time and the steady state attainment. These parameters are important in the design of thermal VOC destruction plants since they influence the abatement efficiency and, therefore, the plant dimension. It has come out that, in comparison with the system diluted in nitrogen, steam induces lower autoignition times and, on the other hand, longer times for the attainment of the steady state. In contrast, for very high water content the autoignition time slightly increases. In particular results have shown that is possible to identify an optimum value of steam content that allows for the attainment of the steady state condition by the lowest residence time. Hydrogen addition to systems diluted in nitrogen promotes the oxidation reactions and anticipates the steady state condition. In steam diluted systems hydrogen delays the autoignition of the mixtures even though anticipates the attainment of the complete destruction of the VOC. The rate of production analysis has showed that the H(2)/O(2) reactions, that promote the ignition and the destruction of VOC, are sensibly modified by the presence of water and hydrogen.

  20. Gamma radiation induces hydrogen absorption by copper in water

    NASA Astrophysics Data System (ADS)

    Lousada, Cláudio M.; Soroka, Inna L.; Yagodzinskyy, Yuriy; Tarakina, Nadezda V.; Todoshchenko, Olga; Hänninen, Hannu; Korzhavyi, Pavel A.; Jonsson, Mats

    2016-04-01

    One of the most intricate issues of nuclear power is the long-term safety of repositories for radioactive waste. These repositories can have an impact on future generations for a period of time orders of magnitude longer than any known civilization. Several countries have considered copper as an outer corrosion barrier for canisters containing spent nuclear fuel. Among the many processes that must be considered in the safety assessments, radiation induced processes constitute a key-component. Here we show that copper metal immersed in water uptakes considerable amounts of hydrogen when exposed to γ-radiation. Additionally we show that the amount of hydrogen absorbed by copper depends on the total dose of radiation. At a dose of 69 kGy the uptake of hydrogen by metallic copper is 7 orders of magnitude higher than when the absorption is driven by H2(g) at a pressure of 1 atm in a non-irradiated dry system. Moreover, irradiation of copper in water causes corrosion of the metal and the formation of a variety of surface cavities, nanoparticle deposits, and islands of needle-shaped crystals. Hence, radiation enhanced uptake of hydrogen by spent nuclear fuel encapsulating materials should be taken into account in the safety assessments of nuclear waste repositories.

  1. Hydrogen production by photosynthetic water splitting

    SciTech Connect

    Greenbaum, E.; Lee, J.W.; Tevault, C.V.

    1996-10-01

    Contrary to the prediction of the {open_quotes}Z-scheme{close_quotes} model of photosynthesis, experiments demonstrated that mutants of Chlamydomonas containing Photosystem II (PSII) but lacking Photosystem I (PSI), can grow photoautotrophically with O{sub 2} evolution and using atmospheric CO{sub 2} as the sole carbon source. Autotrophic photosynthesis by PSI-deficient mutants was stable both under anaerobic conditions and in air (21% O{sub 2}) at an actinic intensity of 200 {mu}E/m{sup -2}{sup {sm_bullet}}s. This {open_quotes}PSII photosynthesis,{close_quotes} sufficient to support cell development and mobility, may also occur in wild-type green algae and higher plants. The mutants can survive under 2000 {mu}E{sup {sm_bullet}}m{sup -2}{sup {sm_bullet}}s{sup -1} with air, although they have less resistance to photoinhibition.

  2. Summary status of advanced water electrolysis and hydrogen storage/transport R and D

    SciTech Connect

    Mezzina, A.

    1984-04-01

    Major projects within the framework of the U.S. DOE Chemical/Hydrogen Energy Systems Program are described. Goals, accomplishments and status of investigations into advanced water electrolysis and hydrogen storage/transport are summarized. Electrolytic hydrogen production systems include: SPE electrolyzers; static feed water electrolysis; high temperature electrolysis; and other advanced concepts. Hydrogen transport studies have emphasized the characterization of hydrogen embrittlement effects on conventional natural gas pipeline steels.

  3. Molecular cobalt pentapyridine catalysts for generating hydrogen from water.

    PubMed

    Sun, Yujie; Bigi, Julian P; Piro, Nicholas A; Tang, Ming Lee; Long, Jeffrey R; Chang, Christopher J

    2011-06-22

    A set of robust molecular cobalt catalysts for the generation of hydrogen from water is reported. The cobalt complex supported by the parent pentadentate polypyridyl ligand PY5Me(2) features high stability and activity and 100% Faradaic efficiency for the electrocatalytic production of hydrogen from neutral water, with a turnover number reaching 5.5 × 10(4) mol of H(2) per mole of catalyst with no loss in activity over 60 h. Control experiments establish that simple Co(II) salts, the free PY5Me(2) ligand, and an isostructural PY5Me(2) complex containing redox-inactive Zn(II) are all ineffective for this reaction. Further experiments demonstrate that the overpotential for H(2) evolution can be tuned by systematic substitutions on the ancillary PY5Me(2) scaffold, presaging opportunities to further optimize this first-generation platform by molecular design.

  4. Generation of hydrogen from photocatalytic cleavage of water

    SciTech Connect

    Mallinson, R.G.; Resasco, D.E.; Lobban, L.L.; Nicholas, K.M.

    1998-08-01

    This paper describes the objectives, methods and early results on the US Department of Energy sponsored project to generate hydrogen from splitting of water using photocatalysts. The approach uses organometallic photosensitizers adsorbed onto platinated titania. Platinized titania is a photocatalyst for water splitting, but does not absorb sunlight in the visible range, where most of the sun`s energy is contained. Organometallic photosensitizers are synthesized, attached to platinized titania and characterized by UV-Vis spectroscopy, cyclic voltammetry, action spectra and hydrogen generation ability. Thus far, Copper, Iron and Ruthenium catalyst systems have been produced and characterized in this manner. Suitable sensitized systems that have the desirable properties have not yet been found.

  5. Direct synthesis of hydrogen peroxide from plasma-water interactions

    NASA Astrophysics Data System (ADS)

    Liu, Jiandi; He, Bangbang; Chen, Qiang; Li, Junshuai; Xiong, Qing; Yue, Guanghui; Zhang, Xianhui; Yang, Size; Liu, Hai; Liu, Qing Huo

    2016-12-01

    Hydrogen peroxide (H2O2) is usually considered to be an important reagent in green chemistry since water is the only by-product in H2O2 involved oxidation reactions. Early studies show that direct synthesis of H2O2 by plasma-water interactions is possible, while the factors affecting the H2O2 production in this method remain unclear. Herein, we present a study on the H2O2 synthesis by atmospheric pressure plasma-water interactions. The results indicate that the most important factors for the H2O2 production are the processes taking place at the plasma-water interface, including sputtering, electric field induced hydrated ion emission, and evaporation. The H2O2 production rate reaches ~1200 μmol/h when the liquid cathode is purified water or an aqueous solution of NaCl with an initial conductivity of 10500 μS cm‑1.

  6. Direct synthesis of hydrogen peroxide from plasma-water interactions.

    PubMed

    Liu, Jiandi; He, Bangbang; Chen, Qiang; Li, Junshuai; Xiong, Qing; Yue, Guanghui; Zhang, Xianhui; Yang, Size; Liu, Hai; Liu, Qing Huo

    2016-12-05

    Hydrogen peroxide (H2O2) is usually considered to be an important reagent in green chemistry since water is the only by-product in H2O2 involved oxidation reactions. Early studies show that direct synthesis of H2O2 by plasma-water interactions is possible, while the factors affecting the H2O2 production in this method remain unclear. Herein, we present a study on the H2O2 synthesis by atmospheric pressure plasma-water interactions. The results indicate that the most important factors for the H2O2 production are the processes taking place at the plasma-water interface, including sputtering, electric field induced hydrated ion emission, and evaporation. The H2O2 production rate reaches ~1200 μmol/h when the liquid cathode is purified water or an aqueous solution of NaCl with an initial conductivity of 10500 μS cm(-1).

  7. Control of microbially generated hydrogen sulfide in produced waters

    SciTech Connect

    Burger, E.D.; Vance, I.; Gammack, G.F.; Duncan, S.E.

    1995-12-31

    Production of hydrogen sulfide in produced waters due to the activity of sulfate-reducing bacteria (SRB) is a potentially serious problem. The hydrogen sulfide is not only a safety and environmental concern, it also contributes to corrosion, solids formation, a reduction in produced oil and gas values, and limitations on water discharge. Waters produced from seawater-flooded reservoirs typically contain all of the nutrients required to support SRB metabolism. Surface processing facilities provide a favorable environment in which SRB flourish, converting water-borne nutrients into biomass and H{sub 2}S. This paper will present results from a field trial in which a new technology for the biochemical control of SRB metabolism was successfully applied. A slip stream of water downstream of separators on a produced water handling facility was routed through a bioreactor in a side-steam device where microbial growth was allowed to develop fully. This slip stream was then treated with slug doses of two forms of a proprietary, nonbiocidal metabolic modifier. Results indicated that H{sub 2}S production was halted almost immediately and that the residual effect of the treatment lasted for well over one week.

  8. Hydrogen isotope analysis of amino acids and whole cells reflects biosynthetic processing of nutrient- and water-derived hydrogen

    NASA Astrophysics Data System (ADS)

    Griffin, P.; Newsome, S.; Steele, A.; Fogel, M. L.

    2011-12-01

    Hydrogen (H) isotopes serve as sensitive tracers of biochemical processes that can be exploited to answer critical questions in biogeochemistry, ecology, and microbiology. Despite this apparent utility, relatively little is known about the specific mechanisms of H isotope fractionation involved in biosynthesis. In order to understand how organisms incorporate hydrogen from their chemical milieu into biomass, we have cultured the model bacterium E. coli MG1655 in a variety of media composed of deuterium-labeled nutrients and waters. Isotopic analysis of bulk cell mass reveals that the H fractionation between media water and cell material varies as a function of the nutrient source, with commonly used organic food sources (glucose and tryptone) leading to far smaller fractionation signals than non-standard ones (such as formamide, adenine, and urea). In addition, we have completed compound specific isotope analysis of amino acids using combined GC-IRMS. Amino acids harvested from E. coli cultured on glucose in water of varied D/H composition posses an extraordinary range of isotopic compositions (400-600 %). Furthermore, these amino acids follow a systematic distribution of D/H where proline is always heaviest and glycine is always lightest. However, when the short-chain peptide tryptone is used in place of glucose, only the non-essential amino acids reflect media water D/H values, suggesting the direct incorporation of some media-borne amino acids into cellular protein. These observations provide a foundation for understanding the cellular routing of hydrogen obtained from food and water sources and indicate that D/H analysis can serve as a powerful probe of biological function.

  9. Recovery of hydrogen and removal of nitrate from water by electrocoagulation process.

    PubMed

    Lakshmi, Jothinathan; Sozhan, Ganapathy; Vasudevan, Subramanyan

    2013-04-01

    The present study provides an optimization of electrocoagulation process for the recovery of hydrogen and removal of nitrate from water. In doing so, the thermodynamic, adsorption isotherm, and kinetic studies were also carried out. Aluminum alloy of size 2 dm(2) was used as anode and as cathode. To optimize the maximum removal efficiency, different parameters like effect of initial concentration, effect of temperature, pH, and effect of current density were studied. The results show that a significant amount of hydrogen can be generated by this process during the removal of nitrate from water. The energy yield calculated from the hydrogen generated is 3.3778 kWh/m(3). The results also showed that the maximum removal efficiency of 95.9% was achieved at a current density of 0.25 A/dm(2), at a pH of 7.0. The adsorption process followed second-order kinetics model. The adsorption of NO3(-) preferably fitting the Langmuir adsorption isotherm suggests monolayer coverage of adsorbed molecules. Thermodynamic studies showed that adsorption was exothermic and spontaneous in nature. The energy yield of generated hydrogen was ~54% of the electrical energy demand of the electrocoagulation process. With the reduction of the net energy demand, electrocoagulation may become a useful technology to treat water associated with power production. The aluminum hydroxide generated in the cell removes the nitrate present in the water and reduced it to a permissible level making the water drinkable.

  10. Hydrogen-on-demand using metallic alloy nanoparticles in water.

    PubMed

    Shimamura, Kohei; Shimojo, Fuyuki; Kalia, Rajiv K; Nakano, Aiichiro; Nomura, Ken-Ichi; Vashishta, Priya

    2014-07-09

    Hydrogen production from water using Al particles could provide a renewable energy cycle. However, its practical application is hampered by the low reaction rate and poor yield. Here, large quantum molecular dynamics simulations involving up to 16,611 atoms show that orders-of-magnitude faster reactions with higher yields can be achieved by alloying Al particles with Li. A key nanostructural design is identified as the abundance of neighboring Lewis acid-base pairs, where water-dissociation and hydrogen-production require very small activation energies. These reactions are facilitated by charge pathways across Al atoms that collectively act as a "superanion" and a surprising autocatalytic behavior of bridging Li-O-Al products. Furthermore, dissolution of Li atoms into water produces a corrosive basic solution that inhibits the formation of a reaction-stopping oxide layer on the particle surface, thereby increasing the yield. These atomistic mechanisms not only explain recent experimental findings but also predict the scalability of this hydrogen-on-demand technology at industrial scales.

  11. Characteristics of hydrogen bond revealed from water clusters

    NASA Astrophysics Data System (ADS)

    Song, Yan; Chen, Hongshan; Zhang, Cairong; Zhang, Yan; Yin, Yuehong

    2014-09-01

    The hydrogen bond network is responsible for the exceptional physical and chemical properties of water, however, the description of hydrogen bond remains a challenge for the studies of condensed water. The investigation of structural and binding properties of water clusters provides a key for understanding the H-bonds in bulk water. In this paper, a new set of geometric parameters are defined to describe the extent of the overlap between the bonding orbital of the donor OH and the nonbonding orbital of the lone-pair of the acceptor molecule. This orbital overlap plays a dominant role for the strength of H-bonds. The dependences of the binding energy of the water dimer on these parameters are studied. The results show that these parameters properly describe the H-bond strength. The ring, book, cage and prism isomers of water hexamer form 6, 7, 8 and 9 H-bonds, and the strength of the bonding in these isomers changes markedly. The internally-solvated and the all-surface structures of (H2O) n for n = 17, 19 and 21 are nearly isoenergetic. The internally-solvated isomers form fewer but stronger H-bonds. The hydrogen bonding in the above clusters are investigated in detail. The geometric parameters can well describe the characters of the H-bonds, and they correlate well with the H-bond strength. For the structures forming stronger H-bonds, the H-bond lengths are shorter, the angle parameters are closer to the optimum values, and their rms deviations are smaller. The H-bonds emanating from DDAA and DDA molecules as H-donor are relatively weak. The vibrational spectra of (H2O) n ( n = 17, 19 and 21) are studied as well. The stretching vibration of the intramolecular OH bond is sensitive to its bonding environment. The H-bond strength judged from the geometric parameters is in good agreement with the bonding strength judged from the stretching frequencies.

  12. Turnover of oxygen and hydrogen isotopes in the body water, CO 2, hair, and enamel of a small mammal

    NASA Astrophysics Data System (ADS)

    Podlesak, David W.; Torregrossa, Ann-Marie; Ehleringer, James R.; Dearing, M. Denise; Passey, Benjamin H.; Cerling, Thure E.

    2008-01-01

    Oxygen and hydrogen isotope signatures of animal tissues are strongly correlated with the isotope signature of local precipitation and as a result, isotope signatures of tissues are commonly used to study resource utilization and migration in animals and to reconstruct climate. To better understand the mechanisms behind these correlations, we manipulated the isotope composition of the drinking water and food supplied to captive woodrats to quantify the relationships between drinking water ( δdw), body water ( δbw), and tissue ( δt). Woodrats were fed an isotopically constant food but were supplied with isotopically depleted or enriched water. Some animals were switched between these waters, allowing simultaneous determination of body water turnover, isotope change recorded in teeth and hair, and fractional contributions of atmospheric O 2, drinking water, and food to the oxygen and hydrogen budgets of the animals. The half-life of the body water turnover was 3-6 days. A mass balance model estimated that drinking water, atmospheric O 2, and food were responsible for 56%, 30%, and 15% of the oxygen in the body water, respectively. Drinking water and food were responsible for 71% and 29% of the hydrogen in the body water, respectively. Published generalized models for lab rats and humans accurately estimated δbw, as did an updated version of a specific model for woodrats. The change in drinking water was clearly recorded in hair and tooth enamel, and multiple-pool and tooth enamel forward models closely predicted these changes in hair and enamel, respectively. Oxygen and hydrogen atoms in the drinking water strongly influence the composition of the body water and tissues such as hair and tooth enamel; however, food and atmospheric O 2 also contribute oxygen and/or hydrogen atoms to tissue. Controlled experiments allow researchers to validate models that estimate δt based on δdw and so will increase the reliability of estimates of resource utilization and climate

  13. Hydrogen peroxide deposition and decomposition in rain and dew waters

    NASA Astrophysics Data System (ADS)

    Ortiz, Vicky; Angélica Rubio, M.; Lissi, Eduardo A.

    Peroxides and hydrogen peroxide were determined by a fluorometric method in dew and rain collected in the atmosphere of Santiago of Chile city. The measured peroxides comprise hydrogen peroxide (the main component) and peroxides not decomposed by catalase. The collected natural peroxides readily decompose in the natural matrix, rendering difficult an estimation of the values present in real-time. In order to establish the kinetics of the process and the factors that condition their decomposition, the kinetics of the decay at several pHs and/or the presence of metal chelators were followed. The kinetics of hydrogen peroxide decomposition in the water matrix was evaluated employing the natural peroxides or hydrogen peroxide externally added. First-order kinetics was followed, with half decay times ranging from 80 to 2300 min. The addition of Fe(II) in the micromolar range increases the decomposition rate, while lowering the pH (<3) notably reduces the rate of the process. The contribution of metals to the decomposition of the peroxides in the natural waters was confirmed by the reduction in decomposition rate elicited by its treatment with Chelex-100. Dew and rain waters were collected in pre-acidified collectors, rendering values considerably higher than those measured in non-treated collectors. This indicates that acidification can be proposed as an easy procedure to stabilize the samples, reducing its decomposition during collection time and the time elapsed between collection and analysis. The weighted average concentration for total peroxides measured in pre-treated collectors was 5.4 μM in rains and 2.2 μM in dews.

  14. A model predicting hydrogen and oxygen isotopes of mammalian hair at the landscape scale

    NASA Astrophysics Data System (ADS)

    Ehleringer, J.; Podlesak, D.; Cerling, T.; Chesson, L.; Bowen, G.

    2006-12-01

    A model has been developed to predict hydrogen and oxygen isotope ratios of keratin in hair of mammalian herbivores and omnivores, incorporating the influences of drinking water and dietary input. The isotopic composition of carbohydrates in food sources and the water in blood and tissues are predicted as intermediate components linking drinking water and dietary sources (environment) with hair (environmental recorder). This model is scaled to landscape and regional levels using geographic information system map predictions of the hydrogen and oxygen isotope ratios of drinking waters and anticipated hydrogen and oxygen isotope ratios of carbohydrate food sources. The model was tested using isotope ratios of human hair (an omnivore) from across the USA. We discuss the application of this model as a tool for providing spatially integrated information about the quality of primary productivity relevant to mammalian herbivores over time, through the effects of varying primary productivity on protein nitrogen balance of the herbivore.

  15. A simple pore water hydrogen diffusion syringe sampler

    USGS Publications Warehouse

    Vroblesky, D.A.; Chapelle, F.H.; Bradley, P.M.

    2007-01-01

    Molecular hydrogen (H2) is an important intermediate product and electron donor in microbial metabolism. Concentrations of dissolved H 2 are often diagnostic of the predominant terminal electron-accepting processes in ground water systems or aquatic sediments. H2 concentrations are routinely measured in ground water monitoring wells but are rarely measured in saturated aquatic sediments due to a lack of simple and practical sampling methods. This report describes the design and development (including laboratory and field testing) of a simple, syringe-based H 2 sampler in (1) saturated, riparian sediments, (2) surface water bed sediments, and (3) packed intervals of a fractured bedrock borehole that are inaccessible by standard pumped methods. ?? 2007 National Ground Water Association.

  16. Historical Doses from Tritiated Water and Tritiated Hydrogen Gas Released to the Atmosphere from Lawrence Livermore National Laboratory (LLNL) Part 1. Description of Tritium Dose Model (DCART) for Routine Releases from LLNL

    SciTech Connect

    Peterson, S R

    2006-09-27

    DCART (Doses from Chronic Atmospheric Releases of Tritium) is a spreadsheet model developed at Lawrence Livermore National Laboratory (LLNL) that calculates doses from inhalation of tritiated hydrogen gas (HT), inhalation and skin absorption of tritiated water (HTO), and ingestion of HTO and organically bound tritium (OBT) to adult, child (age 10), and infant (age 6 months to 1 year) from routine atmospheric releases of HT and HTO. DCART is a deterministic model that, when coupled to the risk assessment software Crystal Ball{reg_sign}, predicts doses with a 95% confidence interval. The equations used by DCART are described and all distributions on parameter values are presented. DCART has been tested against the results of other models and several sets of observations in the Tritium Working Groups of the International Atomic Energy Agency's programs, Biosphere Modeling and Assessment and Environmental Modeling for Radiation Safety. The version of DCART described here has been modified to include parameter values and distributions specific to conditions at LLNL. In future work, DCART will be used to reconstruct dose to the hypothetical maximally exposed individual from annual routine releases of HTO and HT from all LLNL facilities and from the Sandia National Laboratory's Tritium Research Laboratory over the last fifty years.

  17. SOLUBILITY OF WATER ICE IN METALLIC HYDROGEN: CONSEQUENCES FOR CORE EROSION IN GAS GIANT PLANETS

    SciTech Connect

    Wilson, H. F.; Militzer, B.

    2012-01-20

    Using ab initio simulations we investigate whether water ice is stable in the cores of giant planets, or whether it dissolves into the layer of metallic hydrogen above. By Gibbs free energy calculations we find that for pressures between 10 and 40 Mbar the ice-hydrogen interface is thermodynamically unstable at temperatures above approximately 3000 K, far below the temperature of the core-mantle boundaries in Jupiter and Saturn. This implies that the dissolution of core material into the fluid layers of giant planets is thermodynamically favored, and that further modeling of the extent of core erosion is warranted.

  18. Hydrogen evolution from water through metal sulfide reactions

    SciTech Connect

    Saha, Arjun; Raghavachari, Krishnan

    2013-11-28

    Transition metal sulfides play an important catalytic role in many chemical reactions. In this work, we have conducted a careful computational study of the structures, electronic states, and reactivity of metal sulfide cluster anions M{sub 2}S{sub X}{sup −} (M = Mo and W, X = 4–6) using density functional theory. Detailed structural analysis shows that these metal sulfide anions have ground state isomers with two bridging sulfide bonds, notably different in some cases from the corresponding oxides with the same stoichiometry. The chemical reactivity of these metal sulfide anions with water has also been carried out. After a thorough search on the reactive potential energy surface, we propose several competitive, energetically favorable, reaction pathways that lead to the evolution of hydrogen. Selectivity in the initial water addition and subsequent hydrogen migration are found to be the key steps in all the proposed reaction channels. Initial adsorption of water is most favored involving a terminal metal sulfur bond in Mo{sub 2}S{sub 4}{sup −} isomers whereas the most preferred orientation for water addition involves a bridging metal sulfur bond in the case of W{sub 2}S{sub 4}{sup −} and M{sub 2}S{sub 5}{sup −} isomers. In all the lowest energy H{sub 2} elimination steps, the interacting hydrogen atoms involve a metal hydride and a metal hydroxide (or thiol) group. We have also observed a higher energy reaction channel where the interacting hydrogen atoms in the H{sub 2} elimination step involve a thiol (–SH) and a hydroxyl (–OH) group. For all the reaction pathways, the Mo sulfide reactions involve a higher barrier than the corresponding W analogues. We observe for both metals that reactions of M{sub 2}S{sub 4}{sup −} and M{sub 2}S{sub 5}{sup −} clusters with water to liberate H{sub 2} are exothermic and involve modest free energy barriers. However, the reaction of water with M{sub 2}S{sub 6}{sup −} is highly endothermic with a considerable

  19. Hydrogen production from high moisture content biomass in supercritical water

    SciTech Connect

    Antal, M.J. Jr.; Xu, X.

    1998-08-01

    By mixing wood sawdust with a corn starch gel, a viscous paste can be produced that is easily delivered to a supercritical flow reactor by means of a cement pump. Mixtures of about 10 wt% wood sawdust with 3.65 wt% starch are employed in this work, which the authors estimate to cost about $0.043 per lb. Significant reductions in feed cost can be achieved by increasing the wood sawdust loading, but such an increase may require a more complex pump. When this feed is rapidly heated in a tubular flow reactor at pressures above the critical pressure of water (22 MPa), the sawdust paste vaporizes without the formation of char. A packed bed of carbon catalyst in the reactor operating at about 650 C causes the tarry vapors to react with water, producing hydrogen, carbon dioxide, and some methane with a trace of carbon monoxide. The temperature and history of the reactor`s wall influence the hydrogen-methane product equilibrium by catalyzing the methane steam reforming reaction. The water effluent from the reactor is clean. Other biomass feedstocks, such as the waste product of biodiesel production, behave similarly. Unfortunately, sewage sludge does not evidence favorable gasification characteristics and is not a promising feedstock for supercritical water gasification.

  20. Hydrogen isotopes from source water to leaf lipid in a continental-scale sample network

    NASA Astrophysics Data System (ADS)

    Nelson, Daniel; Kahmen, Ansgar

    2015-04-01

    Sedimentary plant waxes are useful paleoclimate proxies because they are preserved in depositional settings on geologic timescales and the isotopic composition of the hydrogen in these molecules reflects that of the source water available during biosynthesis. This application is based largely on empirical calibrations that have demonstrated continental-scale correlations between source water and lipid hydrogen isotope values. However, the importance of variable net isotopic fractionation between source water and lipid for different species and environmental conditions is increasingly recognized. Isotopic enrichment of leaf water during transpiration is key among these secondary factors, and is itself sensitive to changes in hydroclimate. Leaf water enrichment also occurs prior to photosynthetic water uptake, and is therefore independent from cellular-level biomarker synthesis. Mechanistic models can predict the mean leaf water hydrogen isotope composition from readily available meteorological variables. This permits global-scale isoscape maps of leaf water isotopic composition and enrichment above source water to be generated, but these models have not been widely validated at continental spatial scales. We have established a network of twenty-one sites across Europe where we are sampling for leaf-, xylem-, and soil-water isotopes (H and O) at approximately 5-week intervals over the summer growing season. We augment the sample set with weekly to monthly precipitation samples and early- and late-season plant wax lipid samples. Collaborators at each site are conducting the sampling, and most sites are members of the FLUXNET tower network that also record high-resolution meteorological data. We present information on the implementation of the network and preliminary results from the 2014 summer season. The complete dataset will be used to track the evolution of water isotopes from source to leaf water and from leaf water to lipid hydrogen across diverse environments

  1. Statics and dynamics of free and hydrogen-bonded OH groups at the air/water interface.

    PubMed

    Vila Verde, Ana; Bolhuis, Peter G; Campen, R Kramer

    2012-08-09

    We use classical atomistic molecular dynamics simulations of two water models (SPC/E and TIP4P/2005) to investigate the orientation and reorientation dynamics of two subpopulations of OH groups belonging to water molecules at the air/water interface at 300 K: those OH groups that donate a hydrogen bond (called "bonded") and those that do not (called "free"). Free interfacial OH groups reorient in two distinct regimes: a fast regime from 0 to 1 ps and a slow regime thereafter. Qualitatively similar behavior was reported by others for free OH groups near extended hydrophobic surfaces. In contrast, the net reorientation of bonded OH groups occurs at a rate similar to that of bulk water. This similarity in reorientation rate results from compensation of two effects: decreasing frequency of hydrogen-bond breaking/formation (i.e., hydrogen-bond exchange) and faster rotation of intact hydrogen bonds. Both changes result from the decrease in density at the air/water interface relative to the bulk. Interestingly, because of the presence of capillary waves, the slowdown of hydrogen-bond exchange is significantly smaller than that reported for water near extended hydrophobic surfaces, but it is almost identical to that reported for water near small hydrophobic solutes. In this sense water at the air/water interface has characteristics of water of hydration of both small and extended hydrophobic solutes.

  2. New detection method for hydrogen gas for screening hydrogen-producing microorganisms using water-soluble wilkinson's catalyst derivative.

    PubMed

    Katsuda, Tomohisa; Ooshima, Hiroshi; Azuma, Masayuki; Kato, Jyoji

    2006-09-01

    A water-soluble color indicator was developed for the effective screening of hydrogen-producing microorganisms. This indicator consists of a coloring agent and a water-soluble derivative of Wilkinson's catalyst. Wilkinson's catalyst, Tris(triphenylphosphine) rhodium chloride, had been developed as a catalyst for the hydrogenation of olefins. We used a sulfonate of the catalyst for the hydrogenation of coloring agent in an aqueous medium. Several coloring agents, such as methyl orange, methyl red sodium, neutral red and Evan's blue, dissolved in water together with the sulfonated catalyst showed a change in color when hydrogen gas was fed into the solution by sparging at room temperature. We confirmed that methyl orange was decolorized by biologically produced hydrogen, when the photosynthetic bacterial strain Rhodobacter capsulatus ST-410 was grown in a medium containing 0.6 mM catalyst and 0.075 mM methyl orange in test tubes of 5 ml working volume.

  3. Historical Doses from Tritiated Water and Tritiated Hydrogen Gas Relesed to the Atmosphere from Lawrence Livermore National Laboratory (LLNL) Part 1. Description of Tritium Dose Model (DCART) for Chronic Releases from LLNL

    SciTech Connect

    Peterson, S

    2004-06-30

    DCART (Doses from Chronic Atmospheric Releases of Tritium) is a spreadsheet model developed at Lawrence Livermore National Laboratory (LLNL) that calculates doses from inhalation of tritiated hydrogen gas (HT), inhalation and skin absorption of tritiated water (HTO), and ingestion of HTO and organically bound tritium (OBT) to adult, child (age 10), and infant (age 6 months to 1 year) from routine atmospheric releases of HT and HTO. DCART is a deterministic model that, when coupled to the risk assessment software Crystal Ball{reg_sign}, predicts doses with a 95th percentile confidence interval. The equations used by DCART are described and all distributions on parameter values are presented. DCART has been tested against the results of other models and several sets of observations in the Tritium Working Group of the International Atomic Energy Agency's Biosphere Modeling and Assessment Programme. The version of DCART described here has been modified to include parameter values and distributions specific to conditions at LLNL. In future work, DCART will be used to reconstruct dose to the hypothetical maximally exposed individual from annual routine releases of HTO and HT from all LLNL facilities and from the Sandia National Laboratory's Tritium Research Laboratory over the last fifty years.

  4. Modeling of hydrogen sulfide oxidation in concrete corrosion products from sewer pipes.

    PubMed

    Jensen, Henriette Stokbro; Nielsen, Asbjørn Haaning; Hvitved-Jacobsen, Thorkild; Vollertsen, Jes

    2009-04-01

    Abiotic and biotic oxidation of hydrogen sulfide related to concrete corrosion was studied in corrosion products originating from a sewer manhole. The concrete corrosion products were suspended in an acidic solution, mimicking the conditions in the pore water of corroded concrete. The removal of hydrogen sulfide and dissolved oxygen was measured in parallel in the suspension, upon which the suspension was sterilized and the measurement repeated. The results revealed the biotic oxidation to be fast compared with the abiotic oxidation. The stoichiometry of the hydrogen sulfide oxidation was evaluated using the ratio between oxygen and hydrogen sulfide uptake. The ratio for the biotic oxidation pointed in the direction of elemental sulfur being formed as an intermediate in the oxidation of hydrogen sulfide to sulfuric acid. The experimental results were applied to suggest a hypothesis and a mathematical model describing the hydrogen sulfide oxidation pathway in a matrix of corroded concrete.

  5. Toward enhanced hydrogen generation from water using oxygen permeating LCF membranes.

    PubMed

    Wu, Xiao-Yu; Chang, Le; Uddi, Mruthunjaya; Kirchen, Patrick; Ghoniem, Ahmed F

    2015-04-21

    Hydrogen production from water thermolysis can be enhanced by the use of perovskite-type mixed ionic and electronic conducting (MIEC) membranes, through which oxygen permeation is driven by a chemical potential gradient. In this work, water thermolysis experiments were performed using 0.9 mm thick La0.9Ca0.1FeO3-δ (LCF-91) perovskite membranes at 990 °C in a lab-scale button-cell reactor. We examined the effects of the operating conditions such as the gas species concentrations and flow rates on the feed and sweep sides on the water thermolysis rate and oxygen flux. A single step reaction mechanism is proposed for surface reactions, and three-resistance permeation models are derived. Results show that water thermolysis is facilitated by the LCF-91 membrane especially when a fuel is added to the sweep gas. Increasing the gas flow rate and water concentration on the feed side or the hydrogen concentration on the sweep side enhances the hydrogen production rate. In this work, hydrogen is used as the fuel by construction, so that a single-step surface reaction mechanism can be developed and water thermolysis rate parameters can be derived. Both surface reaction rate parameters for oxygen incorporation/dissociation and hydrogen-oxygen reactions are fitted at 990 °C. We compare the oxygen fluxes in water thermolysis and air separation experiments, and identify different limiting steps in the processes involving various oxygen sources and sweep gases for this 0.9 mm thick LCF-91 membrane. In the air feed-inert sweep case, the bulk diffusion and sweep side surface reaction are the two limiting steps. In the water feed-inert sweep case, surface reaction on the feed side dominates the oxygen permeation process. Yet in the water feed-fuel sweep case, surface reactions on both the feed and sweep sides are rate determining when hydrogen concentration in the sweep side is in the range of 1-5 vol%. Furthermore, long term studies show that the surface morphology changes and

  6. Hydrogen bond network topology in liquid water and methanol: a graph theory approach.

    PubMed

    Bakó, Imre; Bencsura, Akos; Hermannson, Kersti; Bálint, Szabolcs; Grósz, Tamás; Chihaia, Viorel; Oláh, Julianna

    2013-09-28

    Networks are increasingly recognized as important building blocks of various systems in nature and society. Water is known to possess an extended hydrogen bond network, in which the individual bonds are broken in the sub-picosecond range and still the network structure remains intact. We investigated and compared the topological properties of liquid water and methanol at various temperatures using concepts derived within the framework of graph and network theory (neighbour number and cycle size distribution, the distribution of local cyclic and local bonding coefficients, Laplacian spectra of the network, inverse participation ratio distribution of the eigenvalues and average localization distribution of a node) and compared them to small world and Erdős-Rényi random networks. Various characteristic properties (e.g. the local cyclic and bonding coefficients) of the network in liquid water could be reproduced by small world and/or Erdős-Rényi networks, but the ring size distribution of water is unique and none of the studied graph models could describe it. Using the inverse participation ratio of the Laplacian eigenvectors we characterized the network inhomogeneities found in water and showed that similar phenomena can be observed in Erdős-Rényi and small world graphs. We demonstrated that the topological properties of the hydrogen bond network found in liquid water systematically change with the temperature and that increasing temperature leads to a broader ring size distribution. We applied the studied topological indices to the network of water molecules with four hydrogen bonds, and showed that at low temperature (250 K) these molecules form a percolated or nearly-percolated network, while at ambient or high temperatures only small clusters of four-hydrogen bonded water molecules exist.

  7. Hirshfeld atom refinement for modelling strong hydrogen bonds.

    PubMed

    Woińska, Magdalena; Jayatilaka, Dylan; Spackman, Mark A; Edwards, Alison J; Dominiak, Paulina M; Woźniak, Krzysztof; Nishibori, Eiji; Sugimoto, Kunihisa; Grabowsky, Simon

    2014-09-01

    High-resolution low-temperature synchrotron X-ray diffraction data of the salt L-phenylalaninium hydrogen maleate are used to test the new automated iterative Hirshfeld atom refinement (HAR) procedure for the modelling of strong hydrogen bonds. The HAR models used present the first examples of Z' > 1 treatments in the framework of wavefunction-based refinement methods. L-Phenylalaninium hydrogen maleate exhibits several hydrogen bonds in its crystal structure, of which the shortest and the most challenging to model is the O-H...O intramolecular hydrogen bond present in the hydrogen maleate anion (O...O distance is about 2.41 Å). In particular, the reconstruction of the electron density in the hydrogen maleate moiety and the determination of hydrogen-atom properties [positions, bond distances and anisotropic displacement parameters (ADPs)] are the focus of the study. For comparison to the HAR results, different spherical (independent atom model, IAM) and aspherical (free multipole model, MM; transferable aspherical atom model, TAAM) X-ray refinement techniques as well as results from a low-temperature neutron-diffraction experiment are employed. Hydrogen-atom ADPs are furthermore compared to those derived from a TLS/rigid-body (SHADE) treatment of the X-ray structures. The reference neutron-diffraction experiment reveals a truly symmetric hydrogen bond in the hydrogen maleate anion. Only with HAR is it possible to freely refine hydrogen-atom positions and ADPs from the X-ray data, which leads to the best electron-density model and the closest agreement with the structural parameters derived from the neutron-diffraction experiment, e.g. the symmetric hydrogen position can be reproduced. The multipole-based refinement techniques (MM and TAAM) yield slightly asymmetric positions, whereas the IAM yields a significantly asymmetric position.

  8. Revisions to the hydrogen gas generation computer model

    SciTech Connect

    Jerrell, J.W.

    1992-08-31

    Waste Management Technology has requested SRTC to maintain and extend a previously developed computer model, TRUGAS, which calculates hydrogen gas concentrations within the transuranic (TRU) waste drums. TRUGAS was written by Frank G. Smith using the BASIC language and is described in the report A Computer Model of gas Generation and Transport within TRU Waste Drums (DP- 1754). The computer model has been partially validated by yielding results similar to experimental data collected at SRL and LANL over a wide range of conditions. The model was created to provide the capability of predicting conditions that could potentially lead to the formation of flammable gas concentrations within drums, and to assess proposed drum venting methods. The model has served as a tool in determining how gas concentrations are affected by parameters such as filter vent sizes, waste composition, gas generation values, the number and types of enclosures, water instrusion into the drum, and curie loading. The success of the TRUGAS model has prompted an interest in the program`s maintenance and enhancement. Experimental data continues to be collected at various sites on such parameters as permeability values, packaging arrangements, filter designs, and waste contents. Information provided by this data is used to improve the accuracy of the model`s predictions. Also, several modifications to the model have been made to enlarge the scope of problems which can be analyzed. For instance, the model has been used to calculate hydrogen concentrations inside steel cabinets containing retired glove boxes (WSRC-RP-89-762). The revised TRUGAS computer model, H2GAS, is described in this report. This report summarizes all modifications made to the TRUGAS computer model and provides documentation useful for making future updates to H2GAS.

  9. Revisions to the hydrogen gas generation computer model

    SciTech Connect

    Jerrell, J.W.

    1992-08-31

    Waste Management Technology has requested SRTC to maintain and extend a previously developed computer model, TRUGAS, which calculates hydrogen gas concentrations within the transuranic (TRU) waste drums. TRUGAS was written by Frank G. Smith using the BASIC language and is described in the report A Computer Model of gas Generation and Transport within TRU Waste Drums (DP- 1754). The computer model has been partially validated by yielding results similar to experimental data collected at SRL and LANL over a wide range of conditions. The model was created to provide the capability of predicting conditions that could potentially lead to the formation of flammable gas concentrations within drums, and to assess proposed drum venting methods. The model has served as a tool in determining how gas concentrations are affected by parameters such as filter vent sizes, waste composition, gas generation values, the number and types of enclosures, water instrusion into the drum, and curie loading. The success of the TRUGAS model has prompted an interest in the program's maintenance and enhancement. Experimental data continues to be collected at various sites on such parameters as permeability values, packaging arrangements, filter designs, and waste contents. Information provided by this data is used to improve the accuracy of the model's predictions. Also, several modifications to the model have been made to enlarge the scope of problems which can be analyzed. For instance, the model has been used to calculate hydrogen concentrations inside steel cabinets containing retired glove boxes (WSRC-RP-89-762). The revised TRUGAS computer model, H2GAS, is described in this report. This report summarizes all modifications made to the TRUGAS computer model and provides documentation useful for making future updates to H2GAS.

  10. Hydration and hydrogen bond network of water around hydrophobic surface investigated by terahertz spectroscopy.

    PubMed

    Shiraga, K; Suzuki, T; Kondo, N; Ogawa, Y

    2014-12-21

    Water conformation around hydrophobic side chains of four amino acids (glycine, L-alanine, L-aminobutyric acid, and L-norvaline) was investigated via changes in complex dielectric constant in the terahertz (THz) region. Each of these amino acids has the same hydrophilic backbone, with successive additions of hydrophobic straight methylene groups (-CH2-) to the side chain. Changes in the degree of hydration (number of dynamically retarded water molecules relative to bulk water) and the structural conformation of the water hydrogen bond (HB) network related to the number of methylene groups were quantitatively measured. Since dielectric responses in the THz region represent water relaxations and water HB vibrations at a sub-picosecond and picosecond timescale, these measurements characterized the water relaxations and HB vibrations perturbed by the methylene apolar groups. We found each successive straight -CH2- group on the side chain restrained approximately two hydrophobic hydration water molecules. Additionally, the number of non-hydrogen-bonded (NHB) water molecules increased slightly around these hydrophobic side chains. The latter result seems to contradict the iceberg model proposed by Frank and Evans, where water molecules are said to be more ordered around apolar surfaces. Furthermore, we compared the water-hydrophilic interactions of the hydrophilic amino acid backbone with those with the water-hydrophobic interactions around the side chains. As the hydrophobicity of the side chain increased, the ordering of the surrounding water HB network was altered from that surrounding the hydrophilic amino acid backbone, thereby diminishing the fraction of NHB water and ordering the surrounding tetrahedral water HB network.

  11. Hydrogen-burn survival: preliminary thermal model and test results

    SciTech Connect

    McCulloch, W.H.; Ratzel, A.C.; Kempka, S.N.; Furgal, D.T.; Aragon, J.J.

    1982-08-01

    This report documents preliminary Hydrogen Burn Survival (HBS) Program experimental and analytical work conducted through February 1982. The effects of hydrogen deflagrations on safety-related equipment in nuclear power plant containment buildings are considered. Preliminary results from hydrogen deflagration experiments in the Sandia Variable Geometry Experimental System (VGES) are presented and analytical predictions for these tests are compared and discussed. Analytical estimates of component thermal responses to hydrogen deflagrations in the upper and lower compartments of an ice condenser, pressurized water reactor are also presented.

  12. Method for simultaneous recovery of hydrogen from water and from hydrocarbons

    DOEpatents

    Willms, R. Scott

    1996-01-01

    Method for simultaneous recovery of hydrogen and hydrogen isotopes from water and from hydrocarbons. A palladium membrane, when utilized in cooperation with a nickel catalyst in a reactor, has been found to drive reactions such as water gas shift, steam reforming and methane cracking to substantial completion by removing the product hydrogen from the reacting mixture. In addition, ultrapure hydrogen is produced, thereby eliminating the need for an additional processing step.

  13. Metal-Free Hydrogen Atom Transfer from Water: Expeditious Hydrogenation of N-Heterocycles Mediated by Diboronic Acid.

    PubMed

    Xia, Yun-Tao; Sun, Xiao-Tao; Zhang, Ling; Luo, Kai; Wu, Lei

    2016-11-21

    A hydrogenation of N-heterocycles mediated by diboronic acid with water as the hydrogen atom source is reported. A variety of N-heterocycles can be hydrogenated with medium to excellent yields within 10 min. Complete deuterium incorporation from stoichiometric D2 O onto substrates further exemplifies the H/D atom sources. Mechanism studies reveal that the reduction proceeds with initial 1,2-addition, in which diboronic acid synergistically activates substrates and water via a six-membered ring transition state.

  14. Water hydrogen bonding in proton exchange and neutral polymer membranes

    NASA Astrophysics Data System (ADS)

    Smedley, Sarah Black

    Understanding the dynamics of water sorbed into polymer films is critical to reveal structure-property relationships in membranes for energy and water treatment applications, where membranes must interact with water to facilitate or inhibit the transport of ions. The chemical structure of the polymer has drastic effects on the transport properties of the membrane due to the morphological structure of the polymer and how water is interacting with the functional groups on the polymer backbone. Therefore studying the dynamics of water adsorbed into a membrane will give insight into how water-polymer interactions influence transport properties of the film. With a better understanding of how to design materials to have specific properties, we can accelerate development of smarter materials for both energy and water treatment applications to increase efficiency and create high-flux materials and processes. The goal of this dissertation is to investigate the water-polymer interactions in proton exchange and uncharged membranes and make correlations to their charge densities and transport properties. A linear Fourier Transform Infrared (FTIR) spectroscopic method for measuring the hydrogen bonding distribution of water sorbed in proton exchange membranes is described in this thesis. The information on the distribution of the microenvironments of water in an ionic polymer is critical to understanding the effects of different acidic groups on the proton conductivity of proton exchange membranes at low relative humidity. The OD stretch of dilute HOD in H2O is a single, well-defined vibrational band. When HOD in dilute H2O is sorbed into a proton exchange membrane, the OD stretch peak shifts based on the microenvironment that water encounters within the nanophase separated structure of the material. This peak shift is a signature of different hydrogen bonding populations within the membrane, which can be deconvoluted rigorously for dilute HOD in H 2O compared to only

  15. Photovoltaic electrolysis - Hydrogen and electricity from water and light

    NASA Astrophysics Data System (ADS)

    Murphy, O. J.; Bockris, J. Om.

    Two photovoltaic couples, consisting of n on p and p on n gallium arsenide, respectively, have been converted into a water splitting device. Light is allowed to fall on the p part of one couple, which is in contact with air, and on the n side platinum is plated, which contacts the solution. On the other couple, the n side is in contact with air, while on the p side ruthenium dioxide is plated, which is in contact with the solution. Such a device gives a performance (8 percent conversion efficiency of solar light to hydrogen) better than that of known photoelectrolysis devices operating without battery assistance. Comparison with a coupled photovoltaic-distant water electrolyzer shows, under certain circumstances, some advantages for the present device.

  16. WATER DRAINAGE MODEL

    SciTech Connect

    J.B. Case

    2000-05-30

    The drainage of water from the emplacement drift is essential for the performance of the EBS. The unsaturated flow properties of the surrounding rock matrix and fractures determine how well the water will be naturally drained. To enhance natural drainage, it may be necessary to introduce engineered drainage features (e.g. drilled holes in the drifts), that will ensure communication of the flow into the fracture system. The purpose of the Water Drainage Model is to quantify and evaluate the capability of the drift to remove water naturally, using the selected conceptual repository design as a basis (CRWMS M&O, 1999d). The analysis will provide input to the Water Distribution and Removal Model of the EBS. The model is intended to be used to provide postclosure analysis of temperatures and drainage from the EBS. It has been determined that drainage from the EBS is a factor important to the postclosure safety case.

  17. Direct synthesis of hydrogen peroxide from plasma-water interactions

    PubMed Central

    Liu, Jiandi; He, Bangbang; Chen, Qiang; Li, Junshuai; Xiong, Qing; Yue, Guanghui; Zhang, Xianhui; Yang, Size; Liu, Hai; Liu, Qing Huo

    2016-01-01

    Hydrogen peroxide (H2O2) is usually considered to be an important reagent in green chemistry since water is the only by-product in H2O2 involved oxidation reactions. Early studies show that direct synthesis of H2O2 by plasma-water interactions is possible, while the factors affecting the H2O2 production in this method remain unclear. Herein, we present a study on the H2O2 synthesis by atmospheric pressure plasma-water interactions. The results indicate that the most important factors for the H2O2 production are the processes taking place at the plasma-water interface, including sputtering, electric field induced hydrated ion emission, and evaporation. The H2O2 production rate reaches ~1200 μmol/h when the liquid cathode is purified water or an aqueous solution of NaCl with an initial conductivity of 10500 μS cm−1. PMID:27917925

  18. Changes of Water Hydrogen Bond Network with Different Externalities

    PubMed Central

    Zhao, Lin; Ma, Kai; Yang, Zi

    2015-01-01

    It is crucial to uncover the mystery of water cluster and structural motif to have an insight into the abundant anomalies bound to water. In this context, the analysis of influence factors is an alternative way to shed light on the nature of water clusters. Water structure has been tentatively explained within different frameworks of structural models. Based on comprehensive analysis and summary of the studies on the response of water to four externalities (i.e., temperature, pressure, solutes and external fields), the changing trends of water structure and a deduced intrinsic structural motif are put forward in this work. The variations in physicochemical and biological effects of water induced by each externality are also discussed to emphasize the role of water in our daily life. On this basis, the underlying problems that need to be further studied are formulated by pointing out the limitations attached to current study techniques and to outline prominent studies that have come up recently. PMID:25884333

  19. Detection by high pressure infrared spectrometry of hydrogen-bonding between water and triacetyl glycerol.

    PubMed

    Mushayakarara, E C; Wong, P T; Mantsch, H H

    1986-01-14

    The barotropic behavior of neat and aqueous 1,2,3-triacetyl glycerol was investigated by FT-IR spectroscopy over the pressure range 0.001 to 35 kbar. The infrared spectrum in the presence of water shows bands characteristic of hydrogen bonded carbonyl groups. An increase in hydrostatic pressure leads to a strengthening of the intermolecular hydrogen bond between water and the lipid ester C = O groups. The pressure-induced formation of ice VI at 9 kbar does not affect this hydrogen bond, however, the formation, at 20 kbar, of ice VII in which the water/water hydrogen bonds are stronger than the lipid C = O/water hydrogen bonds, frees the lipid carbonyl groups from the hydrogen-bonding to water.

  20. Hydrogen production by water dissociation using ceramic membranes - annual report for FY 2008.

    SciTech Connect

    Balachandran, U.; Dorris, S. E.; Emerson, J. E.; Lee, T. H.; Lu, Y.; Park, C. Y.; Picciolo, J. J.; Energy Systems

    2009-03-25

    The objective of this project is to develop dense ceramic membranes that, without using an external power supply or circuitry, can produce hydrogen via coal/coal gas-assisted water dissociation. This project grew from an effort to develop a dense ceramic membrane for separating hydrogen from gas mixtures such as those generated during coal gasification, methane partial oxidation, and water-gas shift reactions. That effort led to the development of various cermet (i.e., ceramic/metal composite) membranes that enable hydrogen production by two methods. In one method, a hydrogen transport membrane (HTM) selectively removes hydrogen from a gas mixture by transporting it through either a mixed protonic/electronic conductor or a hydrogen transport metal. In the other method, an oxygen transport membrane (OTM) generates hydrogen mixed with steam by removing oxygen that is generated through water splitting. This project focuses on the development of OTMs that efficiently produce hydrogen via the dissociation of water. Supercritical boilers offer very high-pressure steam that can be decomposed to provide pure hydrogen by means of OTMs. Oxygen resulting from the dissociation of steam can be used for coal gasification, enriched combustion, or synthesis gas production. Hydrogen and sequestration-ready CO{sub 2} can be produced from coal and steam by using the membrane being developed in this project. Although hydrogen can also be generated by high-temperature steam electrolysis, producing hydrogen by water splitting with a mixed-conducting membrane requires no electric power or electrical circuitry.

  1. Hydrogen production by water dissociation using ceramic membranes. Annual report for FY 2009.

    SciTech Connect

    Balachandran, U.; Dorris, S. E.; Emerson, J. E.; Lee, T. H.; Lu, Y.; Park, C. Y.; Picciolo, J. J.; Energy Systems

    2010-04-20

    The objective of this project is to develop dense ceramic membranes that can produce hydrogen via coal/coal gas-assisted water dissociation without using an external power supply or circuitry. This project grew from an effort to develop a dense ceramic membrane for separating hydrogen from gas mixtures such as those generated during coal gasification, methane partial oxidation, and water-gas shift reactions. That effort led to the development of various cermet (i.e., ceramic/metal composite) membranes that enable hydrogen production by two methods. In one method, a hydrogen transport membrane selectively removes hydrogen from a gas mixture by transporting it through either a mixed protonic/electronic conductor or a hydrogen transport metal. In the other method, an oxygen transport membrane (OTM) generates hydrogen mixed with steam by removing oxygen that is generated through water splitting. This project focuses on the development of OTMs that efficiently produce hydrogen via the dissociation of water. Supercritical boilers offer very high-pressure steam that can be decomposed to provide pure hydrogen by means of OTMs. Oxygen resulting from the dissociation of steam can be used for coal gasification, enriched combustion, or synthesis gas production. Hydrogen and sequestration-ready CO{sub 2} can be produced from coal and steam by using the membrane being developed in this project. Although hydrogen can also be generated by high-temperature steam electrolysis, producing hydrogen by water splitting with a mixed-conducting membrane requires no electric power or electrical circuitry.

  2. Hydrogen production by water dissociation using ceramic membranes - annual report for FY 2010.

    SciTech Connect

    Balachandran, U.; Dorris, S. E.; Emerson, J. E.; Lee, T. H.; Lu, Y.; Park, C. Y.; Picciolo, J. J.

    2011-03-14

    The objective of this project is to develop dense ceramic membranes that can produce hydrogen via coal/coal gas-assisted water dissociation without using an external power supply or circuitry. This project grew from an effort to develop a dense ceramic membrane for separating hydrogen from gas mixtures such as those generated during coal gasification, methane partial oxidation, and water-gas shift reactions. That effort led to the development of various cermet (i.e., ceramic/metal composite) membranes that enable hydrogen production by two methods. In one method, a hydrogen transport membrane (HTM) selectively removes hydrogen from a gas mixture by transporting it through either a mixed protonic/electronic conductor or a hydrogen transport metal. In the other method, an oxygen transport membrane (OTM) generates hydrogen mixed with steam by removing oxygen that is generated through water splitting. This project focuses on the development of OTMs that efficiently produce hydrogen via the dissociation of water. Supercritical boilers offer very high-pressure steam that can be decomposed to provide pure hydrogen using OTMs. Oxygen resulting from the dissociation of steam can be used for coal gasification, enriched combustion, or synthesis gas production. Hydrogen and sequestration-ready CO{sub 2} can be produced from coal and steam by using the membrane being developed in this project. Although hydrogen can also be generated by high-temperature steam electrolysis, producing hydrogen by water splitting with a mixed-conducting membrane requires no electric power or electrical circuitry.

  3. The chemistry of subcritical water reactions of a hardwood derived lignin and lignin model compounds with nitrogen, hydrogen, carbon monoxide and carbon dioxide

    NASA Astrophysics Data System (ADS)

    Hill Bembenic, Meredith A.

    Biofuels, like cellulosic ethanol, may only be cost effective if the lignin byproduct is upgraded to value-added products. However, lignin's inherent aromatic structure and interunit crosslinkages hinder effective conversion. High temperature H2O is considered for lignin conversion, because H2O exhibits unusual properties at higher temperatures (particularly at its supercritical point of 374°C and 3205 psi) including a decreased ion product and a decreased static dielectric constant (similar to those of polar organic solvents at room temperature) such that there is a high solubility for organic compounds, like lignin. Much of the research concerning lignin and supercritical H2O has focused on further decomposition to gases (e.g., H2, CH4, and CO2) where nearly no char formation is expected in the presence of a catalyst. However, the conditions required for supercritical H2O are difficult to maintain, catalysts can be expensive, and gases are not favorable to the current liquid fuel infrastructure. Reactions using Organosolv lignin, subcritical H2O (365°C) and various industrial gases (N2, H2, CO, and CO2 at an initial pressure of 500 psi) for 30 min. were examined to determine both lignin's potential to generate value-added products (e.g., monomer compounds and methanol) and the role (if any) of the H2O and the gases during the reactions. The behavior of H2O at reaction temperature and pressure is expected to be similar to the behavior of supercritical H 2O without the need to maintain supercritical conditions. Different characterization techniques were used for the products collected including primarily GC/FID-TCD of the evolved gases, GC/MS analysis of the organic liquids, solid phase microextraction analysis of the water, and solid state 13C-NMR analysis of the residues. The reactor pressure at temperature was shown to influence the reactivity of the H2O and lignin, and the highest conversions (≈54--62%) were obtained when adding a gas. However, the

  4. EFFECT OF TEMPERATURE AND GLYCEROL ON THE HYDROGEN-BOND DYNAMICS OF WATER

    SciTech Connect

    Ghattyvenkatakrishna, Pavan K; Uberbacher, Edward C

    2013-01-01

    The effect of glycerol, water and glycerol-water binary mixtures on the structure and dynamics of biomolecules has been well studied. However, the effect of varying glycerol concentration and temperature on the dynamics of water has not received due attention. We have studied the effect of concentration and temperature on the hydrogen bonded network formed by water molecules. A strong correlation between the relaxation time of the network and average number of hydrogen bonds per water molecules was found. The radial distribution function of water oxygens and hydrogens clarifies the effect of concentration on the structure and clustering of water.

  5. Effectiveness of water spray mitigation systems for accidental releases of hydrogen fluoride. Volume 9. Wind tunnel modeling of fire monitors for HF vapor cloud mitigation, volume 1. Final report

    SciTech Connect

    Petersen, R.L.; Ratcliff, M.A.; Heskestad, G.; Parce, D.K.

    1992-05-01

    The hazards of hydrogen fluoride (HF) have long been recognized. Standard operating practices have been aimed at on minimizing the possibility of a release and mitigating the effects if a release should occur. These practices are continually monitored and improved to maximize safety protection based on the available technical data. The recent program targeted further improvements based on new technical data. The volume presents the results of wind tunnel simulations of water monitors and a surrogate gas for HF to quantify the effect of water spray/HF release configuration variables on the performance of multiple water monitors.

  6. Modelling the global tropospheric molecular hydrogen cycle

    NASA Astrophysics Data System (ADS)

    Pieterse, G.

    2013-01-01

    show that the global tropospheric budget of H2 can be constrained quite well with available measurements. The study starts with the derivation of a full hydrogen isotope chemistry scheme to use the measured deuterium content in atmospheric H2 as an additional constraint for the global budget. This new chemistry scheme is subsequently evaluated and the most important parameters in the photochemistry are identified. A condensed version of the new chemistry scheme is implemented in the global TM5 model. The new model results are verified using available measurements of H2 mixing ratios and isotopic compositions from two global flask sampling networks and the EuroHydros network. Finally, a new tropospheric budget is derived for H2. The tropospheric burden is estimated at 165±8 Tg and the removal of H2 by deposition and photochemical oxidation are estimated at 53±4 and 23±2 Tg/yr, respectively. The main (photochemical) source is estimated at 37±4 Tg/yr. From these numbers, a tropospheric lifetime of 2.2±0.2 yr for H2 is derived. These new ranges of uncertainty allow for a much more accurate evaluation of the impact of future increases in H2 emissions on air quality and climate.

  7. Hydrogen production from high-moisture content biomass in supercritical water

    SciTech Connect

    Antal, M.J. Jr.; Adschiri, T.; Ekbom, T.

    1996-10-01

    Most hydrogen is produced by steam reforming methane at elevated pressures. The goal of this research is to develop commercial processes for the catalytic steam reforming of biomass and other organic wastes at high pressures. This approach avoids the high cost of gas compression and takes advantage of the unique properties of water at high pressures. Prior to this year the authors reported the ability of carbon to catalyze the decomposition of biomass and related model compounds in supercritical water. The product gas consists of hydrogen, carbon dioxide, carbon monoxide, methane, and traces of higher hydrocarbons. During the past year the authors have: (a) developed a method to extend the catalyst life, (b) begun studies of the role of the shift reaction, (c) completed studies of carbon dioxide absorption from the product effluent by high pressure water, (d) measured the rate of carbon catalyst gasification in supercritical water, (e) discovered the pumpability of oil-biomass slurries, and (f) completed the design and begun fabrication of a flow reactor that will steam reform whole biomass feedstocks (i.e. sewage sludge) and produce a hydrogen rich synthesis gas at very high pressure (>22 MPa).

  8. Hydrogen/halogen fuel cell with improved water management system

    SciTech Connect

    Molter, T.M.; LaConti, A.B.

    1989-04-04

    This patent describes an improved method of operating a hydrogen/halogen fuel cell, comprising: a. introducing hydrogen fuel into the anode chamber of a fuel cell; b. introducing a halogen oxidant into the cathode chamber of a fuel cell; c. contacting the hydrogen fuel with the catalytic anode thereby catalytically disassociating the hydrogen into hydrogen ions and electrons; d. transporting the hydrogen ions through a solid polymer electrolyte membrane to the cathode electrode; e. passing the electrons through an external circuit to the cathode; and f. reacting the oxidant with the hydrogen ions in the presence of the catalytic cathode to produce an acid.

  9. Hydrogen Stark broadening by different kinds of model microfields

    NASA Astrophysics Data System (ADS)

    Seidel, J.

    1980-07-01

    A new model microfield is defined (the theta process) which in conjunction with the kangaroo process, is used to demonstrate the effects of different model microfields on hydrogen line profiles. The differences in the statistical features of the models give an estimate of the uncertainties associated with the method of model microfields. Stark broadening of hydrogen Lyman lines by either electrons or ions is investigated specifically.

  10. Polymer formulation for removing hydrogen and liquid water from an enclosed space

    DOEpatents

    Shepodd, Timothy J.

    2006-02-21

    This invention describes a solution to the particular problem of liquid water formation in hydrogen getters exposed to quantities of oxygen. Water formation is usually desired because the recombination reaction removes hydrogen without affecting gettering capacity and the oxygen removal reduces the chances for a hydrogen explosion once free oxygen is essentially removed. The present invention describes a getter incorporating a polyacrylate compound that can absorb up to 500% of its own weight in liquid water without significantly affecting its hydrogen gettering/recombination properties, but that also is insensitive to water vapor.

  11. EXPERIMENTAL EVIDENCE FOR WATER FORMATION VIA OZONE HYDROGENATION ON DUST GRAINS AT 10 K

    SciTech Connect

    Mokrane, H.; Chaabouni, H.; Accolla, M.; Congiu, E.; Dulieu, F.; Chehrouri, M.; Lemaire, J. L.

    2009-11-10

    The formation of water molecules from the reaction between ozone (O{sub 3}) and D-atoms is studied experimentally for the first time. Ozone is deposited on non-porous amorphous solid water ice (H{sub 2}O), and D-atoms are then sent onto the sample held at 10 K. HDO molecules are detected during the desorption of the whole substrate where isotope mixing takes place, indicating that water synthesis has occurred. The efficiency of water formation via hydrogenation of ozone is of the same order of magnitude as that found for reactions involving O-atoms or O{sub 2} molecules and exhibits no apparent activation barrier. These experiments validate the assumption made by models using ozone as one of the precursors of water formation via solid-state chemistry on interstellar dust grains.

  12. Nano-ferrites for Water Splitting: Unprecedented High Photocatalytic Hydrogen Production under Visible Light

    EPA Science Inventory

    In the present investigation, hydrogen production via water splitting by nano ferrites has been studied using ethanol as the sacrificial donor. The nano ferrite has shown great potential in hydrogen generation with hydrogen yield of 8275 9moles/h/ g of photocatalyst under visible...

  13. Development and Validation of a Model for Hydrogen Reduction of JSC-1A

    NASA Technical Reports Server (NTRS)

    Hegde, U.; Balasubramaniam, R.; Gokoglu, S.

    2009-01-01

    Hydrogen reduction of lunar regolith has been proposed as a viable technology for oxygen production on the moon. Hydrogen reduces FeO present in the lunar regolith to form metallic iron and water. The water may be electrolyzed to recycle the hydrogen and produce oxygen. Depending upon the regolith composition, FeO may be bound to TiO2 as ilmenite or it may be dispersed in glassy substrates. Some testing of hydrogen reduction has been conducted with Apollo-returned lunar regolith samples. However, due to the restricted amount of lunar material available for testing, detailed understanding and modeling of the reduction process in regolith have not yet been developed. As a step in this direction, hydrogen reduction studies have been carried out in more detail with lunar regolith simulants such as JSC-1A by NASA and other organizations. While JSC-1A has some similarities with lunar regolith, it does not duplicate the wide variety of regolith types on the moon, for example, it contains almost no ilmenite. Nonetheless, it is a good starting point for developing an understanding of the hydrogen reduction process with regolith-like material. In this paper, a model utilizing a shrinking core formulation coupled with the reactor flow is described and validated against experimental data on hydrogen reduction of JSC-1A.

  14. A coupled, pore-scale model for methanogenic microbial activity in underground hydrogen storage

    NASA Astrophysics Data System (ADS)

    Ebigbo, Anozie; Golfier, Fabrice; Quintard, Michel

    2013-11-01

    Underground hydrogen storage (UHS) as a means of energy storage is an efficient way of compensating for seasonal fluctuations in the availability of energy. One important factor which influences this technology is the activity of methanogenic microorganisms capable of utilising hydrogen and carbon dioxide for metabolism and leading to a change in the stored gas composition. A coupled, pore-scale model is presented which aids in the investigation of the mechanisms that govern the conversion of hydrogen to methane, i.e. advective hydrogen flow, its diffusion into microbial biofilms of multiple species, and its consumption within these biofilms. The model assumes that spherical grains are coated by a film of residual water and treats the biofilm development within each film in a quasi one-dimensional manner. A sample simulation using the presented model illustrates the biofilm growth process in these films as well as the competition between three different microbial species: methanogens, acetogens, and acetotrophs.

  15. Hydrogen production from salt water by Marine blue green algae and solar radiation

    NASA Technical Reports Server (NTRS)

    Mitsui, A.; Rosner, D.; Kumazawa, S.; Barciela, S.; Phlips, E.

    1985-01-01

    Two marine bluegreen algae, Oscillatoria sp. Miami BG 7 and Synechococcus sp Miami 041511 have been selected as the result of over 10 years continuous and intensive effort of isolation, growth examination, and the screening of hydrogen photoproduction capability in this laboratory. Both strains photoproduced hydrogen for several days at high rates and a quantity of hydrogen was accumulated in a closed vessel. Overall hydrogen donor substance of the hydrogen photoproduction was found to be salt water. Using strain Miami BG 7, a two step method of hydrogen photoproduction from salt water was successfully developed and this was recycled several times over a one month period using both free cells and immobilized cells in both indoor and outdoor under natural sunlight. According to these experiments, a prototype floating hydrogen production system was designed for further development of the biosolar hydrogen production system.

  16. Physiological water model development

    NASA Technical Reports Server (NTRS)

    Doty, Susan

    1993-01-01

    The water of the human body can be categorized as existing in two main compartments: intracellular water and extracellular water. The intracellular water consists of all the water within the cells and constitutes over half of the total body water. Since red blood cells are surrounded by plasma, and all other cells are surrounded by interstitial fluid, the intracellular compartment has been subdivided to represent these two cell types. The extracellular water, which includes all of the fluid outside of the cells, can be further subdivided into compartments which represent the interstitial fluid, circulating blood plasma, lymph, and transcellular water. The interstitial fluid surrounds cells outside of the vascular system whereas plasma is contained within the blood vessels. Avascular tissues such as dense connective tissue and cartilage contain interstitial water which slowly equilibrates with tracers used to determine extracellular fluid volume. For this reason, additional compartments are sometimes used to represent these avascular tissues. The average size of each compartment, in terms of percent body weight, has been determined for adult males and females. These compartments and the forces which cause flow between them are presented. The kidneys, a main compartment, receive about 25 percent of the cardiac output and filters out a fluid similar to plasma. The composition of this filtered fluid changes as it flows through the kidney tubules since compounds are continually being secreted and reabsorbed. Through this mechanism, the kidneys eliminate wastes while conserving body water, electrolytes, and metabolites. Since sodium accounts for over 90 percent of the cations in the extracellular fluid, and the number of cations is balanced by the number of anions, considering the renal handling sodium and water only should sufficiently describe the relationship between the plasma compartment and kidneys. A kidney function model is presented which has been adapted from a

  17. Doubly labeled water method: in vivo oxygen and hydrogen isotope fractionation

    SciTech Connect

    Schoeller, D.A.; Leitch, C.A.; Brown, C.

    1986-12-01

    The accuracy and precision of the doubly labeled water method for measuring energy expenditure are influenced by isotope fractionation during evaporative water loss and CO/sub 2/ excretion. To characterize in vivo isotope fractionation, we collected and isotopically analyzed physiological fluids and gases. Breath and transcutaneous water vapor were isotopically fractionated. The degree of fractionation indicated that the former was fractionated under equilibrium control at 37/sup 0/C, and the latter was kinetically fractionated. Sweat and urine were unfractionated. By use of isotopic balance models, the fraction of water lost via fractionating routes was estimated from the isotopic abundances of body water, local drinking water, and dietary solids. Fractionated water loss averaged 23% (SD = 10%) of water turnover, which agreed with our previous estimates based on metabolic rate, but there was a systematic difference between the results based on O/sub 2/ and hydrogen. Corrections for isotopic fractionation of water lost in breath and (nonsweat) transcutaneous loss should be made when using labeled water to measure water turnover or CO/sub 2/ production.

  18. Hydrogen bonded OH-stretching vibration in the water dimer.

    PubMed

    Schofield, Daniel P; Lane, Joseph R; Kjaergaard, Henrik G

    2007-02-01

    We have calculated the frequencies and intensities of the hydrogen-bonded OH-stretching transitions in the water dimer complex. The potential-energy curve and dipole-moment function are calculated ab initio at the coupled cluster with singles, doubles, and perturbative triples level of theory with correlation-consistent Dunning basis sets. The vibrational frequencies and wavefunctions are found from a numerical solution to a one-dimensional Schrödinger equation. The corresponding transition intensities are found from numerical integration of these vibrational wavefunctions with the ab initio calculated dipole moment function. We investigate the effect of counterpoise correcting both the potential-energy surface and dipole-moment function. We find that the effect of using a numeric potential is significant for higher overtones and that inclusion of a counterpoise correction for basis set superposition error is important.

  19. Elevated atmospheric escape of atomic hydrogen from Mars induced by high-altitude water

    NASA Astrophysics Data System (ADS)

    Chaffin, M. S.; Deighan, J.; Schneider, N. M.; Stewart, A. I. F.

    2017-01-01

    Atmospheric loss has controlled the history of Martian habitability, removing most of the planet’s initial water through atomic hydrogen and oxygen escape from the upper atmosphere to space. In standard models, H and O escape in a stoichiometric 2:1 ratio because H reaches the upper atmosphere via long-lived molecular hydrogen, whose abundance is regulated by a photochemical feedback sensitive to atmospheric oxygen content. The relatively constant escape rates these models predict are inconsistent with known H escape variations of more than an order of magnitude on seasonal timescales, variation that requires escaping H to have a source other than H2. The best candidate source is high-altitude water, detected by the Mars Express spacecraft in seasonally variable concentrations. Here we use a one-dimensional time-dependent photochemical model to show that the introduction of high-altitude water can produce a large increase in the H escape rate on a timescale of weeks, quantitatively linking these observations. This H escape pathway produces prompt H loss that is not immediately balanced by O escape, influencing the oxidation state of the atmosphere for millions of years. Martian atmospheric water loss may be dominated by escape via this pathway, which may therefore potentially control the planet’s atmospheric chemistry. Our findings highlight the influence that seasonal atmospheric variability can have on planetary evolution.

  20. Genesis and evolution of water in a two-mica pluton: A hydrogen isotope study

    USGS Publications Warehouse

    Brigham, R.H.; O'Neil, J.R.

    1985-01-01

    Measurements were made of the hydrogen isotope composition of 74 samples of muscovite, biotite, vein quartz and whole rocks from the Papoose Flat pluton, eastern California, U.S.A., and adjacent metamorphic and sedimentary rocks in order to elucidate the genesis and evolution of water and hydrous minerals in a two-mica granodiorite. Electron microprobe analyses were made of all micas so that the Suzuoki-Epstein equation could be used in evaluating the data. Based on experimental, theoretical and textural evidence of mica paragenesis, a model of hydrogen isotope fractionation between an aqueous vapor and a magma during crystallization has been constructed. This model accounts for the observed hydrogen isotope relations and implies that primary hydrogen isotope compositions have been preserved in a large portion of the pluton. The ?? D-values of biotites vary widely over the range -103 to -66% with most values lying between -90 and -70??? Muscovites, on the other hand, are isotopically more uniform and have ?? D-values of -61 to -41??? with most values lying between -50 and -46??? These data are consistent with the interpretation that biotite formed over a long period of crystallization whereas muscovite formed in a narrow interval, presumably during the final stages of crystallization when alumina and water contents were at their highest. Only 8 of the 21 muscovite-biotite pairs analyzed are in hydrogen isotope equilibrium as calculated from the Suzuoki-Epstein equation. Biotites in the western half of the pluton have relatively low ?? D-values of around -85???, whereas those in the eastern half have higher values of up to -66??? This pattern is a consequence of a loss of permeability associated with the syn-intrusive deformation of the western margin of the pluton. This loss of permeability enhanced the preservation of primary hydrogen isotope relations there by diverting water evolved from the magma out through the eastern half of the pluton where some deuteric

  1. Hydrogen-water vapor mixtures: Control of hydrothermal atmospheres by hydrogen osmosis

    USGS Publications Warehouse

    Shaw, H.R.

    1963-01-01

    Experiments at 700??C and 800 bars total pressure demonstrate positive deviations from ideality for mixtures of hydrogen and H2O gases. The deviations are greater than predicted with Stockmayer's method. The composition of the mixture and the fugacity of hydrogen are controlled by diffusing hydrogen through metallic membranes. The results give the fugacities of both H 2O and oxygen.

  2. A ketone/alcohol polymer for cycle of electrolytic hydrogen-fixing with water and releasing under mild conditions

    NASA Astrophysics Data System (ADS)

    Kato, Ryo; Yoshimasa, Keisuke; Egashira, Tatsuya; Oya, Takahiro; Oyaizu, Kenichi; Nishide, Hiroyuki

    2016-09-01

    Finding a safe and efficient carrier of hydrogen is a major challenge. Recently, hydrogenated organic compounds have been studied as hydrogen storage materials because of their ability to stably and reversibly store hydrogen by forming chemical bonds; however, these compounds often suffer from safety issues and are usually hydrogenated with hydrogen at high pressure and/or temperature. Here we present a ketone (fluorenone) polymer that can be moulded as a plastic sheet and fixes hydrogen via a simple electrolytic hydrogenation at -1.5 V (versus Ag/AgCl) in water at room temperature. The hydrogenated alcohol derivative (the fluorenol polymer) reversibly releases hydrogen by heating (80 °C) in the presence of an aqueous iridium catalyst. Both the use of a ketone polymer and the efficient hydrogen fixing with water as a proton source are completely different from other (de)hydrogenated compounds and hydrogenation processes. The easy handling and mouldable polymers could suggest a pocketable hydrogen carrier.

  3. Molecular hydrogen in drinking water protects against neurodegenerative changes induced by traumatic brain injury.

    PubMed

    Dohi, Kenji; Kraemer, Brian C; Erickson, Michelle A; McMillan, Pamela J; Kovac, Andrej; Flachbartova, Zuzana; Hansen, Kim M; Shah, Gul N; Sheibani, Nader; Salameh, Therese; Banks, William A

    2014-01-01

    Traumatic brain injury (TBI) in its various forms has emerged as a major problem for modern society. Acute TBI can transform into a chronic condition and be a risk factor for neurodegenerative diseases such as Alzheimer's and Parkinson's diseases, probably through induction of oxidative stress and neuroinflammation. Here, we examined the ability of the antioxidant molecular hydrogen given in drinking water (molecular hydrogen water; mHW) to alter the acute changes induced by controlled cortical impact (CCI), a commonly used experimental model of TBI. We found that mHW reversed CCI-induced edema by about half, completely blocked pathological tau expression, accentuated an early increase seen in several cytokines but attenuated that increase by day 7, reversed changes seen in the protein levels of aquaporin-4, HIF-1, MMP-2, and MMP-9, but not for amyloid beta peptide 1-40 or 1-42. Treatment with mHW also reversed the increase seen 4 h after CCI in gene expression related to oxidation/carbohydrate metabolism, cytokine release, leukocyte or cell migration, cytokine transport, ATP and nucleotide binding. Finally, we found that mHW preserved or increased ATP levels and propose a new mechanism for mHW, that of ATP production through the Jagendorf reaction. These results show that molecular hydrogen given in drinking water reverses many of the sequelae of CCI and suggests that it could be an easily administered, highly effective treatment for TBI.

  4. Hydrogen Bonding and Related Properties in Liquid Water: A Car-Parrinello Molecular Dynamics Simulation Study.

    PubMed

    Guardia, Elvira; Skarmoutsos, Ioannis; Masia, Marco

    2015-07-23

    The local hydrogen-bonding structure and dynamics of liquid water have been investigated using the Car-Parrinello molecular dynamics simulation technique. The radial distribution functions and coordination numbers around water molecules have been found to be strongly dependent on the number of hydrogen bonds formed by each molecule, revealing also the existence of local structural heterogeneities in the structure of the liquid. The results obtained have also revealed the strong effect of the local hydrogen-bonding network on the local tetrahedral structure and entropy. The investigation of the dynamics of the local hydrogen-bonding network in liquid water has shown that this network is very labile, and the hydrogen bonds break and reform very rapidly. Nevertheless, it has been found that the hydrogen-bonding states associated with the formation of four hydrogen bonds by a water molecule exhibit the largest survival probability and corresponding lifetime. The reorientational motions of water molecules have also been found to be strongly dependent on their initial hydrogen-bonding state. Finally, the dependence of the librational and vibrational modes of water molecules on the local hydrogen-bonding network has been carefully examined, revealing a significant effect upon the libration and bond-stretching peak frequencies. The calculated low frequency peaks come in agreement with previously reported interpretations of the experimental low-frequency Raman spectrum of liquid water.

  5. System level permeability modeling of porous hydrogen storage materials.

    SciTech Connect

    Kanouff, Michael P.; Dedrick, Daniel E.; Voskuilen, Tyler

    2010-01-01

    A permeability model for hydrogen transport in a porous material is successfully applied to both laboratory-scale and vehicle-scale sodium alanate hydrogen storage systems. The use of a Knudsen number dependent relationship for permeability of the material in conjunction with a constant area fraction channeling model is shown to accurately predict hydrogen flow through the reactors. Generally applicable model parameters were obtained by numerically fitting experimental measurements from reactors of different sizes and aspect ratios. The degree of channeling was experimentally determined from the measurements and found to be 2.08% of total cross-sectional area. Use of this constant area channeling model and the Knudsen dependent Young & Todd permeability model allows for accurate prediction of the hydrogen uptake performance of full-scale sodium alanate and similar metal hydride systems.

  6. The single donator-single acceptor hydrogen bonding structure in water probed by Raman spectroscopy.

    PubMed

    Sun, Qiang

    2010-02-07

    In this work, the Raman spectra of aqueous C(12)E(5) solutions are recorded and utilized to demonstrate the existence of single donator-single acceptor (DA) hydrogen bonding in water. From Raman OH stretching bands of aqueous C(12)E(5) solutions, the relative intensity of 3430 cm(-1) subband increases with C(12)E(5) concentrations. For confined water, the DA hydrogen bonding can be expected to be the important hydrogen bonding species. Therefore, the 3430 cm(-1) component can be ascribed to OH vibration engaged in DA hydrogen bonding. This is in agreement with our recent explanation on Raman OH stretching band of water. For water at ambient conditions, the double donor-double acceptor (DDAA) and DA should be the dominant hydrogen bonding species, the ratio of DDAA to DA can be approximately to be 0.75:1, and the mean hydrogen bonding can be determined to be 2.75.

  7. The single donator-single acceptor hydrogen bonding structure in water probed by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Sun, Qiang

    2010-02-01

    In this work, the Raman spectra of aqueous C12E5 solutions are recorded and utilized to demonstrate the existence of single donator-single acceptor (DA) hydrogen bonding in water. From Raman OH stretching bands of aqueous C12E5 solutions, the relative intensity of 3430 cm-1 subband increases with C12E5 concentrations. For confined water, the DA hydrogen bonding can be expected to be the important hydrogen bonding species. Therefore, the 3430 cm-1 component can be ascribed to OH vibration engaged in DA hydrogen bonding. This is in agreement with our recent explanation on Raman OH stretching band of water. For water at ambient conditions, the double donor-double acceptor (DDAA) and DA should be the dominant hydrogen bonding species, the ratio of DDAA to DA can be approximately to be 0.75:1, and the mean hydrogen bonding can be determined to be 2.75.

  8. Solar hydrogen by thermochemical water splitting cycles: design, modeling, and demonstration of a novel receiver/reactor for the high temperature decomposition of zno using concentrated sunlight

    NASA Astrophysics Data System (ADS)

    Kaiser, Zachary David Epping

    Documenting the presence of rare bat species can be difficult. The current summer survey protocol for the federally endangered Indiana bat ( Myotis sodalis) requires passive acoustic sampling with directional microphones (e.g., Anabats), but there are still questions about best practices for choosing survey sites and appropriate detector models. Indiana bats are capable of foraging in an array of cover types, including structurally-complex, interior forests. Further, data acquisition among different commercially available bat detectors is likely highly variable, due to the use of proprietary microphones with different frequency responses, sensitivities, and directionality. We paired omnidirectional Wildlife Acoustic SM2BAT+ (SM2) and directional Titley Scientific Anabat SD2 (Anabat) detectors at 71 random points near Indianapolis, Indiana from May-August 2012-2013 to compare data acquisition by phonic group (low, mid, Myotis) and to determine what factors affect probability of detection and site occupancy for Indiana bats when sampling with acoustics near an active maternity colony (0.20--8.39 km away). Weatherproofing for Anabat microphones was 45° angle PVC tubes and for SM2 microphones was their foam shielding; microphones were paired at 2 m and 5 m heights. Habitat and landscape covariates were measured in the field or via ArcGIS. We adjusted file parameters to make SM2 and Anabat data comparable. Files were identified using Bat Call ID software, with visual inspection of Indiana bat calls. The effects of detector type, phonic group, height, and their interactions on mean files recorded per site were assessed using generalized estimating equations and LSD pairwise comparisons. We reduced probability of detection (p) and site occupancy (ψ) model covariates with Pearson's correlation and PCA. We used Presence 6.1 software and Akaike's Information Criteria to assess models for p and ψ. Anabats and SM2s did not perform equally. Anabats recorded more low and

  9. Sims Analysis of Water Abundance and Hydrogen Isotope in Lunar Highland Plagioclase

    NASA Technical Reports Server (NTRS)

    Hui, Hejiu; Guan, Yunbin; Chen, Yang; Peslier, Anne H.; Zhang, Youxue; Liu, Yang; Rossman, George R.; Eiler, John M.; Neal, Clive R.

    2015-01-01

    The detection of indigenous water in mare basaltic glass beads has challenged the view established since the Apollo era of a "dry" Moon. Since this discovery, measurements of water in lunar apatite, olivine-hosted melt inclusions, agglutinates, and nominally anhydrous minerals have confirmed that lunar igneous materials contain water, implying that some parts of lunar mantle may have as much water as Earth's upper mantle. The interpretation of hydrogen (H) isotopes in lunar samples, however, is controversial. The large variation of H isotope ratios in lunar apatite (delta Deuterium = -202 to +1010 per mille) has been taken as evidence that water in the lunar interior comes from the lunar mantle, solar wind protons, and/or comets. The very low deuterium/H ratios in lunar agglutinates indicate that solar wind protons have contributed to their hydrogen content. Conversely, H isotopes in lunar volcanic glass beads and olivine-hosted melt inclusions being similar to those of common terrestrial igneous rocks, suggest a common origin for water in both Earth and Moon. Lunar water could be inherited from carbonaceous chondrites, consistent with the model of late accretion of chondrite-type materials to the Moon as proposed by. One complication about the sources of lunar water, is that geologic processes (e.g., late accretion and magmatic degassing) may have modified the H isotope signatures of lunar materials. Recent FTIR analyses have shown that plagioclases in lunar ferroan anorthosite contain approximately 6 ppm H2O. So far, ferroan anorthosite is the only available lithology that is believed to be a primary product of the lunar magma ocean (LMO). A possible consequence is that the LMO could have contained up to approximately 320 ppm H2O. Here we examine the possible sources of water in the LMO through measurements of water abundances and H isotopes in plagioclase of two ferroan anorthosites and one troctolite from lunar highlands.

  10. Electron-induced hydrogen loss in uracil in a water cluster environment

    SciTech Connect

    Smyth, M.; Kohanoff, J.; Fabrikant, I. I.

    2014-05-14

    Low-energy electron-impact hydrogen loss due to dissociative electron attachment (DEA) to the uracil and thymine molecules in a water cluster environment is investigated theoretically. Only the A{sup ′}-resonance contribution, describing the near-threshold behavior of DEA, is incorporated. Calculations are based on the nonlocal complex potential theory and the multiple scattering theory, and are performed for a model target with basic properties of uracil and thymine, surrounded by five water molecules. The DEA cross section is strongly enhanced when the attaching molecule is embedded in a water cluster. This growth is due to two effects: the increase of the resonance lifetime and the negative shift in the resonance position due to interaction of the intermediate negative ion with the surrounding water molecules. A similar effect was earlier found in DEA to chlorofluorocarbons.

  11. Temperature and water vapor pressure effects on the friction coefficient of hydrogenated diamondlike carbon films.

    SciTech Connect

    Dickrell, P. L.; Sawyer, W. G.; Eryilmaz, O. L.; Erdemir, A.; Energy Technology; Univ. of Florida

    2009-07-01

    Microtribological measurements of a hydrogenated diamondlike carbon film in controlled gaseous environments show that water vapor plays a significant role in the friction coefficient. These experiments reveal an initial high friction transient behavior that does not reoccur even after extended periods of exposure to low partial pressures of H{sub 2}O and O{sub 2}. Experiments varying both water vapor pressure and sample temperature show trends of a decreasing friction coefficient as a function of both the decreasing water vapor pressure and the increasing substrate temperature. Theses trends are examined with regard to first order gas-surface interactions. Model fits give activation energies on the order of 40 kJ/mol, which is consistent with water vapor desorption.

  12. Seasonal variations of hydrogen peroxide and water vapor on Mars: Further indications of heterogeneous chemistry

    NASA Astrophysics Data System (ADS)

    Encrenaz, T.; Greathouse, T. K.; Lefèvre, F.; Montmessin, F.; Forget, F.; Fouchet, T.; DeWitt, C.; Richter, M. J.; Lacy, J. H.; Bézard, B.; Atreya, S. K.

    2015-06-01

    We have completed our seasonal monitoring of hydrogen peroxide and water vapor on Mars using ground-based thermal imaging spectroscopy, by observing the planet in March 2014, when water vapor is maximum, and July 2014, when, according to photochemical models, hydrogen peroxide is expected to be maximum. Data have been obtained with the Texas Echelon Cross Echelle Spectrograph (TEXES) mounted at the 3 m-Infrared Telescope Facility (IRTF) at Maunakea Observatory. Maps of HDO and H2O2 have been obtained using line depth ratios of weak transitions of HDO and H2O2 divided by CO2. The retrieved maps of H2O2 are in good agreement with predictions including a chemical transport model, for both the March data (maximum water vapor) and the July data (maximum hydrogen peroxide). The retrieved maps of HDO are compared with simulations by Montmessin et al. (2005, J. Geophys. Res., 110, 03006) and H2O maps are inferred assuming a mean martian D/H ratio of 5 times the terrestrial value. For regions of maximum values of H2O and H2O2, we derive, for March 1 2014 (Ls = 96°), H2O2 = 20+/-7 ppbv, HDO = 450 +/-75 ppbv (45 +/-8 pr-nm), and for July 3, 2014 (Ls = 156°), H2O2 = 30+/-7 ppbv, HDO = 375+/-70 ppbv (22+/-3 pr-nm). In addition, the new observations are compared with LMD global climate model results and we favor simulations of H2O2 including heterogeneous reactions on water-ice clouds.

  13. Identification of intrinsic catalytic activity for electrochemical reduction of water molecules to generate hydrogen.

    PubMed

    Shinagawa, Tatsuya; Takanabe, Kazuhiro

    2015-06-21

    Insufficient hydronium ion activities at near-neutral pH and under unbuffered conditions induce diffusion-limited currents for hydrogen evolution, followed by a reaction with water molecules to generate hydrogen at elevated potentials. The observed constant current behaviors at near neutral pH reflect the intrinsic electrocatalytic reactivity of the metal electrodes for water reduction.

  14. Electron, proton and hydrogen-atom transfers in photosynthetic water oxidation.

    PubMed Central

    Tommos, Cecilia

    2002-01-01

    When photosynthetic organisms developed so that they could use water as an electron source to reduce carbon dioxide, the stage was set for efficient proliferation. Algae and plants spread globally and provided the foundation for our atmosphere and for O(2)-based chemistry in biological systems. Light-driven water oxidation is catalysed by photosystem II, the active site of which contains a redox-active tyrosine denoted Y(Z), a tetramanganese cluster, calcium and chloride. In 1995, Gerald Babcock and co-workers presented the hypothesis that photosynthetic water oxidation occurs as a metallo-radical catalysed process. In this model, the oxidized tyrosine radical is generated by coupled proton/electron transfer and re-reduced by abstracting hydrogen atoms from substrate water or hydroxide-ligated to the manganese cluster. The proposed function of Y(Z) requires proton transfer from the tyrosine site upon oxidation. The oxidation mechanism of Y(Z) in an inhibited and O(2)-evolving photosystem II is discussed. Domino-deprotonation from Y(Z) to the bulk solution is shown to be consistent with a variety of data obtained on metal-depleted samples. Experimental data that suggest that the oxidation of Y(Z) in O(2)-evolving samples is coupled to proton transfer in a hydrogen-bonding network are described. Finally, a dielectric-dependent model for the proton release that is associated with the catalytic cycle of photosystem II is discussed. PMID:12437877

  15. Consumption of hydrogen water prevents atherosclerosis in apolipoprotein E knockout mice.

    PubMed

    Ohsawa, Ikuroh; Nishimaki, Kiyomi; Yamagata, Kumi; Ishikawa, Masahiro; Ohta, Shigeo

    2008-12-26

    Oxidative stress is implicated in atherogenesis; however most clinical trials with dietary antioxidants failed to show marked success in preventing atherosclerotic diseases. We have found that hydrogen (dihydrogen; H(2)) acts as an effective antioxidant to reduce oxidative stress [I. Ohsawa, M. Ishikawa, K. Takahashi, M. Watanabe, K. Nishimaki, K. Yamagata, K. Katsura, Y. Katayama, S, Asoh, S. Ohta, Hydrogen acts as a therapeutic antioxidant by selectively reducing cytotoxic oxygen radicals, Nat. Med. 13 (2007) 688-694]. Here, we investigated whether drinking H(2)-dissolved water at a saturated level (H(2)-water) ad libitum prevents arteriosclerosis using an apolipoprotein E knockout mouse (apoE(-/-)), a model of the spontaneous development of atherosclerosis. ApoE(-/-) mice drank H(2)-water ad libitum from 2 to 6 month old throughout the whole period. Atherosclerotic lesions were significantly reduced by ad libitum drinking of H(2)-water (p=0.0069) as judged by Oil-Red-O staining series of sections of aorta. The oxidative stress level of aorta was decreased. Accumulation of macrophages in atherosclerotic lesions was confirmed. Thus, consumption of H(2)-dissolved water has the potential to prevent arteriosclerosis.

  16. Hydrogen bond dynamics and water structure in glucose-water solutions by depolarized Rayleigh scattering and low-frequency Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Paolantoni, Marco; Sassi, Paola; Morresi, Assunta; Santini, Sergio

    2007-07-01

    The effect of glucose on the relaxation process of water at picosecond time scales has been investigated by depolarized Rayleigh scattering (DRS) experiments. The process is assigned to the fast hydrogen bonding dynamics of the water network. In DRS spectra this contribution can be safely separated from the slower relaxation process due to the sugar. The detected relaxation time is studied at different glucose concentrations and modeled considering bulk and hydrating water contributions. As a result, it is found that in diluted conditions the hydrogen bond lifetime of proximal water molecules becomes about three times slower than that of the bulk. The effect of the sugar on the hydrogen bond water structure is investigated by analyzing the low-frequency Raman (LFR) spectrum sensitive to intermolecular modes. The addition of glucose strongly reduces the intensity of the band at 170cm-1 assigned to a collective stretching mode of water molecules arranged in cooperative tetrahedral domains. These findings indicate that proximal water molecules partially lose the tetrahedral ordering typical of the bulk leading to the formation of high density environments around the sugar. Thus the glucose imposes a new local order among water molecules localized in its hydration shell in which the hydrogen bond breaking dynamics is sensitively retarded. This work provides new experimental evidences that support recent molecular dynamics simulation and thermodynamics results.

  17. Hydrogen bond dynamics and water structure in glucose-water solutions by depolarized Rayleigh scattering and low-frequency Raman spectroscopy.

    PubMed

    Paolantoni, Marco; Sassi, Paola; Morresi, Assunta; Santini, Sergio

    2007-07-14

    The effect of glucose on the relaxation process of water at picosecond time scales has been investigated by depolarized Rayleigh scattering (DRS) experiments. The process is assigned to the fast hydrogen bonding dynamics of the water network. In DRS spectra this contribution can be safely separated from the slower relaxation process due to the sugar. The detected relaxation time is studied at different glucose concentrations and modeled considering bulk and hydrating water contributions. As a result, it is found that in diluted conditions the hydrogen bond lifetime of proximal water molecules becomes about three times slower than that of the bulk. The effect of the sugar on the hydrogen bond water structure is investigated by analyzing the low-frequency Raman (LFR) spectrum sensitive to intermolecular modes. The addition of glucose strongly reduces the intensity of the band at 170 cm(-1) assigned to a collective stretching mode of water molecules arranged in cooperative tetrahedral domains. These findings indicate that proximal water molecules partially lose the tetrahedral ordering typical of the bulk leading to the formation of high density environments around the sugar. Thus the glucose imposes a new local order among water molecules localized in its hydration shell in which the hydrogen bond breaking dynamics is sensitively retarded. This work provides new experimental evidences that support recent molecular dynamics simulation and thermodynamics results.

  18. Glycerol and bioglycerol conversion in supercritical water for hydrogen production.

    PubMed

    Yu-Wu, Q M; Weiss-Hortala, E; Barna, R; Boucard, H; Bulza, S

    2012-01-01

    Catalytic transesterification of vegetable oils leads to biodiesel and an alkaline feed (bioglycerol and organic residues, such as esters, alcohols. . .). The conversion ofbioglycerol into valuable organic molecules represents a sustainable industrial process leading to the valorization of a renewable organic resource. The physicochemical properties in the supercritical domain (T > 374 degrees C, P > 22.1 MPa) transform water into a solvent for organics and a reactant favouring radical reactions. In this context, the conversion ofbioglycerol in supercritical water (SCW) into platform molecules and/or high energetic gases (hydrogen, hydrocarbons) could represent an interesting valorization process. The reported research results concern the conversion of bioglycerol compared to pure glycerol. The experiments have been done in batch autoclaves (5 ml and 500 ml stirred). Solutions of pure (5 or 10 wt%) and crude (3.5 wt%) glycerol have been processed with or without catalyst (K2CO3 1.5 wt%) in the range of 450-600 degrees C. The molecular formula of bioglycerol was determined as C4.3H9.7O1.8Na0.1Si0.08. Glycerol was partially decomposed in the batch systems during the heating (42% before reaching 420 degrees C) and some intermediates (propanediol, ethylene glycol . . .) were quantified, leading to a proposition of a reaction pathway. Acrolein, a valuable platform molecule, was mainly produced in the absence of catalyst. No solid phase was recovered after SCW conversion of pure and bioglycerol in batch reactors. The optimal parameters for gasification were 600 degrees C, 25 MPa for bioglycerol and 525 degrees C, 25 MPa, for pure glycerol. In these operating conditions, 1 kg of pure or bioglycerol leads to 15 and, respectively, 10 mol of hydrogen. Supercritical water gasification of crude glycerol favoured the generation of light hydrocarbons, while pure glycerol promoted H2 production. SCW conversion of glycerol (pure and crude) allows to obtain simultaneously energetic

  19. Tuning epitaxial graphene sensitivity to water by hydrogen intercalation.

    PubMed

    Melios, C; Winters, M; Strupiński, W; Panchal, V; Giusca, C E; Imalka Jayawardena, K D G; Rorsman, N; Silva, S Ravi P; Kazakova, O

    2017-03-09

    The effects of humidity on the electronic properties of quasi-free standing one layer graphene (QFS 1LG) are investigated via simultaneous magneto-transport in the van der Pauw geometry and local work function measurements in a controlled environment. QFS 1LG on 4H-SiC(0001) is obtained by hydrogen intercalation of the interfacial layer. In this system, the carrier concentration experiences a two-fold increase in sensitivity to changes in relative humidity as compared to the as-grown epitaxial graphene. This enhanced sensitivity to water is attributed to the lowering of the hydrophobicity of QFS 1LG, which results from spontaneous polarization of 4H-SiC(0001) strongly influencing the graphene. Moreover, the superior carrier mobility of the QFS 1LG system is retained even at the highest humidity. The work function maps constructed from Kelvin probe force microscopy also revealed higher sensitivity to water for 1LG compared to 2LG in both QFS 1LG and as-grown systems. These results point to a new field of applications for QFS 1LG, i.e., as humidity sensors, and the corresponding need for metrology in calibration of graphene-based sensors and devices.

  20. Surface Water Response Modeling

    EPA Science Inventory

    During response to spills, or for facility planning, the vulnerability of downstream water resources is a major concern. How long and at what concentration do spilled contaminants reach downstream receptors? Models have the potential to answer these questions, but only if they ...

  1. WATER QUALITY MODELING RESEARCH

    EPA Science Inventory

    The multi-year planning science question of what additions to models are most needed for the TMDL process for priority stressors is addressed. Our research provides both the needed process research and the necessary technology (watershed hydrologic, hydrodynamic, and water quali...

  2. Dielectron attachment and hydrogen evolution reaction in water clusters.

    PubMed

    Barnett, Robert N; Giniger, Rina; Cheshnovsky, Ori; Landman, Uzi

    2011-06-30

    Binding of excess electrons to nanosize water droplets, with a focus on the hitherto largely unexplored properties of doubly-charged clusters, were investigated experimentally using mass spectrometry and theoretically with large-scale first-principles simulations based on spin-density-functional theory, with all the valence electrons (that is, 8e per water molecule) and excess electrons treated quantum mechanically. Singly-charged clusters (H(2)O)(n)(-1) were detected for n = 6-250, and our calculated vertical detachment energies agree with previously measured values in the entire range 15 ≤ n ≤ 105, giving a consistent interpretation in terms of internal, surface and diffuse states of the excess electron. Doubly-charged clusters were measured in the range of 83 ≤ n ≤ 123, with (H(2)O)(n)(-2) clusters found for 83 ≤ n < 105, and mass-shifted peaks corresponding to (H(2)O)(n-2)(OH(-))(2) detected for n ≥ 105. The simulations revealed surface and internal dielectron, e(-)(2), localization modes and elucidated the mechanism of the reaction (H(2)O)(n)(-2) → (H(2)O)(n-2) (OH(-))(2) + H(2) (for n ≥ 105), which was found to occur via concerted approach of a pair of protons belonging to two water molecules located in the first shell of the dielectron internal hydration cavity, culminating in formation of a hydrogen molecule 2H(+) + e(-)(2) → H(2). Instability of the dielectron internal localization impedes the reaction for smaller (n < 105) doubly-charged clusters.

  3. WATER-GAS SHIFT WITH INTEGRATED HYDROGEN SEPARATION PROCESS

    SciTech Connect

    Maria Flytzani-Stephanopoulos; Xiaomei Qi; Scott Kronewitter

    2004-02-01

    This project involved fundamental research and development of novel cerium oxide-based catalysts for the water-gas-shift reaction and the integration of these catalysts with Pd-alloy H{sub 2} -separation membranes supplying high purity hydrogen for fuel cell use. Conditions matching the requirements of coal gasifier-exit gas streams were examined in the project. Cu-cerium oxide was identified as the most promising high-temperature water-gas shift catalyst for integration with H{sub 2}-selective membranes. Formulations containing iron oxide were found to deactivate in the presence of CO{sub 2}. Cu-containing ceria catalysts, on the other hand, showed high stability in CO{sub 2}-rich gases. This type gas will be present over much of the catalyst, as the membrane removes the hydrogen produced from the shift reaction. The high-temperature shift catalyst composition was optimized by proper selection of dopant type and amount in ceria. The formulation 10at%Cu-Ce(30at%La)O{sub x} showed the best performance, and was selected for further kinetic studies. WGS reaction rates were measured in a simulated coal-gas mixture. The apparent activation energy, measured over aged catalysts, was equal to 70.2 kJ/mol. Reaction orders in CO, H{sub 2}O, CO{sub 2} and H{sub 2} were found to be 0.8, 0.2, -0.3, and -0.3, respectively. This shows that H{sub 2}O has very little effect on the reaction rate, and that both CO{sub 2} and H{sub 2} weakly inhibit the reaction. Good stability of catalyst performance was found in 40-hr long tests. A flat (38 cm{sup 2}) Pd-Cu alloy membrane reactor was used with the catalyst washcoated on oxidized aluminum screens close coupled with the membrane. To achieve higher loadings, catalyst granules were layered on the membrane itself to test the combined HTS activity/ H{sub 2} -separation efficiency of the composite. Simulated coal gas mixtures were used and the effect of membrane on the conversion of CO over the catalyst was evidenced at high space

  4. Selected bibliography on heavy water, tritiated water and hydrogen isotopes (1981-1992)

    NASA Astrophysics Data System (ADS)

    Gopalakrishnan, V. T.; Sutawane, U. B.; Rathi, B. N.

    A selected bibliography on heavy water, tritiated water and hydrogen isotopes is presented. This bibliography covers the period 1981-1992 and is in continuation to Division's earlier report BARC-1192 (1983). The sources of information for this compilation are Chemical Abstracts, INIS Atom Index and also some scattered search through journals and reports available in our library. No claim is made towards exhaustiveness of this bibliography even though sincere attempts have been made for a wide coverage. The bibliography is arranged under the headings: (1) production, purification, recovery, reprocessing and storage; (2) isotope exchange; (3) isotope analysis; (4) properties; and (5) miscellaneous. Total number of references in the bibliography are 1762.

  5. Ab initio path integral simulations for the fluoride ion-water clusters: competitive nuclear quantum effect between F(-)-water and water-water hydrogen bonds.

    PubMed

    Kawashima, Yukio; Suzuki, Kimichi; Tachikawa, Masanori

    2013-06-20

    Small hydrated fluoride ion complexes, F(-)(H2O)n (n = 1-3), have been studied by ab initio hybrid Monte Carlo (HMC) and ab initio path integral hybrid Monte Carlo (PIHMC) simulations. Because of the quantum effect, our simulation shows that the average hydrogen-bonded F(-)···HO distance in the quantum F(-)(H2O) is shorter than that in the classical one, while the relation inverts at the three water molecular F(-)(H2O)3 cluster. In the case of F(-)(H2O)3, we have found that the nuclear quantum effect enhances the formation of hydrogen bonds between two water molecules. In F(-)(H2O)2 and F(-)(H2O)3, the nuclear quantum effect on two different kinds of hydrogen bonds, F(-)-water and water-water hydrogen bonds, competes against each other. In F(-)(H2O)3, thus, the nuclear quantum effect on the water-water hydrogen bond leads to the elongation of hydrogen-bonded F(-)···HO distance, which we suggest this as the possible origin of the structural inversion from F(-)(H2O) to F(-)(H2O)3.

  6. Isotope Dependence and Quantum Effects on Atomic Hydrogen Diffusion in Liquid Water.

    PubMed

    Walker, J A; Mezyk, S P; Roduner, E; Bartels, D M

    2016-03-03

    Relative diffusion coefficients were determined in water for the D, H, and Mu isotopes of atomic hydrogen by measuring their diffusion-limited spin-exchange rate constants with Ni(2+) as a function of temperature. H and D atoms were generated by pulse radiolysis of water and measured by time-resolved pulsed EPR. Mu atoms are detected by muonium spin resonance. To isolate the atomic mass effect from solvent isotope effect, we measured all three spin-exchange rates in 90% D2O. The diffusion depends on the atomic mass, demonstrating breakdown of Stokes-Einstein behavior. The diffusion can be understood using a combination of water "cavity diffusion" and "hopping" mechanisms, as has been proposed in the literature. The H/D isotope effect agrees with previous modeling using ring polymer molecular dynamics. The "quantum swelling" effect on muonium due to its larger de Broglie wavelength does not seem to slow its "hopping" diffusion as much as predicted in previous work. Quantum effects of both the atom mass and the water librations have been modeled using RPMD and a qTIP4P/f quantized flexible water model. These results suggest that the muonium diffusion is very sensitive to the Mu versus water potential used.

  7. Atomic hydrogen distribution. [in Titan atmospheric model

    NASA Technical Reports Server (NTRS)

    Tabarie, N.

    1974-01-01

    Several possible H2 vertical distributions in Titan's atmosphere are considered with the constraint of 5 km-A a total quantity. Approximative calculations show that hydrogen distribution is quite sensitive to two other parameters of Titan's atmosphere: the temperature and the presence of other constituents. The escape fluxes of H and H2 are also estimated as well as the consequent distributions trapped in the Saturnian system.

  8. Phase transformation of oxide film in zirconium alloy in high temperature hydrogenated water

    SciTech Connect

    Kim, Taeho; Kim, Jongjin; Choi, Kyoung Joon; Yoo, Seung Chang; Kim, Seung Hyun; Kim, Ji Hyun

    2015-07-23

    The effect of the variation of the dissolved hydrogen concentration on the oxide phase transformation under high-temperature hydrogenated water conditions was investigated using in situ Raman spectroscopy. The Raman spectrum in 50 cm(3)/kg of dissolved hydrogen concentration indicated the formation of monoclinic and tetragonal zirconium oxide at the water-substrate interface. As the dissolved hydrogen concentration decreased to 30 cm(3)/kg, the Raman peaks corresponding to the zirconium oxide phase changed, indicating an oxide phase transformation. And, the results of SEM and TEM analyses were compared with those of in situ analyses obtained for the oxide structure formed on the zirconium alloy.

  9. Hydrogen Ingress in Steels During High-Temperature Oxidation in Water Vapor

    SciTech Connect

    Brady, Michael P; Fayek, Mostafa; Keiser, James R; Meyer III, Harry M; More, Karren Leslie; Anovitz, Lawrence {Larry} M; Wesolowski, David J; Cole, David R

    2011-01-01

    It is well established that hydrogen derived from water vapour can penetrate oxidizing alloys with detrimental effect. However, the complexities of tracking hydrogen in these materials have prevented the direct profiling of hydrogen ingress needed to understand these phenomena. Here we report hydrogen profiles in industrially-relevant alumina- and chromia- forming steels correlated with the local oxide-metal nano/microstructure by use of SIMS D2O tracer studies and experimental protocols to optimize D retention. The D profiles unexpectedly varied markedly among the alloys examined, which indicates mechanistic complexity but also the potential to mitigate detrimental water vapour effects by manipulation of alloy chemistry.

  10. Electrostatic model for hydrogen bonds in alcohols

    SciTech Connect

    Giguere, P.A.; Pigeon-Gosselin, M.

    1988-11-01

    The authors have measured the Raman spectra of liquid methanol at temperatures between 50/sup 0/ and -77/sup 0/C. The weak O-H stretching bands appear, under amplification, more and more asymmetric as the temperature is lowered. They can be decomposed into three Gaussian components centered at about 3220, 3310, and 3400 cm/sup -1/. The former, predominant at low temperature, corresponds to single, linear hydrogen bonds (LHB) between two molecules. The other two are assigned to branched hydrogen bonds, respectively bifurcated (BHB), between three molecules, and trifurcated (THB), between four molecules. They conclude that the molecular structure of liquid alcohols is not chain-like, as presumed so far, but a three-dimensional network featuring a mixture of single (LBH), and multiple hydrogen bonds (BHB, and THB). They are mainly electrostatic in nature, their relative proportions and geometry governed by the packing conditions for minimum energy. They form distinct trimers and tetramers in dilute solutions of alcohols in inert solvents and frozen matrices, and the latter even in the vapor.

  11. New porous water ice metastable at atmospheric pressure obtained by emptying a hydrogen-filled ice.

    PubMed

    Del Rosso, Leonardo; Celli, Milva; Ulivi, Lorenzo

    2016-11-07

    The properties of some forms of water ice reserve still intriguing surprises. Besides the several stable or metastable phases of pure ice, solid mixtures of water with gases are precursors of other ices, as in some cases they may be emptied, leaving a metastable hydrogen-bound water structure. We present here the first characterization of a new form of ice, obtained from the crystalline solid compound of water and molecular hydrogen called C0-structure filled ice. By means of Raman spectroscopy, we measure the hydrogen release at different temperatures and succeed in rapidly removing all the hydrogen molecules, obtaining a new form of ice (ice XVII). Its structure is determined by means of neutron diffraction measurements. Of paramount interest is that the emptied crystal can adsorb again hydrogen and release it repeatedly, showing a temperature-dependent hysteresis.

  12. New porous water ice metastable at atmospheric pressure obtained by emptying a hydrogen-filled ice

    NASA Astrophysics Data System (ADS)

    Del Rosso, Leonardo; Celli, Milva; Ulivi, Lorenzo

    2016-11-01

    The properties of some forms of water ice reserve still intriguing surprises. Besides the several stable or metastable phases of pure ice, solid mixtures of water with gases are precursors of other ices, as in some cases they may be emptied, leaving a metastable hydrogen-bound water structure. We present here the first characterization of a new form of ice, obtained from the crystalline solid compound of water and molecular hydrogen called C0-structure filled ice. By means of Raman spectroscopy, we measure the hydrogen release at different temperatures and succeed in rapidly removing all the hydrogen molecules, obtaining a new form of ice (ice XVII). Its structure is determined by means of neutron diffraction measurements. Of paramount interest is that the emptied crystal can adsorb again hydrogen and release it repeatedly, showing a temperature-dependent hysteresis.

  13. New porous water ice metastable at atmospheric pressure obtained by emptying a hydrogen-filled ice

    PubMed Central

    del Rosso, Leonardo; Celli, Milva; Ulivi, Lorenzo

    2016-01-01

    The properties of some forms of water ice reserve still intriguing surprises. Besides the several stable or metastable phases of pure ice, solid mixtures of water with gases are precursors of other ices, as in some cases they may be emptied, leaving a metastable hydrogen-bound water structure. We present here the first characterization of a new form of ice, obtained from the crystalline solid compound of water and molecular hydrogen called C0-structure filled ice. By means of Raman spectroscopy, we measure the hydrogen release at different temperatures and succeed in rapidly removing all the hydrogen molecules, obtaining a new form of ice (ice XVII). Its structure is determined by means of neutron diffraction measurements. Of paramount interest is that the emptied crystal can adsorb again hydrogen and release it repeatedly, showing a temperature-dependent hysteresis. PMID:27819265

  14. Infrared spectroscopy of water clusters co-adsorbed with hydrogen molecules on a sodium chloride film

    NASA Astrophysics Data System (ADS)

    Yamakawa, Koichiro; Fukutani, Katsuyuki

    2016-06-01

    Hydrogen gas containing a trace of water vapor was dosed on a vacuum-evaporated sodium chloride film at 13 K, and water clusters formed on the substrate were investigated by infrared absorption spectroscopy. Absorption bands due to (H2O)n clusters with n = 3-6 and an induced absorption band due to hydrogen were clearly observed. With increasing gas dosage, the intensities of the cluster bands increased linearly while the intensity of the hydrogen band was constant. This suggests that the water clusters were formed in two-dimensional matrices of hydrogen. We found that the water clusters did exist on the surface upon heating even after the hydrogen molecules had desorbed. A further rise of the substrate temperature up to 27 K yielded the formation of larger clusters, (H2O)n with n > 6 . We also discuss the origins of the two bands of the trimer in terms of pseudorotation and a metastable isomer.

  15. Graphene-based materials for hydrogen generation from light-driven water splitting.

    PubMed

    Xie, Guancai; Zhang, Kai; Guo, Beidou; Liu, Qian; Fang, Liang; Gong, Jian Ru

    2013-07-26

    Hydrogen production from solar water splitting has been considered as an ultimate solution to the energy and environmental issues. Over the past few years, graphene has made great contribution to improving the light-driven hydrogen generation performance. This article provides a comprehensive overview of the recent research progress on graphene-based materials for hydrogen evolution from light-driven water splitting. It begins with a brief introduction of the current status and basic principles of hydrogen generation from solar water splitting, and tailoring properties of graphene for application in this area. Then, the roles of graphene in hydrogen generation reaction, including an electron acceptor and transporter, a cocatalyst, a photocatalyst, and a photosensitizer, are elaborated respectively. After that, the comparison between graphene and other carbon materials in solar water splitting is made. Last, this review is concluded with remarks on some challenges and perspectives in this emerging field.

  16. Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water

    NASA Astrophysics Data System (ADS)

    Cortright, R. D.; Davda, R. R.; Dumesic, J. A.

    2002-08-01

    Concerns about the depletion of fossil fuel reserves and the pollution caused by continuously increasing energy demands make hydrogen an attractive alternative energy source. Hydrogen is currently derived from nonrenewable natural gas and petroleum, but could in principle be generated from renewable resources such as biomass or water. However, efficient hydrogen production from water remains difficult and technologies for generating hydrogen from biomass, such as enzymatic decomposition of sugars, steam-reforming of bio-oils and gasification, suffer from low hydrogen production rates and/or complex processing requirements. Here we demonstrate that hydrogen can be produced from sugars and alcohols at temperatures near 500K in a single-reactor aqueous-phase reforming process using a platinum-based catalyst. We are able to convert glucose-which makes up the major energy reserves in plants and animals-to hydrogen and gaseous alkanes, with hydrogen constituting 50% of the products. We find that the selectivity for hydrogen production increases when we use molecules that are more reduced than sugars, with ethylene glycol and methanol being almost completely converted into hydrogen and carbon dioxide. These findings suggest that catalytic aqueous-phase reforming might prove useful for the generation of hydrogen-rich fuel gas from carbohydrates extracted from renewable biomass and biomass waste streams.

  17. Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water.

    PubMed

    Cortright, R D; Davda, R R; Dumesic, J A

    2002-08-29

    Concerns about the depletion of fossil fuel reserves and the pollution caused by continuously increasing energy demands make hydrogen an attractive alternative energy source. Hydrogen is currently derived from nonrenewable natural gas and petroleum, but could in principle be generated from renewable resources such as biomass or water. However, efficient hydrogen production from water remains difficult and technologies for generating hydrogen from biomass, such as enzymatic decomposition of sugars, steam-reforming of bio-oils and gasification, suffer from low hydrogen production rates and/or complex processing requirements. Here we demonstrate that hydrogen can be produced from sugars and alcohols at temperatures near 500 K in a single-reactor aqueous-phase reforming process using a platinum-based catalyst. We are able to convert glucose -- which makes up the major energy reserves in plants and animals -- to hydrogen and gaseous alkanes, with hydrogen constituting 50% of the products. We find that the selectivity for hydrogen production increases when we use molecules that are more reduced than sugars, with ethylene glycol and methanol being almost completely converted into hydrogen and carbon dioxide. These findings suggest that catalytic aqueous-phase reforming might prove useful for the generation of hydrogen-rich fuel gas from carbohydrates extracted from renewable biomass and biomass waste streams.

  18. Modelling of hydrogen infrastructure for vehicle refuelling in London

    NASA Astrophysics Data System (ADS)

    Joffe, D.; Hart, D.; Bauen, A.

    One of the principal barriers to the widespread use of hydrogen as a road transport fuel is the need for a refuelling infrastructure to be established. The lack of an adequate refuelling infrastructure would severely inhibit an uptake of hydrogen vehicles. On the other hand, without significant penetration of these vehicles, the demand for hydrogen would be insufficient to make a widespread conventional refuelling infrastructure economic. The infrastructure is likely to develop initially in cities, due to the high concentration of vehicles and the anticipated air quality benefits of a switch to hydrogen as a road transport fuel. While trial schemes such as the Clean Urban Transport for Europe (CUTE) bus project will establish initial hydrogen refuelling sites, it is not clear how a transition to a widespread refuelling infrastructure will occur. Indeed, the number of possible different ways and scales of producing and distributing hydrogen means that the possible configurations for such an infrastructure are almost endless. Imperial College London is examining transition strategies for a hydrogen infrastructure for vehicle refuelling in London under a project funded by the UK Engineering and Physical Sciences Research Council (EPSRC). Imperial has five project partners from industry and local government to assist in this study: the Greater London Authority (GLA), BP, BOC, BMW and Air Products. This paper presents initial results from technical modelling of hydrogen infrastructure technologies and how they could be deployed to provide an initial facility for the refuelling of hydrogen fuel-cell buses in London. The results suggest that the choice of H 2 production technology can have significant effects on when the infrastructure would be installed, and the timing of hydrogen production, and bus refuelling.

  19. Ultrafast conversions between hydrogen bonded structures in liquid water observed by femtosecond x-ray spectroscopy

    NASA Astrophysics Data System (ADS)

    Wen, Haidan; Huse, Nils; Schoenlein, Robert W.; Lindenberg, Aaron M.

    2009-12-01

    We present the first femtosecond soft x-ray spectroscopy in liquids, enabling the observation of changes in hydrogen bond structures in water via core-hole excitation. The oxygen K-edge of vibrationally excited water is probed with femtosecond soft x-ray pulses, exploiting the relation between different water structures and distinct x-ray spectral features. After excitation of the intramolecular OH stretching vibration, characteristic x-ray absorption changes monitor the conversion of strongly hydrogen-bonded water structures to more disordered structures with weaker hydrogen-bonding described by a single subpicosecond time constant. The latter describes the thermalization time of vibrational excitations and defines the characteristic maximum rate with which nonequilibrium populations of more strongly hydrogen-bonded water structures convert to less-bonded ones. On short time scales, the relaxation of vibrational excitations leads to a transient high-pressure state and a transient absorption spectrum different from that of statically heated water.

  20. Ultrafast conversions between hydrogen bonded structures in liquid water observed by femtosecond x-ray spectroscopy

    SciTech Connect

    Wen, Haidan; Huse, Nils; Schoenlein, Robert W.; Lindenberg, Aaron M.

    2010-05-01

    We present the first femtosecond soft x-ray spectroscopy in liquids, enabling the observation of changes in hydrogen bond structures in water via core-hole excitation. The oxygen K-edge of vibrationally excited water is probed with femtosecond soft x-ray pulses, exploiting the relation between different water structures and distinct x-ray spectral features. After excitation of the intramolecular OH stretching vibration, characteristic x-ray absorption changes monitor the conversion of strongly hydrogen-bonded water structures to more disordered structures with weaker hydrogen-bonding described by a single subpicosecond time constant. The latter describes the thermalization time of vibrational excitations and defines the characteristic maximum rate with which nonequilibrium populations of more strongly hydrogen-bonded water structures convert to less-bonded ones. On short time scales, the relaxation of vibrational excitations leads to a transient high-pressure state and a transient absorption spectrum different from that of statically heated water.

  1. Hydrogen production by water dissociation using ceramic membranes. Annual report for FY 2007.

    SciTech Connect

    Balachandran, U.; Chen, L.; Dorris, S. E.; Emerson, J. E.; Lee, T. H.; Park, C. Y.; Picciolo, J. J.; Song, S. J.; Energy Systems

    2008-03-04

    The objective of this project is to develop dense ceramic membranes that, without using an external power supply or circuitry, can produce hydrogen via coal/coal gas-assisted water dissociation. This project grew out of an effort to develop a dense ceramic membrane for separating hydrogen from gas mixtures such as those generated during coal gasification, methane partial oxidation, and water-gas shift reactions [1]. That effort led to the development of various cermet (i.e., ceramic/metal composite) membranes that enable hydrogen to be produced by two methods. In one method, a hydrogen transport membrane (HTM) selectively removes hydrogen from a gas mixture by transporting it through either a mixed protonic/electronic conductor or a hydrogen transport metal. In the other method, an oxygen transport membrane (OTM) generates hydrogen mixed with steam by removing oxygen that is generated through water splitting [1, 2]. This project focuses on the development of OTMs that efficiently produce hydrogen via the dissociation of water. Supercritical boilers offer very high-pressure steam that can be decomposed to provide pure hydrogen by means of OTMs. Oxygen resulting from the dissociation of steam can be used for coal gasification, enriched combustion, or synthesis gas production. Hydrogen and sequestration-ready CO{sub 2} can be produced from coal and steam by using the membrane being developed in this project. Although hydrogen can also be generated by high-temperature steam electrolysis, producing hydrogen by water splitting with a mixed-conducting membrane requires no electric power or electrical circuitry.

  2. Effects of Mild Water Stress and Diurnal Changes in Temperature and Humidity on the Stable Oxygen and Hydrogen Isotopic Composition of Leaf Water in Cornus stolonifera L. 1

    PubMed Central

    Flanagan, Lawrence B.; Ehleringer, James R.

    1991-01-01

    In this paper we make comparisons between the observed stable isotopic composition of leaf water and the predictions of the Craig-Gordon model of isotopic enrichment when plants (Cornus stolonifera L.) were exposed to natural, diurnal changes in temperature and humidity in a glasshouse. In addition, we determined the effects of mild water stress on the isotopic composition of leaf water. The model predicted different patterns of diurnal change for the oxygen and hydrogen isotopic composition of leaf water. The observed leaf water isotopic composition followed qualitatively similar patterns of diurnal change to those predicted by the model. At midday, however, the model always predicted a higher degree of heavy isotope enrichment than was actually observed in leaves. There was no effect of mild water stress on the hydrogen isotopic composition of leaf water. For the oxygen isotopic composition of leaf water, there was either no significant difference between control and water-stressed plants or the stressed plants had lower δ18O values, despite the enriched stem water isotopic composition observed for the stressed plants. PMID:16668385

  3. Separation of gaseous hydrogen from a water-hydrogen mixture in a fuel cell power system operating in a weightless environment

    NASA Technical Reports Server (NTRS)

    Romanowski, William E. (Inventor); Suljak, George T. (Inventor)

    1989-01-01

    A fuel cell power system for use in a weightless environment, such as in space, includes a device for removing water from a water-hydrogen mixture condensed from the exhaust from the fuel cell power section of the system. Water is removed from the mixture in a centrifugal separator, and is fed into a holding, pressure operated water discharge valve via a Pitot tube. Entrained nondissolved hydrogen is removed from the Pitot tube by a bleed orifice in the Pitot tube before the water reaches the water discharge valve. Water discharged from the valve thus has a substantially reduced hydrogen content.

  4. The History of Water on Venus: a Scenario Accounting for Present Neon and Hydrogen Isotopic Ratios

    NASA Astrophysics Data System (ADS)

    Gillmann, C.; Chassefiere, E.; Lognonne, P.

    2009-12-01

    In order to study the evolution of the primitive atmosphere of Venus, we developped a time dependent model of hydrogen hydrodynamic escape powered by solar EUV (Extreme UV) flux and solar wind, and accounting for oxygen frictional escape We study specifically the isotopic fractionation of noble gases resulting from hydrodynamic escape. The fractionation’s primary cause is the effect of diffusive/gravitational separation between the homopause and the base of the escape. Heavy noble gases such as Kr and Xe are not fractionated. Ar is only marginally fractionated whereas Ne is moderately fractionated. We also take into account oxygen dragged off along with hydrogen by hydrodynamic process. In that case, most of the available energy is consumed by oxygen and the amount of energy available for the escape of hydrogen is reduced by one order of magnitude. We find nonetheless scenarios that are compatible with present-day Ne and Ar fractionation in Venus atmosphere. Our model suggests that during the first 100 Myr of the planetary accretion of Venus, no more than the content of five terrestrial oceans (5 TO) of water have been lost to space. Our preferred scenario shows that around 60% of the oxygen contained in this water was left behind in the atmosphere. During the end of the accretion, the atmospheric water vapor pressure could have been maintained at the value required to maintain the surface temperature above the liquidus. We argue that hydrodynamic escape could have controlled the solidification rate of the magma ocean during the end of the accretion period by pumping the water out of the magma, through the atmosphere, remaining at a pressure of around 300 bar. After most of the water in the magma has been extracted, the atmosphere progressively dried up, and the magma ocean crystallized, leading to a final collapse of the hydrodynamic escape. The end of the hydrodynamic escape phase and the crystallization of the primitive magma ocean would thus roughly coincide

  5. Structure of hydrogen-bonded associates in supercritical water under low and high pressures

    NASA Astrophysics Data System (ADS)

    Antipova, M. L.; Gurina, D. L.; Petrenko, V. E.

    2013-03-01

    The character and structural features of hydrogen-bonded associates in sub- and supercritical water are studied by analyzing distributions of the dipole moments of water molecules at P = 40, 80, and 100 MPa and T = 373-773 K, calculated using Car-Parrinello molecular dynamics. The main types of hydrogen-bonded structures and their changes upon isobaric heating are determined. It is shown that clusters with tetrahedral configurations exist in supercritical water only under high pressure.

  6. Hydrogen water reduces NSE, IL-6, and TNF-α levels in hypoxic-ischemic encephalopathy

    PubMed Central

    Yang, Lin

    2016-01-01

    Abstract This study retrospectively analyzed the efficacy of hydrogen water in the treatment of neonatal hypoxic-ischemic encephalopathy (HIE) and its effect on serum neuron-specific enolase (NSE), interleukin-6 (IL-6), and tumor necrosis factor-α (TNF-α) levels. Forty newborns with HIE who received treatment from April 2014 to April 2015 were divided into a conventional care group and a hydrogen water group according to the different treatment methods applied. Twenty healthy full-term newborns comprised the control group. In the hydrogen water group, 5-mL/kg hydrogen water was orally administered two days after birth daily for 10 days in addition to conventional treatment. After 10 days, efficacy indicators were examined in the HIE groups. The NSE, IL-6, and TNF-α levels were compared among all three groups. The efficacy indicators were significantly lower in the hydrogen water group compared with the conventional group. Before treatment, the serum NSE, IL-6, and TNF-α levels in the HIE groups were higher than those in the control group. After treatment, these levels in the hydrogen water group were lower than those in the conventional group. Hydrogen water lowers serum NSE, IL-6, and TNF-α levels in HIE newborns, thereby exerting a protective effect. PMID:28352827

  7. An alternative near-neighbor definition of hydrogen bonding in water.

    PubMed

    Hammerich, A D; Buch, V

    2008-03-21

    A definition of hydrogen bonding in water is proposed in which an H...O pair forms a hydrogen bond if (a) an oxygen atom is the nearest nonchemically bonded neighbor of a hydrogen atom; and (b) the hydrogen is the first or the second intermolecular near-neighbor of the oxygen. Unlike the commonly employed hydrogen-bond definitions, this definition does not depend on the choice of geometric or energetic cutoffs applied to continuous distributions of properties. With the present definition, the distribution of O...H bond lengths decays smoothly to zero in a physically reasonable range. After correction for the presence of intermittent hydrogen bonds, this definition appears to provide a more stable description of hydrogen bonds and coordination shells than the more conventional cutoff-based definition. "Partial" H bonds satisfying only one of the two bonding requirements serve as transition states in the H-bond network evolution.

  8. Concerted hydrogen-bond breaking by quantum tunneling in the water hexamer prism.

    PubMed

    Richardson, Jeremy O; Pérez, Cristóbal; Lobsiger, Simon; Reid, Adam A; Temelso, Berhane; Shields, George C; Kisiel, Zbigniew; Wales, David J; Pate, Brooks H; Althorpe, Stuart C

    2016-03-18

    The nature of the intermolecular forces between water molecules is the same in small hydrogen-bonded clusters as in the bulk. The rotational spectra of the clusters therefore give insight into the intermolecular forces present in liquid water and ice. The water hexamer is the smallest water cluster to support low-energy structures with branched three-dimensional hydrogen-bond networks, rather than cyclic two-dimensional topologies. Here we report measurements of splitting patterns in rotational transitions of the water hexamer prism, and we used quantum simulations to show that they result from geared and antigeared rotations of a pair of water molecules. Unlike previously reported tunneling motions in water clusters, the geared motion involves the concerted breaking of two hydrogen bonds. Similar types of motion may be feasible in interfacial and confined water.

  9. Distillation Kinetics of Solid Mixtures of Hydrogen Peroxide and Water and the Isolation of Pure Hydrogen Peroxide in Ultrahigh Vacuum

    NASA Technical Reports Server (NTRS)

    Teolis, B. D.; Baragiola, R. A.

    2006-01-01

    We present results of the growth of thin films of crystalline H2O2 and H2O2.2H2O (dihydrate) in ultrahigh vacuum by distilling an aqueous solution of hydrogen peroxide. We traced the process using infrared reflectance spectroscopy, mass loss on a quartz crystal microbalance, and in a few cases ultraviolet-visible reflectance. We find that the different crystalline phases-water, dihydrate, and hydrogen peroxide-have very different sublimation rates, making distillation efficient to isolate the less volatile component, crystalline H2O2.

  10. Mechanisms of hydrogen bond formation between ionic liquids and cellulose and the influence of water content.

    PubMed

    Rabideau, Brooks D; Ismail, Ahmed E

    2015-02-28

    We study the dynamics of the formation of multiple hydrogen bonds between ionic liquid anions and cellulose using molecular dynamics simulations. We examine fifteen different ionic liquids composed of 1-alkyl-3-methylimidazolium cations ([Cnmim], n = 1, 2, 3, 4, 5) paired with either chloride, acetate or dimethylphosphate. We map the transitions of anions hydrogen bonded to cellulose into different bonding states. We find that increased tail length in the ionic liquids has only a very minor effect on these transitions, tending to slow the dynamics of the transitions and increasing the hydrogen bond lifetimes. Each anion can form up to four hydrogen bonds with cellulose. We find that this hydrogen bond "redundancy" leads to multiply bonded anions having lifetimes three to four times that of singly bound anions. Such redundant hydrogen bonds account for roughly half of all anion-cellulose hydrogen bonds. Additional simulations for [C2mim]Cl, [C2mim]Ac and [C2mim]DMP were performed at different water concentrations between 70 mol% and 90 mol%. It was found that water crowds the hydrogen bond-accepting sites of the anions, preventing interactions with cellulose. The more water that is present in the system, the more crowded these sites become. Thus, if a hydrogen bond between an anion and cellulose breaks, the likelihood that it will be replaced by a nearby water molecule increases as well. We show that the formation of these "redundant" hydrogen bonding states is greatly affected by the presence of water, leading to steep drops in hydrogen bonding between the anions and cellulose.

  11. Lotic Water Hydrodynamic Model

    SciTech Connect

    Judi, David Ryan; Tasseff, Byron Alexander

    2015-01-23

    Water-related natural disasters, for example, floods and droughts, are among the most frequent and costly natural hazards, both socially and economically. Many of these floods are a result of excess rainfall collecting in streams and rivers, and subsequently overtopping banks and flowing overland into urban environments. Floods can cause physical damage to critical infrastructure and present health risks through the spread of waterborne diseases. Los Alamos National Laboratory (LANL) has developed Lotic, a state-of-the-art surface water hydrodynamic model, to simulate propagation of flood waves originating from a variety of events. Lotic is a two-dimensional (2D) flood model that has been used primarily for simulations in which overland water flows are characterized by movement in two dimensions, such as flood waves expected from rainfall-runoff events, storm surge, and tsunamis. In 2013, LANL developers enhanced Lotic through several development efforts. These developments included enhancements to the 2D simulation engine, including numerical formulation, computational efficiency developments, and visualization. Stakeholders can use simulation results to estimate infrastructure damage and cascading consequences within other sets of infrastructure, as well as to inform the development of flood mitigation strategies.

  12. Clusters of classical water models

    NASA Astrophysics Data System (ADS)

    Kiss, Péter T.; Baranyai, András

    2009-11-01

    The properties of clusters can be used as tests of models constructed for molecular simulation of water. We searched for configurations with minimal energies for a small number of molecules. We identified topologically different structures close to the absolute energy minimum of the system by calculating overlap integrals and enumerating hydrogen bonds. Starting from the dimer, we found increasing number of topologically different, low-energy arrangements for the trimer(3), the tetramer(6), the pentamer(6), and the hexamer(9). We studied simple models with polarizable point dipole. These were the BSV model [J. Brodholt et al., Mol. Phys. 86, 149 (1995)], the DC model [L. X. Dang and T. M. Chang, J. Chem. Phys. 106, 8149 (1997)], and the GCP model [P. Paricaud et al., J. Chem. Phys. 122, 244511 (2005)]. As an alternative the SWM4-DP and the SWM4-NDP charge-on-spring models [G. Lamoureux et al., Chem. Phys. Lett. 418, 245 (2006)] were also investigated. To study the impact of polarizability restricted to the plane of the molecule we carried out calculations for the SPC-FQ and TIP4P-FQ models, too [S. W. Rick et al., J. Chem. Phys. 101, 6141 (1994)]. In addition to them, justified by their widespread use even for near critical or surface behavior calculations, we identified clusters for five nonpolarizable models of ambient water, SPC/E [H. J. C. Berendsen et al., J. Phys. Chem. 91, 6269 (1987)], TIP4P [W. L. Jorgensen et al., J. Chem. Phys. 79, 926 (1983)], TIP4P-EW [H. W. Horn et al., J. Chem. Phys. 120, 9665 (2004)], and TIP4P/2005 [J. L. F. Abascal and C. Vega, J. Chem. Phys. 123, 234505 (2005)]. The fifth was a five-site model named TIP5P [M. W. Mahoney and W. L. Jorgensen, J. Chem. Phys. 112, 8910 (2000)]. To see the impact of the vibrations we studied the flexible SPC model. [K. Toukan and A. Rahman, Phys. Rev. B 31, 2643 (1985)]. We evaluated the results comparing them with experimental data and quantum chemical calculations. The position of the negative

  13. A theoretical study on the hydrogen-bonding interactions between flavonoids and ethanol/water.

    PubMed

    Zheng, Yan-Zhen; Zhou, Yu; Liang, Qin; Chen, Da-Fu; Guo, Rui

    2016-04-01

    Ethanol and water are the solvents most commonly used to extract flavonoids from propolis. Do hydrogen-bonding interactions exist between flavonoids and ethanol/water? In this work, this question was addressed by using density functional theory (DFT) to provide information on the hydrogen-bonding interactions between flavonoids and ethanol/water. Chrysin and Galangin were chosen as the representative flavonoids. The investigated complexes included chrysin-H2O, chrysin-CH3CH2OH, galangin-H2O and galangin-CH3CH2OH dyads. Molecular geometries, hydrogen-bond binding energies, charges of monomers and dyads, and topological analysis were studied at the B3LYP/M062X level of theory with the 6-31++G(d,p) basis set. The main conclusions were: (1) nine and ten optimized hydrogen-bond geometries were obtained for chrysin-H2O/CH3CH2OH and galangin-H2O/CH3CH2OH complexes, respectively. (2) The hydrogen atoms except aromatic H1 and H5 and all of the oxygen atoms can form hydrogen-bonds with H2O and CH3CH2OH. Ethanol and water form strong hydrogen-bonds with the hydroxyl, carbonyl and ether groups in chrysin/galangin and form weak hydrogen-bonds with aromatic hydrogen atoms. Except in structures labeled A and B, chrysin and galangin interact more strongly with H2O than CH3CH2OH. (3) When chrysin and galangin form hydrogen-bonds with H2O and CH3CH2OH, charge transfers from the hydrogen-bond acceptor (H2O and CH3CH2OH in structures A, B, G, H, I, J) to the hydrogen-bond donor (chrysin and galangin in structure A, B, G, H, I, J). The stronger hydrogen-bond makes the hydrogen-bond donor lose more charge (A> B> G> H> I> J). (4) Most of the hydrogen-bonds in chrysin/galangin-H2O/CH3CH2OH complexes may be considered as electrostatic dominant, while C-O2···H in structures labeled E and C-O5···H in structures labeled J are hydrogen-bonds combined of electrostatic and covalent characters. H9, H7, and O4 are the preferred hydrogen-bonding sites.

  14. Hydrogen-rich water attenuates brain damage and inflammation after traumatic brain injury in rats.

    PubMed

    Tian, Runfa; Hou, Zonggang; Hao, Shuyu; Wu, Weichuan; Mao, Xiang; Tao, Xiaogang; Lu, Te; Liu, Baiyun

    2016-04-15

    Inflammation and oxidative stress are the two major causes of apoptosis after traumatic brain injury (TBI). Most previous studies of the neuroprotective effects of hydrogen-rich water on TBI primarily focused on antioxidant effects. The present study investigated whether hydrogen-rich water (HRW) could attenuate brain damage and inflammation after traumatic brain injury in rats. A TBI model was induced using a controlled cortical impact injury. HRW or distilled water was injected intraperitoneally daily following surgery. We measured survival rate, brain edema, blood-brain barrier (BBB) breakdown and neurological dysfunction in all animals. Changes in inflammatory cytokines, inflammatory cells and Cho/Cr metabolites in brain tissues were also detected. Our results demonstrated that TBI-challenged rats exhibited significant brain injuries that were characterized by decreased survival rate and increased BBB permeability, brain edema, and neurological dysfunction, while HRW treatment ameliorated the consequences of TBI. HRW treatment also decreased the levels of pro-inflammatory cytokines (TNF-α, IL-1β and HMGB1), inflammatory cell number (Iba1) and inflammatory metabolites (Cho) and increased the levels of an anti-inflammatory cytokine (IL-10) in the brain tissues of TBI-challenged rats. In conclusion, HRW could exert a neuroprotective effect against TBI and attenuate inflammation, which suggests HRW as an effective therapeutic strategy for TBI patients.

  15. Coating permits use of strain gage in water and liquid hydrogen

    NASA Technical Reports Server (NTRS)

    Berven, B. B.

    1966-01-01

    Strain gage installation covered with a three-layer coating of commercial materials makes measurements in water and liquid hydrogen. It consists of a selected foil strain gage bonded with a modified commercial heat-curring epoxy cement. The outer protective layer of the gage installation may develop cracks when immersed in liquid hydrogen.

  16. Laboratory Studies of Hydrogen Gas Generation Using the Cobalt Chloride Catalyzed Sodium Borohydride-Water Reaction

    DTIC Science & Technology

    2015-07-01

    TECHNICAL REPORT 2082 July 2015 Laboratory Studies of Hydrogen Gas Generation Using the Cobalt Chloride Catalyzed Sodium ...describes experiments to generate hydrogen gas using the cobalt chloride catalyzed sodium borohydride-water reaction. Space and Naval Warfare Systems...to inflate LTAs. Of the metal hydrides, we chose to explore the sodium borohydride chemistry. We chose this chemistry because of its energy density

  17. Modeling molecular hydrogen emission in M dwarf exoplanetary systems

    NASA Astrophysics Data System (ADS)

    Evonosky, William; France, Kevin; Kruczek, Nick E.; Youngblood, Allison; Measurements of the Ultraviolet Spectral Characteristics of Low-mass Exoplanet host Stars (MUSCLES)

    2017-01-01

    Exoplanets orbiting low-mass stars are prime candidates for atmospheric characterization due to their astronomical abundance and short orbital periods. These planets orbit stars that are often more active than main sequence solar-type stars. They are exposed to differing levels of ultraviolet radiation which can cause traditional “biosignature” gases to be generated abiotically, potentially causing false-positive identifications of life. We modeled the recently discovered molecular hydrogen emission in the ultraviolet spectra (1350 - 1650 Å) as arising from the stellar surface, excited by radiation generated in the upper chromosphere. The model was compared with observed hydrogen emission from the “Measurements of the Ultraviolet Spectral Characteristics of Low-mass Exoplanet host Stars” (MUSCLES) survey by conducting a grid search and implementing a chi-squared minimization routine. We considered only progressions from the [1, 4] and [1, 7] first excited electronic levels. Our modeling procedure varied the atomic hydrogen column density (in the chromosphere) as well as the photospheric molecular hydrogen column density and temperature. The model required as an input a reconstructed intrinsic Lyman α profile which served as the pumping radiation for the molecular hydrogen. We found that an atomic hydrogen column density of log10N(H I) = 14.13 ± 0.16 cm-2 represents a breaking point above which there is not enough Lyman α flux available to excite a significant molecular hydrogen population into the [1, 7] state. We also present H2 temperatures which may suggest that star spots on low mass stars persist longer, and encompass more area than star spots on solar-type stars.

  18. Energetics of hydrogen bonding in proteins: a model compound study.

    PubMed Central

    Habermann, S. M.; Murphy, K. P.

    1996-01-01

    Differences in the energetics of amide-amide and amide-hydroxyl hydrogen bonds in proteins have been explored from the effect of hydroxyl groups on the structure and dissolution energetics of a series of crystalline cyclic dipeptides. The calorimetrically determined energetics are interpreted in light of the crystal structures of the studied compounds. Our results indicate that the amide-amide and amide-hydroxyl hydrogen bonds both provide considerable enthalpic stability, but that the amide-amide hydrogen bond is about twice that of the amide-hydroxyl. Additionally, the interaction of the hydroxyl group with water is seen most readily in its contributions to entropy and heat capacity changes. Surprisingly, the hydroxyl group shows weakly hydrophobic behavior in terms of these contributions. These results can be used to understand the effects of mutations on the stability of globular proteins. PMID:8819156

  19. Origin of Terrestrial Water: Hydrogen/Deuterium Fractionation into Earth's Core

    NASA Astrophysics Data System (ADS)

    Wu, J.; Buseck, P. R.

    2014-12-01

    Hydrogen isotopic compositions are among the most important constraints on the origin of Earth's water. Earth's bulk water content, which is small but not negligible, is significantly greater than what the thermal gradient of the solar nebula disk would suggest for planetesimal materials condensed at one astronomical unit. The proto-solar nebula is a likely source of early Earth's water, with probable contributions from one or more of the following: water-rich planetesimals, ordinary and carbonaceous meteorites, comets, asteroids, and interplanetary dust particles. However, all of these sources have been questioned, and the proposed proto-solar nebular origin has been disputed in light of the large difference in hydrogen isotopic composition between it and terrestrial water. Current opposition to the solar nebular hypothesis is based on the critical assumption that no processes in the interior of the early Earth changed the isotopic composition of hydrogen. Nevertheless, a hypothesized hydrogenation reaction of liquid iron (2Fe + xH2 ↔ 2FeHx) during core formation likely provided a fractionation mechanism between hydrogen and deuterium (D). We propose that modern D/H ratios at Earth's surface resulted from this isotopic fractionation and that terrestrial water originated from oxidation of proto-solar hydrogen dissolved in the magma ocean in the early Earth by coexisting oxides (such as FeO). Thus, the isotopic composition of water on Earth can be mainly explained by internal terrestrial processes.

  20. Hydrogen production by high-temperature water splitting using electron-conducting membranes

    DOEpatents

    Lee, Tae H.; Wang, Shuangyan; Dorris, Stephen E.; Balachandran, Uthamalingam

    2004-04-27

    A device and method for separating water into hydrogen and oxygen is disclosed. A first substantially gas impervious solid electron-conducting membrane for selectively passing hydrogen is provided and spaced from a second substantially gas impervious solid electron-conducting membrane for selectively passing oxygen. When steam is passed between the two membranes at disassociation temperatures the hydrogen from the disassociation of steam selectively and continuously passes through the first membrane and oxygen selectively and continuously passes through the second membrane, thereby continuously driving the disassociation of steam producing hydrogen and oxygen.

  1. Quantum Calculations On Hydrogen Bonds In Certain Water Clusters Show Cooperative Effects

    PubMed Central

    ZNAMENSKIY, VASILIY S.; GREEN, MICHAEL E.

    2008-01-01

    Water molecules in clefts and small clusters are in a significantly different environment than in bulk water. We have carried out ab initio calculations that demonstrate this in a series of clusters, showing that cooperative effects must be taken into account in the treatment of hydrogen bonds and water clusters in such bounded systems. Hydrogen bonds between water molecules in simulations are treated most frequently by using point charge water potentials, such as TIP3P or SPC, sometimes with a polarizable extension. These produce excellent results in bulk water, for which they are calibrated. Clefts are different from bulk; it is necessary to look at smaller systems, and investigate the effect of limited numbers of neighbors. We start with a study of isolated clusters of water with varying numbers of neighbors of a hydrogen bonded pair of water molecules. The cluster as a whole is in vacuum. The clusters are defined so as to provide the possible arrangements of nearest neighbors of a central hydrogen bonded pair of water molecules. We then scan the length and angles of the central hydrogen bond of the clusters, using density functional theory, for each possible arrangement of donor and acceptor hydrogen bonds on the central hydrogen bonding pair; the potential of interaction of two water molecules varies with the number of donor and of acceptor neighbors. This also involves changes in charge on the water molecules as a function of bond length, and changes in energy and length as a function of number of neighboring donor and acceptor molecules. Energy varies by approximately 6 kBT near room temperature from the highest to the lowest energy when bond length alone is varied, enough to seriously affect simulations. PMID:19169381

  2. Coupling between inter-helical hydrogen bonding and water dynamics in a proton transporter.

    PubMed

    del Val, Coral; Bondar, Luiza; Bondar, Ana-Nicoleta

    2014-04-01

    Long-distance proton transfers by proton pumps occurs in discrete steps that may involve the direct participation of protein sidechains and water molecules, and coupling of protonation changes to structural rearrangements of the protein matrix. Here we explore the role of inter-helical hydrogen bonding in long-distance protein conformational coupling and dynamics of internal water molecules. From molecular dynamics simulations of wild type and nine different bacteriorhodopsin mutants we find that both intra- and inter-helical hydrogen bonds are important determinants of the local protein structure, dynamics, and water interactions. Based on molecular dynamics and bioinformatics analyses, we identify an aspartate/threonine inter-helical hydrogen-bonding motif involved in controlling the local conformational dynamics. Perturbation of inter-helical hydrogen bonds can couple to rapid changes in water dynamics.

  3. Ground-based Infrared Observations of Water Vapor and Hydrogen Peroxide in the Atmosphere of Mars

    NASA Astrophysics Data System (ADS)

    Encrenaz, T.; Greathouse, T. K.; Bitner, M.; Kruger, A.; Richter, M. J.; Lacy, J. H.; Bézard, B.; Fouchet, T.; Lefevre, F.; Forget, F.; Atreya, S. K.

    2008-11-01

    Ground-based observations of water vapor and hydrogen peroxide have been obtained in the thermal infrared range, using the TEXES instrument at the NASA Infrared Telescope Facility, for different times of the seasonal cycle.

  4. Solar-hydrogen energy system model for Libya

    SciTech Connect

    Eljrushi, G.S.

    1987-01-01

    A solar-hydrogen energy-system model for Libya was developed, obtaining relationships for and between the main energy and energy related parameters of Libya and the world. The parameters included are: population, energy demand, fossil-fuel production, fossil-fuel resources, hydrogen production, hydrogen introduction rates, energy prices, gross domestic product, pollution and quality of life. The trends of these parameters with and without hydrogen introduction were investigated over a period of time - through the year 2100. The results indicate that the fossil-fuel resources in Libya could be exhausted, due to production for local and export demands, within three to four decades unless serious measures for reducing production are taken. The results indicate that adopting solar-hydrogen energy system would extend the availability of fossil-fuel resources for a longer time period, reduce pollution, improve quality of life and establish a permanent energy system for Libya. It also shows that eventually Libya could export hydrogen in lieu of oil and natural gas.

  5. Theoretical model of HZE particle fragmentation by hydrogen targets

    NASA Technical Reports Server (NTRS)

    Townsend, L.W.; Cucinotta, F. A; Bagga, R.; Tripathi, R. K.

    1996-01-01

    The fragmenting of high energy, heavy ions (HZE particles) by hydrogen targets is an important, physical process in several areas of space radiation research. In this work quantum mechanical optical model methods for estimating cross sections for HZE particle fragmentation by hydrogen targets are presented. The cross sections are calculated using a modified abrasion-ablation collision formalism adapted from a nucleus-nucleus collision model. Elemental and isotopic production cross sections are estimated and compared with reported measurements for the breakup of neon, sulphur, and iron, nuclei at incident energies between 400 and 910 Mev/nucleon. Good agreement between theory and experiment is obtained.

  6. Increasing Hydrogen Ion Activity of Water in Two Reservoirs Supplying the San Francisco Bay Area, California

    NASA Astrophysics Data System (ADS)

    McColl, J. G.

    1981-10-01

    The hydrogen ion activity (H+) of water in two Sierra Nevada reservoirs (Pardee and Hetch Hetchy) that supply the San Francisco Bay area has been increasing with time over the period 1954-1979. This conclusion is based on weekly measurements ofpH at the two reservoirs and is supported by measurements of alkalinity which decreased at Pardee over the period 1944-1979. Based on linear models, the rate of the increasing (H+) was the same at both reservoirs, and (H+) varied concomitantly from year to year, suggesting a common, general cause. Mean monthly variation in (H+) corresponded to mean monthly variation in atmospheric pollution from a nine-county area around San Francisco Bay. The most likely cause of the increasing (H+) of reservoir waters is NOx from automobile exhausts primarily from the San Francisco Bay area.

  7. Hydrogen production

    NASA Technical Reports Server (NTRS)

    England, C.; Chirivella, J. E.; Fujita, T.; Jeffe, R. E.; Lawson, D.; Manvi, R.

    1975-01-01

    The state of hydrogen production technology is evaluated. Specific areas discussed include: hydrogen production fossil fuels; coal gasification processes; electrolysis of water; thermochemical production of hydrogen; production of hydrogen by solar energy; and biological production of hydrogen. Supply options are considered along with costs of hydrogen production.

  8. Photochemical formation of hydrogen peroxide in surface and ground waters exposed to sunlight

    SciTech Connect

    Cooper, W.J.; Zika, R.G.

    1983-05-13

    A rapid increase in the concentration of hydrogen peroxide was observed when samples of natural surface and ground water from various locations in the United States were exposed to sunlight. The hydrogen peroxide is photochemically generated from organic constitutents present in the water; humic materials are believed to be the primary agent producing the peroxide. Studies with superoxide dismutase suggest that the superoxide anion is the precursor of the peroxide.

  9. Carbon-13 in black sea waters and implications for the origin of hydrogen sulfide.

    PubMed

    Deuser, W G

    1970-06-26

    A combination of measurements of carbon-13 and the hydrogen sulfide content in Black Sea waters with available data on the total carbon dioxide in these waters indicates that the contribution of organic sulfur to the hydrogen sulfide lies between 3 and 5 percent and increases with depth. Likely causes for the increase are increasing productivity or upward movement of the anoxic zone during the facts last 2000 year.

  10. Modeling hydrogen starvation conditions in proton-exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Ohs, Jan Hendrik; Sauter, Ulrich; Maass, Sebastian; Stolten, Detlef

    In this study, a steady state and isothermal 2D-PEM fuel cell model is presented. By simulation of a single cell along the channel and in through-plane direction, its behaviour under hydrogen starvation due to nitrogen dilution is analysed. Under these conditions, carbon corrosion and water electrolysis are observed on the cathode side. This phenomenon, causing severe cell degradation, is known as reverse current decay mechanism in literature. Butler-Volmer equations are used to model the electrochemical reactions. In addition, we account for permeation of gases through the membrane and for the local water content within the membrane. The results show that the membrane potential locally drops in areas starved from hydrogen. This leads to potential gradients >1.2 V between electrode and membrane on the cathode side resulting in significant carbon corrosion and electrolysis reaction rates. The model enables the analysis of sub-stoichiometric states occurring during anode gas recirculation or load transients.

  11. Accelerated shallow water modeling

    NASA Astrophysics Data System (ADS)

    Gandham, Rajesh; Medina, David; Warburton, Timothy

    2015-04-01

    ln this talk we will describe our ongoing developments in accelerated numerical methods for modeling tsunamis, and oceanic fluid flows using two dimensional shallow water model and/or three dimensional incompressible Navier Stokes model discretized with high order discontinuous Galerkin methods. High order discontinuous Galerkin methods can be computationally demanding, requiring extensive computational time to simulate real time events on traditional CPU architectures. However, recent advances in computing architectures and hardware aware algorithms make it possible to reduce simulation time and provide accurate predictions in a timely manner. Hence we tailor these algorithms to take advantage of single instruction multiple data (SIMD) architecture that is seen in modern many core compute devices such as GPUs. We will discuss our unified and extensive many-core programming library OCCA that alleviates the need to completely re-design the solvers to keep up with constantly evolving parallel programming models and hardware architectures. We will present performance results for the flow simulations demonstrating performance leveraging multiple different multi-threading APIs on GPU and CPU targets.

  12. Phase Equilibria of Water/CO2 and Water/n-Alkane Mixtures from Polarizable Models.

    PubMed

    Jiang, Hao; Economou, Ioannis G; Panagiotopoulos, Athanassios Z

    2017-02-16

    Phase equilibria of water/CO2 and water/n-alkane mixtures over a range of temperatures and pressures were obtained from Monte Carlo simulations in the Gibbs ensemble. Three sets of Drude-type polarizable models for water, namely the BK3, GCP, and HBP models, were combined with a polarizable Gaussian charge CO2 (PGC) model to represent the water/CO2 mixture. The HBP water model describes hydrogen bonds between water and CO2 explicitly. All models underestimate CO2 solubility in water if standard combining rules are used for the dispersion interactions between water and CO2. With the dispersion parameters optimized to phase compositions, the BK3 and GCP models were able to represent the CO2 solubility in water, however, the water composition in CO2-rich phase is systematically underestimated. Accurate representation of compositions for both water- and CO2-rich phases cannot be achieved even after optimizing the cross interaction parameters. By contrast, accurate compositions for both water- and CO2-rich phases were obtained with hydrogen bonding parameters determined from the second virial coefficient for water/CO2. Phase equilibria of water/n-alkane mixtures were also studied using the HBP water and an exponenial-6 united-atom n-alkanes model. The dispersion interactions between water and n-alkanes were optimized to Henry's constants of methane and ethane in water. The HBP water and united-atom n-alkane models underestimate water content in the n-alkane-rich phase; this underestimation is likely due to the neglect of electrostatic and induction energies in the united-atom model.

  13. Spontaneous hydrogen generation from organic-capped Al nanoparticles and water.

    PubMed

    Bunker, Christopher E; Smith, Marcus J; Fernando, K A Shiral; Harruff, Barbara A; Lewis, William K; Gord, Joseph R; Guliants, Elena A; Phelps, Donald K

    2010-01-01

    The development of technologies that would lead toward the adoption of a hydrogen economy requires readily available, safe, and environmentally friendly access to hydrogen. This can be achieved using the aluminum-water reaction; however, the protective nature and stability of aluminum oxide is a clear detriment to its application. Here, we demonstrate the spontaneous generation of hydrogen gas from ordinary room-temperature tap water when combined with aluminum-oleic acid core-shell nanoparticles obtained via sonochemistry. The reaction is found to be near-complete (>95% yield hydrogen) with a tunable rate from 6.4x10(-4) to 0.01 g of H2/s/g of Al and to yield an environmentally benign byproduct. The potential of these nanoparticles as a source of hydrogen gas for power generation is demonstrated using a simple fuel cell with an applied load.

  14. Mechanism for forming hydrogen chloride and sodium sulfate from sulfur trioxide, water, and sodium chloride

    NASA Technical Reports Server (NTRS)

    Anderson, A. B.

    1984-01-01

    A molecular orbital study of sodium sulfate and hydrogen chloride formation from sulfur trioxide, water, and sodium chloride shows no activation barrier, in agreement with recent experimental work of Kohl, Fielder, and Stearns. Two overall steps are found for the process. First, gas-phase water reacts with sulfur trioxide along a pathway involving a linear O-H-O transition state yielding closely associated hydroxyl and bisulfite which rearrange to become a hydrogen sulfate molecule. Then the hydrogen sulfate molecule transfers a hydrogen atom to a surface chloride in solid sodium chloride while an electron and a sodium cation simultaneously transfer to yield sodium bisulfate and gas-phase hydrogen chloride. This process repeats. Both of these steps represent well-known reactions for which mechanisms have not been previously determined.

  15. Ground Water Modeling Research

    EPA Pesticide Factsheets

    EPA is supporting region, state, and tribal partners at Superfund sites and brownfields to develop new methods to better characterize, monitor, and treat ground water contamination; in order to protect drinking water, surface water, and indoor air.

  16. Nano-ferrites for water splitting: unprecedented high photocatalytic hydrogen production under visible light.

    PubMed

    Mangrulkar, Priti A; Polshettiwar, Vivek; Labhsetwar, Nitin K; Varma, Rajender S; Rayalu, Sadhana S

    2012-08-21

    In the present investigation, hydrogen production via water splitting by nano-ferrites was studied using ethanol as the sacrificial donor and Pt as co-catalyst. Nano-ferrite is emerging as a promising photocatalyst with a hydrogen evolution rate of 8.275 μmol h(-1) and a hydrogen yield of 8275 μmol h(-1) g(-1) under visible light compared to 0.0046 μmol h(-1) for commercial iron oxide (tested under similar experimental conditions). Nano-ferrites were tested in three different photoreactor configurations. The rate of hydrogen evolution by nano-ferrite was significantly influenced by the photoreactor configuration. Altering the reactor configuration led to sevenfold (59.55 μmol h(-1)) increase in the hydrogen evolution rate. Nano-ferrites have shown remarkable stability in hydrogen production up to 30 h and the cumulative hydrogen evolution rate was observed to be 98.79 μmol h(-1). The hydrogen yield was seen to be influenced by several factors like photocatalyst dose, illumination intensity, irradiation time, sacrificial donor and presence of co-catalyst. These were then investigated in detail. It was evident from the experimental data that nano-ferrites under optimized reaction conditions and photoreactor configuration could lead to remarkable hydrogen evolution activity under visible light. Temperature had a significant role in enhancing the hydrogen yield.

  17. Predictive Models for the Free Energy of Hydrogen Bonded Complexes with Single and Cooperative Hydrogen Bonds.

    PubMed

    Glavatskikh, Marta; Madzhidov, Timur; Solov'ev, Vitaly; Marcou, Gilles; Horvath, Dragos; Varnek, Alexandre

    2016-12-01

    In this work, we report QSPR modeling of the free energy ΔG of 1 : 1 hydrogen bond complexes of different H-bond acceptors and donors. The modeling was performed on a large and structurally diverse set of 3373 complexes featuring a single hydrogen bond, for which ΔG was measured at 298 K in CCl4 . The models were prepared using Support Vector Machine and Multiple Linear Regression, with ISIDA fragment descriptors. The marked atoms strategy was applied at fragmentation stage, in order to capture the location of H-bond donor and acceptor centers. Different strategies of model validation have been suggested, including the targeted omission of individual H-bond acceptors and donors from the training set, in order to check whether the predictive ability of the model is not limited to the interpolation of H-bond strength between two already encountered partners. Successfully cross-validating individual models were combined into a consensus model, and challenged to predict external test sets of 629 and 12 complexes, in which donor and acceptor formed single and cooperative H-bonds, respectively. In all cases, SVM models outperform MLR. The SVM consensus model performs well both in 3-fold cross-validation (RMSE=1.50 kJ/mol), and on the external test sets containing complexes with single (RMSE=3.20 kJ/mol) and cooperative H-bonds (RMSE=1.63 kJ/mol).

  18. Thermodynamics of hydrogen bond patterns in supramolecular assemblies of water molecules.

    PubMed

    Henry, Marc

    2002-07-02

    The PACHA (Partial Atomic Charges and Hardnesses Analysis) formalism is applied to various supramolecular assemblies of water molecules. After a detailed study of all available crystal structures for ice polymorphs, we shown that the hydrogen bond strength is roughly constant below 1 GPa and considerably weakened above that value. New hydrogen bond patterns are proposed for ice IV, V, and VI after (EB) (electrostatic balance) minimization. For other polymorphs, there is an almost perfect coincidence between experimental and predicted hydrogen bond patterns. The evolution of hydrogen bond energy as a function of molecular geometry in water clusters with up to 280 water molecules and in large supramolecular compounds is quantitatively described. Intermolecular hydrogen bonds are found to lie between -9 and -32 kJ mol-1, the stronger interaction occurs within the spherical fully disordered water droplet buried at the heart of Müller's superfullerene keplerate. The weakest one occurs in a chiral molecular snub cube built from six calix[4]resorcinarene and eight water molecules. Intramolecular hydrogen bonds are found in the range -10-100 kJ mol-1 and can thus be considerably stronger than intermolecular bonds. Finally, through the investigation of a clathrate type I compound, it was possible to obtain a deep insight of the host-guest interactions and self-assembly rules of water cages in these materials.

  19. Acetonitrile-water hydrogen-bonded interaction: Matrix-isolation infrared and ab initio computation

    NASA Astrophysics Data System (ADS)

    Gopi, R.; Ramanathan, N.; Sundararajan, K.

    2015-08-01

    The 1:1 hydrogen-bonded complex of acetonitrile (CH3CN) and water (H2O) was trapped in Ar and N2 matrices and studied using infrared technique. Ab initio computations showed two types of complexes formed between CH3CN and H2O, a linear complex A with a Ctbnd N⋯H interaction between nitrogen of CH3CN and hydrogen of H2O and a cyclic complex B, in which the interactions are between the hydrogen of CH3CN with oxygen of H2O and hydrogen of H2O with π cloud of sbnd Ctbnd N of CH3CN. Vibrational wavenumber calculations revealed that both the complexes A and B were minima on the potential energy surface. Interaction energies computed at B3LYP/6-311++G(d,p) showed that linear complex A is more stable than cyclic complex B. Computations identified a blue shift of ∼11.5 cm-1 and a red shift of ∼6.5 cm-1 in the CN stretching mode for the complexes A and B, respectively. Experimentally, we observed a blue shift of ∼15.0 and ∼8.3 cm-1 in N2 and Ar matrices, respectively, in the CN stretching mode of CH3CN, which supports the formation of complex A. The Onsager Self Consistent Reaction Field (SCRF) model was used to explain the influence of matrices on the complexes A and B. To understand the nature of the interactions, Atoms in Molecules (AIM) and Natural Bond Orbital (NBO) analyses were carried out for the complexes A and B.

  20. Theoretical studies of hydrogen bonding in water cyanides and in the base pair Gu Cy

    NASA Astrophysics Data System (ADS)

    Rivelino, Roberto; Ludwig, Valdemir; Rissi, Eduardo; Canuto, Sylvio

    2002-09-01

    Density-functional (DFT) and many-body-perturbation theories (MBPT/CC) are used to study the hydrogen bonding in the water-cyanide complexes H-CN⋯H 2O, H 3C-CN⋯H 2O and (CH 3) 3C-CN⋯H 2O. Structures, binding energies and changes in vibrational frequencies are analyzed. The calculated CN stretching frequency is found to shift to the blue upon complexation in H-CN⋯H 2O and H 3C-CN⋯H 2O. To investigate electron correlation effects on the binding energies of these complexes, single-point calculations are performed at the MBPT/CC (MP2, MP3, MP4, CCSD and CCSD(T)) levels using the optimized MP2 geometries. Binding energies are also obtained at different levels of DFT (B3LYP and PW91) and compared with the MBPT/CC results. All calculations include corrections for basis set superposition error (BSSE) and zero-point vibrational energies. Additionally, the triple hydrogen-bonded guanine-cytosine (Gu-Cy) base pair is analyzed. The binding energy of the Watson-Crick model for Gu-Cy is calculated using the Hartree-Fock calculations and DFT (B3LYP and BP86) methods. The results for the hydrogen bonding distances and binding energies are in good agreement with experimental and recent theoretical values. The calculated dipole moment of the Gu-Cy complex is compared with the direct vector sum of the isolated bases. After taking into account the BSSE effects we find that the electron polarization due to the hydrogen binding leads to an increase of ˜20% of the calculated dipole moment of the complex.

  1. Effect of species, life stage, and water temperature on the toxicity of hydrogen peroxide to fish

    USGS Publications Warehouse

    Rach, J.J.; Schreier, T.M.; Howe, G.E.; Redman, S.D.

    1997-01-01

    Hydrogen peroxide is a drug of low regulatory priority status that is effective in treating fish and fish eggs infected by fungi. However, only limited information is available to guide fish culturists in administering hydrogen peroxide to diseased fish. Laboratory tests were conducted to determine (1) the sensitivity of brown trout Salmo trutta, lake trout Salvelinus namaycush, fathead minnow Pimephales promelas, walleye Stizostedion vitreum, channel catfish Ictalurus punctatus, and bluegill Lepomis, machrochirus to hydrogen peroxide treatments; (2) the sensitivity of various life stages of rainbow trout Oncorhynchus mykiss to hydrogen peroxide treatments; and (3) the effect of water temperature on the acute toxicity of hydrogen peroxide to three fish species. Fish were exposed to hydrogen peroxide concentrations ranging from 100 to 5,000 mu L/L (ppm) for 15-min or 45-min treatments every other day for four consecutive treatments to determine the sensitivity of various species and life stages of fish. Except for walleye, most species of fish tested (less than or equal to 2 g) tolerated hydrogen peroxide of 1,000 mu L/L or greater. Walleyes were sensitive to hydrogen peroxide concentrations as low as 100 mu L/L. A correlation was found between the toxicity of hydrogen peroxide and the life stages of rainbow trout; larger fish were more sensitive. Generally, the toxicity of hydrogen peroxide increased for all species as water temperature increased. The results of these experiments demonstrate that it is important to consider the effects of species, life stage, and water temperature when conducting hydrogen peroxide treatments.

  2. WATER DIVERSION MODEL

    SciTech Connect

    J.B. Case

    1999-12-21

    The distribution of seepage in the proposed repository will be highly variable due in part to variations in the spatial distribution of percolations. The performance of the drip shield and the backfill system may divert the water flux around the waste packages to the invert. Diversion will occur along the drift surface, within the backfill, at the drip shield, and at the Waste Package (WP) surface, even after the drip shield and WP have been breached by corrosion. The purpose and objective of this Analysis and Modeling Report (AMR) are to develop a conceptual model and constitutive properties for bounding the volume and rate of seepage water that flows around the drip shield (CRWMS M&O 1999c). This analysis model is to be compatible with the selected repository conceptual design (Wilkins and Heath, 1999) and will be used to evaluate the performance of the Engineered Barrier System (EBS), and to provide input to the EBS Water Distribution and Removal Model. This model supports the Engineered Barrier System (EBS) postclosure performance assessment for the Site Recommendation (SR). This document characterizes the hydrological constitutive properties of the backfill and invert materials (Section 6.2) and a third material that represents a mixture of the two. These include the Overton Sand which is selected as a backfill (Section 5.2), crushed tuff which is selected as the invert (Section 5.1), and a combined material (Sections 5.9 and 5.10) which has retention and hydraulic conductivity properties intermediate to the selected materials for the backfill and the invert. The properties include the grain size distribution, the dry bulk density and porosity, the moisture retention, the intrinsic permeability, the relative permeability, and the material thermal properties. The van Genuchten relationships with curve fit parameters are used to define the basic retention relationship of moisture potential to volumetric moisture content, and the basic relationship of unsaturated

  3. Installations for separation of hydrogen isotopes by the method of chemical isotopic exchange in the `water-hydrogen` system

    SciTech Connect

    Andreev, B.M.; Sakharovsky, Y.A.; Rozenkevich, M.B.; Magomedbekov, E.P.; Park, Y.S.; Uborskiy, V.V.; Trenin, V.D.; Alekseev, I.A.; Fedorchenko, O.A.; Karpov, S.P.; Konoplev, K.A.

    1995-10-01

    The paper presents the results of more than a year of running a pilot setup for separation of hydrogen isotopes using catalytic isotopic exchange between hydrogen and liquid water. The setup is 5 m high, has the inner diameter of 28 mm, and is equipped with upper and lower reflux devices. The experimental values of HETP vary from 15 cm at T=333 K to 38 cm at T=293 K. The setup is capable of upgrading diluted heavy water with 85-90% deuterium content up to [D{sub 2}O] > 99.95 at.%, yielding daily 4 kg of the product. We also report on the progress in constructing a similar setup for eliminating tritium and an industrial setup, for which the one reported is a prototype. 10 refs., 1 fig., 3 tabs.

  4. Modeling the reaction kinetics of a hydrogen generator onboard a fuel cell -- Electric hybrid motorcycle

    NASA Astrophysics Data System (ADS)

    Ganesh, Karthik

    Owing to the perceived decline of the fossil fuel reserves in the world and environmental issues like pollution, conventional fuels may be replaced by cleaner alternative fuels. The potential of hydrogen as a fuel in vehicular applications is being explored. Hydrogen as an energy carrier potentially finds applications in internal combustion engines and fuel cells because it is considered a clean fuel and has high specific energy. However, at 6 to 8 per kilogram, not only is hydrogen produced from conventional methods like steam reforming expensive, but also there are storage and handling issues, safety concerns and lack of hydrogen refilling stations across the country. The purpose of this research is to suggest a cheap and viable system that generates hydrogen on demand through a chemical reaction between an aluminum-water slurry and an aqueous sodium hydroxide solution to power a 2 kW fuel cell on a fuel cell hybrid motorcycle. This reaction is essentially an aluminum-water reaction where sodium hydroxide acts as a reaction promoter or catalyst. The Horizon 2000 fuel cell used for this purpose has a maximum hydrogen intake rate of 28 lpm. The study focuses on studying the exothermic reaction between the reactants and proposes a rate law that best describes the rate of generation of hydrogen in connection to the surface area of aluminum available for the certain reaction and the concentration of the sodium hydroxide solution. Further, the proposed rate law is used in the simulation model of the chemical reactor onboard the hybrid motorcycle to determine the hydrogen flow rate to the fuel cell with time. Based on the simulated rate of production of hydrogen from the chemical system, its feasibility of use on different drive cycles is analyzed. The rate of production of hydrogen with a higher concentration of sodium hydroxide and smaller aluminum powder size was found to enable the installation of the chemical reactor on urban cycles with frequent stops and starts

  5. Hydrogen from Water in a Novel Recombinant Cyanobacterial System

    SciTech Connect

    Weyman, Philip D; Smith, Hamillton O.

    2014-12-03

    Photobiological processes are attractive routes to renewable H2 production. With the input of solar energy, photosynthetic microbes such as cyanobacteria and green algae carry out oxygenic photosynthesis, using sunlight energy to extract protons and high energy electrons from water. These protons and high energy electrons can be fed to a hydrogenase system yielding H2. However, most hydrogen-evolving hydrogenases are inhibited by O2, which is an inherent byproduct of oxygenic photosynthesis. The rate of H2 production is thus limited. Certain photosynthetic bacteria are reported to have an O2-tolerant evolving hydrogenase, yet these microbes do not split water, and require other more expensive feedstocks. To overcome these difficulties, the goal of this work has been to construct novel microbial hybrids by genetically transferring O2-tolerant hydrogenases from other bacteria into a class of photosynthetic bacteria called cyanobacteria. These hybrid organisms will use the photosynthetic machinery of the cyanobacterial hosts to perform the water-oxidation reaction with the input of solar energy, and couple the resulting protons and high energy electrons to the O2-tolerant bacterial hydrogenase, all within the same microbe (Fig. 1). The ultimate goal of this work has been to overcome the sensitivity of the hydrogenase enzyme to O2 and address one of the key technological hurdles to cost-effective photobiological H2 production which currently limits the production of hydrogen in algal systems. In pursuit of this goal, work on this project has successfully completed many subtasks leading to a greatly increased understanding of the complicated [NiFe]-hydrogenase enzymes. At the beginning of this project, [NiFe] hydrogenases had never been successfully moved across wide species barriers and had never been heterologously expressed in cyanobacteria. Furthermore, the idea that whole, functional genes could be extracted from complicated, mixed-sequence meta-genomes was not

  6. Combustion characteristics of nanoaluminum, liquid water, and hydrogen peroxide mixtures

    SciTech Connect

    Sabourin, J.L.; Yetter, R.A.; Risha, G.A.; Son, S.F.; Tappan, B.C.

    2008-08-15

    An experimental investigation of the combustion characteristics of nanoaluminum (nAl), liquid water (H{sub 2}O{sub (l)}), and hydrogen peroxide (H{sub 2}O{sub 2}) mixtures has been conducted. Linear and mass-burning rates as functions of pressure, equivalence ratio ({phi}), and concentration of H{sub 2}O{sub 2} in H{sub 2}O{sub (l)} oxidizing solution are reported. Steady-state burning rates were obtained at room temperature using a windowed pressure vessel over an initial pressure range of 0.24 to 12.4 MPa in argon, using average nAl particle diameters of 38 nm, {phi} from 0.5 to 1.3, and H{sub 2}O{sub 2} concentrations between 0 and 32% by mass. At a nominal pressure of 3.65 MPa, under stoichiometric conditions, mass-burning rates per unit area ranged between 6.93 g/cm{sup 2} s (0% H{sub 2}O{sub 2}) and 37.04 g/cm{sup 2} s (32% H{sub 2}O{sub 2}), which corresponded to linear burning rates of 9.58 and 58.2 cm/s, respectively. Burning rate pressure exponents of 0.44 and 0.38 were found for stoichiometric mixtures at room temperature containing 10 and 25% H{sub 2}O{sub 2}, respectively, up to 5 MPa. Burning rates are reduced above {proportional_to}5 MPa due to the pressurization of interstitial spaces of the packed reactant mixture with argon gas, diluting the fuel and oxidizer mixture. Mass burning rates were not measured above {proportional_to}32% H{sub 2}O{sub 2} due to an anomalous burning phenomena, which caused overpressurization within the quartz sample holder, leading to tube rupture. High-speed imaging displayed fingering or jetting ahead of the normal flame front. Localized pressure measurements were taken along the sample length, determining that the combustion process proceeded as a normal deflagration prior to tube rupture, without significant pressure buildup within the tube. In addition to burning rates, chemical efficiencies of the combustion reaction were determined to be within approximately 10% of the theoretical maximum under all conditions

  7. A statistical mechanical theory for a two-dimensional model of water

    NASA Astrophysics Data System (ADS)

    Urbic, Tomaz; Dill, Ken A.

    2010-06-01

    We develop a statistical mechanical model for the thermal and volumetric properties of waterlike fluids. Each water molecule is a two-dimensional disk with three hydrogen-bonding arms. Each water interacts with neighboring waters through a van der Waals interaction and an orientation-dependent hydrogen-bonding interaction. This model, which is largely analytical, is a variant of the Truskett and Dill (TD) treatment of the "Mercedes-Benz" (MB) model. The present model gives better predictions than TD for hydrogen-bond populations in liquid water by distinguishing strong cooperative hydrogen bonds from weaker ones. We explore properties versus temperature T and pressure p. We find that the volumetric and thermal properties follow the same trends with T as real water and are in good general agreement with Monte Carlo simulations of MB water, including the density anomaly, the minimum in the isothermal compressibility, and the decreased number of hydrogen bonds for increasing temperature. The model reproduces that pressure squeezes out water's heat capacity and leads to a negative thermal expansion coefficient at low temperatures. In terms of water structuring, the variance in hydrogen-bonding angles increases with both T and p, while the variance in water density increases with T but decreases with p. Hydrogen bonding is an energy storage mechanism that leads to water's large heat capacity (for its size) and to the fragility in its cagelike structures, which are easily melted by temperature and pressure to a more van der Waals-like liquid state.

  8. Energetic Efficiency of Hydrogen Photoevolution by Algal Water Splitting

    PubMed Central

    Greenbaum, Elias

    1988-01-01

    Absolute thermodynamic efficiencies of conversion of light energy into chemical-free energy of molecular hydrogen by intact microalgae have been measured with an original physical measuring technique using a tin-oxide semiconducting gas sensor. Thin films of microalgae comprising of 5 to 20 cellular monolayers have been entrapped on filter paper, thereby constraining them in a well-defined circular geometry. Based on absolute light absorption of visible polychromatic illumination in the low-intensity region of the light saturation curve, conversion efficiencies of 6 to 24% have been obtained. These values are the highest ever measured for hydrogen evolution by green algae. PMID:19431729

  9. Antioxidant activities of nano-bubble hydrogen-dissolved water assessed by ESR and 2,2'-bipyridyl methods.

    PubMed

    Kato, Shinya; Matsuoka, Daigo; Miwa, Nobuhiko

    2015-08-01

    We prepared nano-bubble hydrogen-dissolved water (nano-H water) which contained hydrogen nano-bubbles of <717-nm diameter for 54% of total bubbles. In the DMPO-spin trap electron spin resonance (ESR) method, the DMPO-OH:MnO ratio, being attributed to amounts of hydroxyl radicals (OH), was 2.78 for pure water (dissolved hydrogen [DH]≤0.01 ppm, oxidation-reduction potential [ORP]=+324 mV), 2.73 for tap water (0.01 ppm, +286 mV), 2.93 for commercially available hydrogen water (0.075 ppm, +49 mV), and 2.66 for manufactured hydrogen water (0.788 ppm, -614 mV), whereas the nano-H water (0.678 ppm, -644 mV) exhibited 2.05, showing the superiority of nano-H water to other types of hydrogen water in terms of OH-scavenging activity. Then, the reduction activity of nano-H water was assessed spectrophotometrically by the 2,2'-bipyridyl method. Differential absorbance at 530 nm was in the order: 0.018 for pure water, 0.055 for tap water, 0.079 for nano-H water, 0.085 for commercially available hydrogen water, and 0.090 for manufactured hydrogen water, indicating a prominent reduction activity of hydrogen water and nano-H water against oxidation in ascorbate-coupled ferric ion-bipyridyl reaction. Thus, nano-H water has an improved antioxidant activity as compared to hydrogen water of similar DH-level, indicating the more marked importance of nano-bubbles rather than the concentration of hydrogen in terms of OH-scavenging.

  10. Hydrogen generation via photoelectrochemical water splitting using chemically exfoliated MoS{sub 2} layers

    SciTech Connect

    Joshi, R. K. E-mail: alwarappan@cecri.res.in; Sahajwalla, V.; Shukla, S.; Saxena, S.; Lee, G.-H.; Alwarappan, S. E-mail: alwarappan@cecri.res.in

    2016-01-15

    Study on hydrogen generation has been of huge interest due to increasing demand for new energy sources. Photoelectrochemical reaction by catalysts was proposed as a promising technique for hydrogen generation. Herein, we report the hydrogen generation via photoelectrochecmial reaction using films of exfoliated 2-dimensional (2D) MoS{sub 2}, which acts as an efficient photocatalyst. The film of chemically exfoliated MoS{sub 2} layers was employed for water splitting, leading to hydrogen generation. The amount of hydrogen was qualitatively monitored by observing overpressure of a water container. The high photo-current generated by MoS{sub 2} film resulted in hydrogen evolution. Our work shows that 2D MoS{sub 2} is one of the promising candidates as a photocatalyst for light-induced hydrogen generation. High photoelectrocatalytic efficiency of the 2D MoS{sub 2} shows a new way toward hydrogen generation, which is one of the renewable energy sources. The efficient photoelectrocatalytic property of the 2D MoS{sub 2} is possibly due to availability of catalytically active edge sites together with minimal stacking that favors the electron transfer.

  11. Separating hydrogen and oxygen evolution in alkaline water electrolysis using nickel hydroxide

    NASA Astrophysics Data System (ADS)

    Chen, Long; Dong, Xiaoli; Wang, Yonggang; Xia, Yongyao

    2016-05-01

    Low-cost alkaline water electrolysis has been considered a sustainable approach to producing hydrogen using renewable energy inputs, but preventing hydrogen/oxygen mixing and efficiently using the instable renewable energy are challenging. Here, using nickel hydroxide as a redox mediator, we decouple the hydrogen and oxygen production in alkaline water electrolysis, which overcomes the gas-mixing issue and may increase the use of renewable energy. In this architecture, the hydrogen production occurs at the cathode by water reduction, and the anodic Ni(OH)2 is simultaneously oxidized into NiOOH. The subsequent oxygen production involves a cathodic NiOOH reduction (NiOOH-->Ni(OH)2) and an anodic OH- oxidization. Alternatively, the NiOOH formed during hydrogen production can be coupled with a zinc anode to form a NiOOH-Zn battery, and its discharge product (that is, Ni(OH)2) can be used to produce hydrogen again. This architecture brings a potential solution to facilitate renewables-to-hydrogen conversion.

  12. Separating hydrogen and oxygen evolution in alkaline water electrolysis using nickel hydroxide

    PubMed Central

    Chen, Long; Dong, Xiaoli; Wang, Yonggang; Xia, Yongyao

    2016-01-01

    Low-cost alkaline water electrolysis has been considered a sustainable approach to producing hydrogen using renewable energy inputs, but preventing hydrogen/oxygen mixing and efficiently using the instable renewable energy are challenging. Here, using nickel hydroxide as a redox mediator, we decouple the hydrogen and oxygen production in alkaline water electrolysis, which overcomes the gas-mixing issue and may increase the use of renewable energy. In this architecture, the hydrogen production occurs at the cathode by water reduction, and the anodic Ni(OH)2 is simultaneously oxidized into NiOOH. The subsequent oxygen production involves a cathodic NiOOH reduction (NiOOH→Ni(OH)2) and an anodic OH− oxidization. Alternatively, the NiOOH formed during hydrogen production can be coupled with a zinc anode to form a NiOOH-Zn battery, and its discharge product (that is, Ni(OH)2) can be used to produce hydrogen again. This architecture brings a potential solution to facilitate renewables-to-hydrogen conversion. PMID:27199009

  13. Separating hydrogen and oxygen evolution in alkaline water electrolysis using nickel hydroxide.

    PubMed

    Chen, Long; Dong, Xiaoli; Wang, Yonggang; Xia, Yongyao

    2016-05-20

    Low-cost alkaline water electrolysis has been considered a sustainable approach to producing hydrogen using renewable energy inputs, but preventing hydrogen/oxygen mixing and efficiently using the instable renewable energy are challenging. Here, using nickel hydroxide as a redox mediator, we decouple the hydrogen and oxygen production in alkaline water electrolysis, which overcomes the gas-mixing issue and may increase the use of renewable energy. In this architecture, the hydrogen production occurs at the cathode by water reduction, and the anodic Ni(OH)2 is simultaneously oxidized into NiOOH. The subsequent oxygen production involves a cathodic NiOOH reduction (NiOOH→Ni(OH)2) and an anodic OH(-) oxidization. Alternatively, the NiOOH formed during hydrogen production can be coupled with a zinc anode to form a NiOOH-Zn battery, and its discharge product (that is, Ni(OH)2) can be used to produce hydrogen again. This architecture brings a potential solution to facilitate renewables-to-hydrogen conversion.

  14. Modeling hydrogen-cyanide absorption in fires

    NASA Technical Reports Server (NTRS)

    Cagliostro, D. E.; Islas, A.

    1981-01-01

    A mathematical model is developed for predicting blood concentrations of cyanide as functions of exposure time to constant levels of cyanide in the atmosphere. A toxic gas (which may form as a result of decomposition of combustion materials used in transportation vehicles) is breathed into the alveolar space and transferred from the alveolar space to the blood by a first-order process, dependent on the concentration of the toxicant in the alveolar space. The model predicts that blood cyanide levels are more sensitive to the breathing cycle than to blood circulation. A model estimate of the relative effects of CO and HCN atmospheres, generated in an experimental chamber with an epoxy polymer, shows that toxic effects of cyanide occur long before those of carbon monoxide.

  15. Two-temperature modeling of laser sustained hydrogen plasmas

    NASA Astrophysics Data System (ADS)

    Mertogul, Ayhan E.; Krier, Herman

    1994-10-01

    A kinetic nonequilibrium model of laser sustained hydrogen plasmas has been formulated and solved for the prediction of steady-state energy transport processes. This model is the first of its kind and includes a discretized beam ray-trace with a variable index of refraction based upon plasma electron number density for a 10.6-micron CO2 laser input. Model results for fraction of incident laser power absorbed, and fraction of incident laser power retained by the hydrogen gas have compared favorably with experimental results. The model has been used to provide predictions of laser sustained plasma (LSP) performance well outside the realm of experiments to incident powers as high as 700 kW. At the gas pressures studied, minimal kinetic nonequilibrium was observed in LSP core regions, even for 700-kW laser power.

  16. Preliminary ECLSS waste water model

    NASA Technical Reports Server (NTRS)

    Carter, Donald L.; Holder, Donald W., Jr.; Alexander, Kevin; Shaw, R. G.; Hayase, John K.

    1991-01-01

    A preliminary waste water model for input to the Space Station Freedom (SSF) Environmental Control and Life Support System (ECLSS) Water Processor (WP) has been generated for design purposes. Data have been compiled from various ECLSS tests and flight sample analyses. A discussion of the characterization of the waste streams comprising the model is presented, along with a discussion of the waste water model and the rationale for the inclusion of contaminants in their respective concentrations. The major objective is to establish a methodology for the development of a waste water model and to present the current state of that model.

  17. The effect of hydrogen bonds on diffusion mechanism of water inside single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Chen, Qu; Wang, Qi; Liu, Ying-Chun; Wu, Tao

    2014-06-01

    Nanopores can serve as a molecule channel for transport of fluid, where water diffusion differs remarkably from that of simple particles. Hydrogen bonds play an essential role in the diffusion anomaly. Detailed investigations are carried out on the systems of rigid (6, 6), (7, 7), (8, 8), (9, 9), and (10, 10) armchair carbon nanotubes, solvated with Lennard-Jones water fluids. The role of hydrogen bonds is examined by diffusivity statistics and animation snapshots. It is found that in small (6,6) CNT, hydrogen bonds tend to aggregate water into a wire and lead to rapid collective drift. Confinement can stabilize the hydrogen bond of water molecules and enhance its lifetime. In relatively smaller CNTs, the diffusion mechanism could be altered by the temperature. Moreover, in larger nanotubes hydrogen bonding network allows the water to form regional concentrated clusters. This allows water fluid in extremely low density exhibit rather slow self-diffusion motion. This fundamental study attempts to provide insights in understanding nanoscale delivery system in aqueous solution.

  18. Computational study of the interaction of indole-like molecules with water and hydrogen sulfide

    NASA Astrophysics Data System (ADS)

    Cabaleiro-Lago, Enrique M.; Rodríguez-Otero, Jesús; Peña-Gallego, Ángeles

    2011-10-01

    The characteristics of the interaction between water and hydrogen sulfide with indole and a series of analogs obtained by substituting the NH group of indole by different heteroatoms have been studied by means of ab initio calculations. In all cases, minima were found corresponding to structures where water and hydrogen sulfide interact by means of X-H...π contacts. The interaction energies for all these π complexes are quite similar, spanning from -13.5 to -18.8 kJ/mol, and exhibiting the stability sequence NH > CH2 ≈ PH > Se ≈ S > O, for both water and hydrogen sulfide. Though interaction energies are similar, hydrogen sulfide complexes are slightly favored over their water counterparts when interacting with the π cloud. σ-Type complexes were also considered for the systems studied, but only in the case of water complexes this kind of complexes is relevant. Only for complexes formed by water and indole, a significantly more stable σ-type complex was found with an interaction energy amounting to -23.6 kJ/mol. Oxygen and phosphorous derivatives also form σ-type complexes of similar stability as that observed for π ones. Despite the similar interaction energies exhibited by complexes with water and hydrogen sulfide, the nature of the interaction is very different. For π complexes with water the main contributions to the interaction energy are electrostatic and dispersive contributing with similar amounts, though slightly more from electrostatics. On the contrary, in hydrogen sulfide complexes dispersion is by far the main stabilizing contribution. For the σ-type complexes, the interaction is clearly dominated by the electrostatic contribution, especially in the indole-water complex.

  19. A model for pressurized hydrogen induced thin film blisters

    NASA Astrophysics Data System (ADS)

    van den Bos, R. A. J. M.; Reshetniak, V.; Lee, C. J.; Benschop, J.; Bijkerk, F.

    2016-12-01

    We introduce a model for hydrogen induced blister formation in nanometer thick thin films. The model assumes that molecular hydrogen gets trapped under a circular blister cap causing it to deflect elastically outward until a stable blister is formed. In the first part, the energy balance required for a stable blister is calculated. From this model, the adhesion energy of the blister cap, the internal pressure, and the critical H-dose for blister formation can be calculated. In the second part, the flux balance required for a blister to grow to a stable size is calculated. The model is applied to blisters formed in a Mo/Si multilayer after being exposed to hydrogen ions. From the model, the adhesion energy of the Mo/Si blister cap was calculated to be around 1.05 J/m2 with internal pressures in the range of 175-280 MPa. Based on the model, a minimum ion dose for the onset of blister formation was calculated to be d = 4.2 × 1018 ions/cm2. From the flux balance equations, the diffusion constant for the Mo/Si blister cap was estimated to be DH2=(10 ±1 )×10-18 cm2/s .

  20. The Hydrogen Futures Simulation Model (H[2]Sim) technical description.

    SciTech Connect

    Jones, Scott A.; Kamery, William; Baker, Arnold Barry; Drennen, Thomas E.; Lutz, Andrew E.; Rosthal, Jennifer Elizabeth

    2004-10-01

    Hydrogen has the potential to become an integral part of our energy transportation and heat and power sectors in the coming decades and offers a possible solution to many of the problems associated with a heavy reliance on oil and other fossil fuels. The Hydrogen Futures Simulation Model (H2Sim) was developed to provide a high level, internally consistent, strategic tool for evaluating the economic and environmental trade offs of alternative hydrogen production, storage, transport and end use options in the year 2020. Based on the model's default assumptions, estimated hydrogen production costs range from 0.68 $/kg for coal gasification to as high as 5.64 $/kg for centralized electrolysis using solar PV. Coal gasification remains the least cost option if carbon capture and sequestration costs ($0.16/kg) are added. This result is fairly robust; for example, assumed coal prices would have to more than triple or the assumed capital cost would have to increase by more than 2.5 times for natural gas reformation to become the cheaper option. Alternatively, assumed natural gas prices would have to fall below $2/MBtu to compete with coal gasification. The electrolysis results are highly sensitive to electricity costs, but electrolysis only becomes cost competitive with other options when electricity drops below 1 cent/kWhr. Delivered 2020 hydrogen costs are likely to be double the estimated production costs due to the inherent difficulties associated with storing, transporting, and dispensing hydrogen due to its low volumetric density. H2Sim estimates distribution costs ranging from 1.37 $/kg (low distance, low production) to 3.23 $/kg (long distance, high production volumes, carbon sequestration). Distributed hydrogen production options, such as on site natural gas, would avoid some of these costs. H2Sim compares the expected 2020 per mile driving costs (fuel, capital, maintenance, license, and registration) of current technology internal combustion engine (ICE) vehicles

  1. Oxidation of polynuclear aromatic hydrocarbons in water. 4: Ozone combined with hydrogen peroxide

    SciTech Connect

    Beltran, F.J.; Rivas, J.; Ovejero, G.

    1996-03-01

    Three polynuclear aromatic hydrocarbons, fluorene, phenanthrene, and acenaphthene, have been treated in water with ozone combined with hydrogen peroxide. The effect of hydrogen peroxide concentration, pH, and bicarbonate ions has been investigated. The process goes through direct and radical reactions in the case of fluorene and phenanthrene oxidation, while acenaphthene is removed exclusively by direct ozonation. At concentrations of hydrogen peroxide higher than 10{sup {minus}5} M, ozone mass transfer controls the process rate, regardless of pH. In any case, however, the presence of hydrogen peroxide does not improve the oxidation rate compared to ozonation alone due to the importance of the direct reactions. Intermediate compounds identified during oxidation with ozone alone and combined with UV radiation or hydrogen peroxide are similar and justify the high consumption of ozone in these processes.

  2. [Hydrogen and oxygen isotopes of lake water and geothermal spring water in arid area of south Tibet].

    PubMed

    Xiao, Ke; Shen, Li-Cheng; Wang, Peng

    2014-08-01

    The condition of water cycles in Tibet Plateau is a complex process, and the hydrogen and oxygen isotopes contain important information of this process. Based on the analysis of isotopic composition of freshwater lake, saltwater lake and geothermal water in the southern Tibetan Plateau, this study investigated water cycling, composition and variation of hydrogen and oxygen isotopes and the influencing factors in the study area. The study found that the mean values of delta18O and deltaD in Daggyaima lake water (-17.0 per thousand for delta18O and -138. 6 per thousand for deltaD), Langcuo lake water (-6.4 per thousand for delta18O and -87.4 per thousand for deltaD) and Dagejia geothermal water (-19.2 per thousand for delta18 and -158.2 per thousand for deltaD) all showed negative delta18O and deltaD values in Tibetan Plateau by the influence of altitude effects. Lake water and geothermal water were influenced by evaporation effects in inland arid area, and the slope of evaporation line was less than 8. Deuterium excess parameters of lake water and geothermal water were all negative. The temperature of geothermal reservoirs in Dagejia geothermal field was high,and oxygen shift existed in the relationship of hydrogen and oxygen isotopes.

  3. Ammonium recovery from reject water combined with hydrogen production in a bioelectrochemical reactor.

    PubMed

    Wu, Xue; Modin, Oskar

    2013-10-01

    In this study, a bioelectrochemical reactor was investigated for simultaneous hydrogen production and ammonium recovery from reject water, which is an ammonium-rich side-stream produced from sludge treatment processes at wastewater treatment plants. In the anode chamber of the reactor, microorganisms converted organic material into electrical current. The electrical current was used to generate hydrogen gas at the cathode with 96±6% efficiency. Real or synthetic reject water was fed to the cathode chamber where proton reduction into hydrogen gas resulted in a pH increase which led to ammonium being converted into volatile ammonia. The ammonia could be stripped from the solution and recovered in acid. Overall, ammonium recovery efficiencies reached 94% with synthetic reject water and 79% with real reject water. This process could potentially be used to make wastewater treatment plants more resource-efficient and further research is warranted.

  4. High Efficiency Generation of Hydrogen Fuels Using Solar Thermochemical Splitting of Water

    SciTech Connect

    Heske, Clemens; Moujaes, Samir; Weimer, Alan; Wong, Bunsen; Siegal, Nathan; McFarland, Eric; Miller, Eric; Lewis, Michele; Bingham, Carl; Roth, Kurth; Sabacky, Bruce; Steinfeld, Aldo

    2011-09-29

    The objective of this work is to identify economically feasible concepts for the production of hydrogen from water using solar energy. The ultimate project objective was to select one or more competitive concepts for pilot-scale demonstration using concentrated solar energy. Results of pilot scale plant performance would be used as foundation for seeking public and private resources for full-scale plant development and testing. Economical success in this venture would afford the public with a renewable and limitless source of energy carrier for use in electric power load-leveling and as a carbon-free transportation fuel. The Solar Hydrogen Generation Research (SHGR) project embraces technologies relevant to hydrogen research under the Office of Hydrogen Fuel Cells and Infrastructure Technology (HFCIT) as well as concentrated solar power under the Office of Solar Energy Technologies (SET). Although the photoelectrochemical work is aligned with HFCIT, some of the technologies in this effort are also consistent with the skills and technologies found in concentrated solar power and photovoltaic technology under the Office of Solar Energy Technologies (SET). Hydrogen production by thermo-chemical water-splitting is a chemical process that accomplishes the decomposition of water into hydrogen and oxygen using only heat or a combination of heat and electrolysis instead of pure electrolysis and meets the goals for hydrogen production using only water and renewable solar energy as feed-stocks. Photoelectrochemical hydrogen production also meets these goals by implementing photo-electrolysis at the surface of a semiconductor in contact with an electrolyte with bias provided by a photovoltaic source. Here, water splitting is a photo-electrolytic process in which hydrogen is produced using only solar photons and water as feed-stocks. The thermochemical hydrogen task engendered formal collaborations among two universities, three national laboratories and two private sector

  5. Multisample conversion of water to hydrogen by zinc for stable isotope determination

    USGS Publications Warehouse

    Kendall, C.; Coplen, T.B.

    1985-01-01

    Two techniques for the conversion of water to hydrogen for stable isotope ratio determination have been developed that are especially suited for automated multisample analysis. Both procedures involve reaction of zinc shot with a water sample at 450 ??C. in one method designed for water samples in bottles, the water is put in capillaries and is reduced by zinc in reaction vessels; overall savings in sample preparation labor of 75% have been realized over the standard uranium reduction technique. The second technique is for waters evolved under vacuum and is a sealed-tube method employing 9 mm o.d. quartz tubing. Problems inherent with zinc reduction include surface inhomogeneity of the zinc and exchange of hydrogen both with the zinc and with the glass walls of the vessels. For best results, water/zinc and water/glass surface area ratios of vessels should be kept as large as possible.

  6. A DFT study of the role of water in the rhodium-catalyzed hydrogenation of acetone.

    PubMed

    Polo, Victor; Schrock, Richard R; Oro, Luis A

    2016-11-24

    The positive effect of the addition of water to acetone hydrogenation by [RhH2(PR3)2S2](+) catalysts has been studied by DFT calculations. The studied energetic profiles reveal that the more favourable mechanistic path involves a hydride migration to the ketone followed by a reductive elimination that is assisted by two water molecules.

  7. Photogeneration of active formate decomposition catalysts to produce hydrogen from formate and water

    DOEpatents

    King, Jr., Allen D.; King, Robert B.; Sailers, III, Earl L.

    1983-02-08

    A process for producing hydrogen from formate and water by photogenerating an active formate decomposition catalyst from transition metal carbonyl precursor catalysts at relatively low temperatures and otherwise mild conditions is disclosed. Additionally, this process may be expanded to include the generation of formate from carbon monoxide and hydroxide such that the result is the water gas shift reaction.

  8. Mechanism of Action of Sulforaphane as a Superoxide Radical Anion and Hydrogen Peroxide Scavenger by Double Hydrogen Transfer: A Model for Iron Superoxide Dismutase.

    PubMed

    Prasad, Ajit Kumar; Mishra, P C

    2015-06-25

    The mechanism of action of sulforaphane as a scavenger of superoxide radical anion (O2(•-)) and hydrogen peroxide (H2O2) was investigated using density functional theory (DFT) in both gas phase and aqueous media. Iron superoxide dismutase (Fe-SOD) involved in scavenging superoxide radical anion from biological media was modeled by a complex consisting of the ferric ion (Fe(3+)) attached to three histidine rings. Reactions related to scavenging of superoxide radical anion by sulforaphane were studied using DFT in the presence and absence of Fe-SOD represented by this model in both gas phase and aqueous media. The scavenging action of sulforaphane toward both superoxide radical anion and hydrogen peroxide was found to involve the unusual mechanism of double hydrogen transfer. It was found that sulforaphane alone, without Fe-SOD, cannot scavenge superoxide radical anion in gas phase or aqueous media efficiently as the corresponding reaction barriers are very high. However, in the presence of Fe-SOD represented by the above-mentioned model, the scavenging reactions become barrierless, and so sulforaphane scavenges superoxide radical anion by converting it to hydrogen peroxide efficiently. Further, sulforaphane was found to scavenge hydrogen peroxide also very efficiently by converting it into water. Thus, the mechanism of action of sulforaphane as an excellent antioxidant has been unravelled.

  9. HIERARCHICAL METHODOLOGY FOR MODELING HYDROGEN STORAGE SYSTEMS PART II: DETAILED MODELS

    SciTech Connect

    Hardy, B; Donald L. Anton, D

    2008-12-22

    There is significant interest in hydrogen storage systems that employ a media which either adsorbs, absorbs or reacts with hydrogen in a nearly reversible manner. In any media based storage system the rate of hydrogen uptake and the system capacity is governed by a number of complex, coupled physical processes. To design and evaluate such storage systems, a comprehensive methodology was developed, consisting of a hierarchical sequence of models that range from scoping calculations to numerical models that couple reaction kinetics with heat and mass transfer for both the hydrogen charging and discharging phases. The scoping models were presented in Part I [1] of this two part series of papers. This paper describes a detailed numerical model that integrates the phenomena occurring when hydrogen is charged and discharged. A specific application of the methodology is made to a system using NaAlH{sub 4} as the storage media.

  10. Hydrogen production by high temperature water splitting using electron conducting membranes

    DOEpatents

    Balachandran, Uthamalingam; Wang, Shuangyan; Dorris, Stephen E.; Lee, Tae H.

    2006-08-08

    A device and method for separating water into hydrogen and oxygen is disclosed. A first substantially gas impervious solid electron-conducting membrane for selectively passing protons or hydrogen is provided and spaced from a second substantially gas impervious solid electron-conducting membrane for selectively passing oxygen. When steam is passed between the two membranes at dissociation temperatures the hydrogen from the dissociation of steam selectively and continuously passes through the first membrane and oxygen selectively and continuously passes through the second membrane, thereby continuously driving the dissociation of steam producing hydrogen and oxygen. The oxygen is thereafter reacted with methane to produce syngas which optimally may be reacted in a water gas shift reaction to produce CO2 and H2.

  11. Modeling of hydrogen atom diffusion and response behavior of hydrogen sensors in Pd–Y alloy nanofilm

    PubMed Central

    Liu, Yi; Li, Yanli; Huang, Pengcheng; Song, Han; Zhang, Gang

    2016-01-01

    To detect hydrogen gas leakage rapidly, many types of hydrogen sensors containing palladium alloy film have been proposed and fabricated to date. However, the mechanisms and factors that determine the response rate of such hydrogen sensor have not been established theoretically. The manners in which response time is forecasted and sensitive film is designed are key issues in developing hydrogen sensors with nanometer film. In this paper, a unilateral diffusion model of hydrogen atoms in Pd alloy based on Fick’s second law is proposed to describe the Pd–H reaction process. Model simulation shows that the hydrogen sensor response time with Pd alloy film is dominated by two factors (film thickness and hydrogen diffusion coefficient). Finally, a series of response rate experiments with varying thicknesses of Pd–Y (yttrium) alloy film are implemented to verify model validity. Our proposed model can help researchers in the precise optimization of film thickness to realize a simultaneously speedy and sensitive hydrogen sensor. This study also aids in evaluating the influence of manufacturing errors on performances and comparing the performances of sensors with different thicknesses. PMID:27845408

  12. Modeling of hydrogen atom diffusion and response behavior of hydrogen sensors in Pd-Y alloy nanofilm.

    PubMed

    Liu, Yi; Li, Yanli; Huang, Pengcheng; Song, Han; Zhang, Gang

    2016-11-15

    To detect hydrogen gas leakage rapidly, many types of hydrogen sensors containing palladium alloy film have been proposed and fabricated to date. However, the mechanisms and factors that determine the response rate of such hydrogen sensor have not been established theoretically. The manners in which response time is forecasted and sensitive film is designed are key issues in developing hydrogen sensors with nanometer film. In this paper, a unilateral diffusion model of hydrogen atoms in Pd alloy based on Fick's second law is proposed to describe the Pd-H reaction process. Model simulation shows that the hydrogen sensor response time with Pd alloy film is dominated by two factors (film thickness and hydrogen diffusion coefficient). Finally, a series of response rate experiments with varying thicknesses of Pd-Y (yttrium) alloy film are implemented to verify model validity. Our proposed model can help researchers in the precise optimization of film thickness to realize a simultaneously speedy and sensitive hydrogen sensor. This study also aids in evaluating the influence of manufacturing errors on performances and comparing the performances of sensors with different thicknesses.

  13. Modeling of hydrogen atom diffusion and response behavior of hydrogen sensors in Pd–Y alloy nanofilm

    NASA Astrophysics Data System (ADS)

    Liu, Yi; Li, Yanli; Huang, Pengcheng; Song, Han; Zhang, Gang

    2016-11-01

    To detect hydrogen gas leakage rapidly, many types of hydrogen sensors containing palladium alloy film have been proposed and fabricated to date. However, the mechanisms and factors that determine the response rate of such hydrogen sensor have not been established theoretically. The manners in which response time is forecasted and sensitive film is designed are key issues in developing hydrogen sensors with nanometer film. In this paper, a unilateral diffusion model of hydrogen atoms in Pd alloy based on Fick’s second law is proposed to describe the Pd–H reaction process. Model simulation shows that the hydrogen sensor response time with Pd alloy film is dominated by two factors (film thickness and hydrogen diffusion coefficient). Finally, a series of response rate experiments with varying thicknesses of Pd–Y (yttrium) alloy film are implemented to verify model validity. Our proposed model can help researchers in the precise optimization of film thickness to realize a simultaneously speedy and sensitive hydrogen sensor. This study also aids in evaluating the influence of manufacturing errors on performances and comparing the performances of sensors with different thicknesses.

  14. Treatment of ammonia contaminated water by ozone and hydrogen peroxide

    SciTech Connect

    Yuan, F.; Hill, D.O.; Kuo, C.H.

    1995-12-31

    The present research concerns kinetics of oxidation of ammonia by ozone and ozone-hydrogen peroxide mixtures in alkaline solutions. Experiments were carried out at 15 to 35{degrees}C in solutions with pH values varying from 8 to 10 utilizing a stopped-flow spectrophotometer system. Fractions of free ammonia present in acidic and neutral solutions are negligible, and the reaction is very slow. This confirms that only free ammonia can react with ozone in the aqueous phase. The reaction proceeds at moderate rates in the alkaline solutions requiring four moles of ozone to react with each mole of ammonia. The free ammonia is oxidized and converted completely to nitrate in the solutions. The overall reaction between ammonia and ozone is second order with first order in each reactant. The reaction rate constant increases with temperature and pH value of the solution. The average activation energy is 59 Kcal/gmol for all systems investigated at different pH values. The results of the kinetic experiments suggest that the reaction is predominated by the direct oxidation between ammonia and ozone molecules, and that the hydroxyl radical reactions play insignificant roles in the ozonation process. The oxidation rate of ammonia is enhanced considerably in the presence of hydrogen peroxide and ozone mixtures. The formation of hydroxyl radical from interactions between ozone and hydrogen peroxide and the subsequent free radical reactions of ammonia seem important in controlling the destruction rate of free ammonia, as suggested by the results of this study.

  15. On the formation of hydrogen gas on copper in anoxic water.

    PubMed

    Johansson, Adam Johannes; Lilja, Christina; Brinck, Tore

    2011-08-28

    Hydrogen gas has been detected in a closed system containing copper and pure anoxic water [P. Szakalos, G. Hultquist, and G. Wikmark, Electrochem. Solid-State Lett. 10, C63 (2007) and G. Hultquist, P. Szakalos, M. Graham, A. Belonoshko, G. Sproule, L. Grasjo, P. Dorogokupets, B. Danilov, T. Aastrup, G. Wikmark, G. Chuah, J. Eriksson, and A. Rosengren, Catal. Lett. 132, 311 (2009)]. Although bulk corrosion into any of the known phases of copper is thermodynamically forbidden, the present paper shows how surface reactions lead to the formation of hydrogen gas in limited amounts. While water cleavage on copper has been reported and investigated before, formation of molecular hydrogen at a single-crystal Cu[100] surface is here explored using density functional theory and transition state theory. It is found that although solvent catalysis seems possible, the fastest route to the formation of molecular hydrogen is the direct combination of hydrogen atoms on the copper surface. The activation free energy (ΔG(s)(‡)(f)) of hydrogen formation in condensed phase is 0.70 eV, which corresponds to a rate constant of 10 s(-1) at 298.15 K, i.e., a relatively rapid process. It is estimated that at least 2.4 ng hydrogen gas could form per cm(2) on a perfect copper surface.

  16. On the formation of hydrogen gas on copper in anoxic water

    NASA Astrophysics Data System (ADS)

    Johansson, Adam Johannes; Lilja, Christina; Brinck, Tore

    2011-08-01

    Hydrogen gas has been detected in a closed system containing copper and pure anoxic water [P. Szakalos, G. Hultquist, and G. Wikmark, Electrochem. Solid-State Lett. 10, C63 (2007), 10.1149/1.2772085 and G. Hultquist, P. Szakalos, M. Graham, A. Belonoshko, G. Sproule, L. Grasjo, P. Dorogokupets, B. Danilov, T. Aastrup, G. Wikmark, G. Chuah, J. Eriksson, and A. Rosengren, Catal. Lett. 132, 311 (2009), 10.1007/s10562-009-0113-x]. Although bulk corrosion into any of the known phases of copper is thermodynamically forbidden, the present paper shows how surface reactions lead to the formation of hydrogen gas in limited amounts. While water cleavage on copper has been reported and investigated before, formation of molecular hydrogen at a single-crystal Cu[100] surface is here explored using density functional theory and transition state theory. It is found that although solvent catalysis seems possible, the fastest route to the formation of molecular hydrogen is the direct combination of hydrogen atoms on the copper surface. The activation free energy (△Gs‡f) of hydrogen formation in condensed phase is 0.70 eV, which corresponds to a rate constant of 10 s-1 at 298.15 K, i.e., a relatively rapid process. It is estimated that at least 2.4 ng hydrogen gas could form per cm2 on a perfect copper surface.

  17. High Efficiency Hydrogen Production from Nuclear Energy: Laboratory Demonstration of S-I Water-Splitting

    SciTech Connect

    Buckingham, R.; Russ, B.; Brown, L.; Besenbruch, G.E.; Gelbard, F.; Pickard F.S.; Leybros, J.; Le Duigou, A.; Borgard, J.M.

    2004-11-30

    The objective of the French CEA, US-DOE INERI project is to perform a lab scale demonstration of the sulfur iodine (S-I) water splitting cycle, and assess the potential of this cycle for application to nuclear hydrogen production. The project will design, construct and test the three major component reaction sections that make up the S-I cycle. The CEA will design and test the prime (Bunsen) reaction section. General Atomics will develop and test the HI decomposition section, and SNL will develop and test the H2SO4 decomposition section. Activities for this period included initial program coordination and information exchange, the development of models and analyses that will support the design of the component sections, and preliminary designs for the component reaction sections. The sections are being designed to facilitate integration into a closed loop demonstration in a later stage of the program.

  18. Hydrogen bond lifetime for water in classic and quantum molecular dynamics

    NASA Astrophysics Data System (ADS)

    Antipova, M. L.; Petrenko, V. E.

    2013-07-01

    The lifetime of hydrogen bonds in water at T = 298 K and p = 0.1 MPa is computed by means of classic molecular dynamics with eight different potentials of pair lifetime interaction and Car-Parinello molecular dynamics. The results obtained using various computational techniques for hydrogen bond life-times are compared. It is shown that they can differ from one another by several times. The dependence for the hydrogen bond lifetime computed in our numerical experiment upon the method of its determination is found.

  19. Hydrogen bonds in ethylene glycol, monoethanolamine, and ethylenediamine complexes with water

    NASA Astrophysics Data System (ADS)

    Krest'yaninov, M. A.; Titova, A. G.; Zaichikov, A. M.

    2017-02-01

    The structures of ethylene glycol, aminoethanol, and ethylenediamine complexes with water and the formation of hydrogen bonds of different types are optimized using the B3LYP hybrid functional and the aug-CC-pVTZ basis. The parameters of the hydrogen bonds, their energies of interaction, and their oscillation frequencies are calculated, and NBO and QTAIM analyses are performed. The order of hydrogen bonds according to strength is obtained: O-HW···N > O-HW···O > O-H···OW.

  20. Hydrogen-bonding Interactions between Apigenin and Ethanol/Water: A Theoretical Study

    NASA Astrophysics Data System (ADS)

    Zheng, Yan-Zhen; Zhou, Yu; Liang, Qin; Chen, Da-Fu; Guo, Rui; Lai, Rong-Cai

    2016-10-01

    In this work, hydrogen-bonding interactions between apigenin and water/ethanol were investigated from a theoretical perspective using quantum chemical calculations. Two conformations of apigenin molecule were considered in this work. The following results were found. (1) For apigenin monomer, the molecular structure is non-planar, and all of the hydrogen and oxygen atoms can be hydrogen-bonding sites. (2) Eight and seven optimized geometries are obtained for apigenin (I)–H2O/CH3CH2OH and apigenin (II)–H2O/CH3CH2OH complexes, respectively. In apigenin, excluding the aromatic hydrogen atoms in the phenyl substituent, all other hydrogen atoms and the oxygen atoms form hydrogen-bonds with H2O and CH3CH2OH. (3) In apigenin–H2O/CH3CH2OH complexes, the electron density and the E(2) in the related localized anti-bonding orbital are increased upon hydrogen-bond formation. These are the cause of the elongation and red-shift of the X‑H bond. The sum of the charge change transfers from the hydrogen-bond acceptor to donor. The stronger interaction makes the charge change more intense than in the less stable structures. (4) Most of the hydrogen-bonds in the complexes are electrostatic in nature. However, the C4‑O5···H, C9‑O4···H and C13‑O2···H hydrogen-bonds have some degree of covalent character. Furthermore, the hydroxyl groups of the apigenin molecule are the preferred hydrogen-bonding sites.

  1. Hydrogen-bonding Interactions between Apigenin and Ethanol/Water: A Theoretical Study

    PubMed Central

    Zheng, Yan-Zhen; Zhou, Yu; Liang, Qin; Chen, Da-Fu; Guo, Rui; Lai, Rong-Cai

    2016-01-01

    In this work, hydrogen-bonding interactions between apigenin and water/ethanol were investigated from a theoretical perspective using quantum chemical calculations. Two conformations of apigenin molecule were considered in this work. The following results were found. (1) For apigenin monomer, the molecular structure is non-planar, and all of the hydrogen and oxygen atoms can be hydrogen-bonding sites. (2) Eight and seven optimized geometries are obtained for apigenin (I)–H2O/CH3CH2OH and apigenin (II)–H2O/CH3CH2OH complexes, respectively. In apigenin, excluding the aromatic hydrogen atoms in the phenyl substituent, all other hydrogen atoms and the oxygen atoms form hydrogen-bonds with H2O and CH3CH2OH. (3) In apigenin–H2O/CH3CH2OH complexes, the electron density and the E(2) in the related localized anti-bonding orbital are increased upon hydrogen-bond formation. These are the cause of the elongation and red-shift of the X−H bond. The sum of the charge change transfers from the hydrogen-bond acceptor to donor. The stronger interaction makes the charge change more intense than in the less stable structures. (4) Most of the hydrogen-bonds in the complexes are electrostatic in nature. However, the C4−O5···H, C9−O4···H and C13−O2···H hydrogen-bonds have some degree of covalent character. Furthermore, the hydroxyl groups of the apigenin molecule are the preferred hydrogen-bonding sites. PMID:27698481

  2. Bioremediation of chlorobenzene-contaminated ground water in an in situ reactor mediated by hydrogen peroxide.

    PubMed

    Vogt, Carsten; Alfreider, Albin; Lorbeer, Helmut; Hoffmann, Doreen; Wuensche, Lothar; Babel, Wolfgang

    2004-01-01

    New in situ reactive barrier technologies were tested nearby a local aquifer in Bitterfeld, Saxonia-Anhalt, Germany, which is polluted mainly by chlorobenzene (CB), in concentrations up to 450 microM. A reactor filled with original aquifer sediment was designed for the microbiological remediation of the ground water by indigenous bacterial communities. Two remediation variants were examined: (a) the degradation of CB under anoxic conditions in the presence of nitrate; (b) the degradation of CB under mixed electron acceptor conditions (oxygen+nitrate) using hydrogen peroxide as the oxygen-releasing compound. Under anoxic conditions, no definite degradation of CB was observed. Adding hydrogen peroxide (2.94 mM) and nitrate (2 mM) led to the disappearance of CB (ca. 150 microM) in the lower part of the reactor, accompanied by a strong increase of the number of cultivable aerobic CB degrading bacteria in reactor water and sediment samples, indicating that CB was degraded mainly by productive bacterial metabolism. Several aerobic CB degrading bacteria, mostly belonging to the genera Pseudomonas and Rhodococcus, were isolated from reactor water and sediments. In laboratory experiments with reactor water, oxygen was rapidly released by hydrogen peroxide, whereas biotic-induced decomposition reactions of hydrogen peroxide were almost four times faster than abiotic-induced decomposition reactions. A clear chemical degradation of CB mediated by hydrogen peroxide was not observed. CB was also completely degraded in the reactor after reducing the hydrogen peroxide concentration to 880 microM. The CB degradation completely collapsed after reducing the hydrogen peroxide concentration to 440 microM. In the following, the hydrogen peroxide concentrations were increased again (to 880 microM, 2.94 mM, and 880 microM, respectively), but the oxygen demand for CB degradation was higher than observed before, indicating a shift in the bacterial population. During the whole experiment

  3. Uncertainty propagation in modeling of plasma-assisted hydrogen production from biogas

    NASA Astrophysics Data System (ADS)

    Zaherisarabi, Shadi; Venkattraman, Ayyaswamy

    2016-10-01

    With the growing concern of global warming and the resulting emphasis on decreasing greenhouse gas emissions, there is an ever-increasing need to utilize energy-production strategies that can decrease the burning of fossil fuels. In this context, hydrogen remains an attractive clean-energy fuel that can be oxidized to produce water as a by-product. In spite of being an abundant species, hydrogen is seldom found in a form that is directly usable for energy-production. While steam reforming of methane is one popular technique for hydrogen production, plasma-assisted conversion of biogas (carbon dioxide + methane) to hydrogen is an attractive alternative. Apart from producing hydrogen, the other advantage of using biogas as raw material is the fact that two potent greenhouse gases are consumed. In this regard, modeling is an important tool to understand and optimize plasma-assisted conversion of biogas. The primary goal of this work is to perform a comprehensive statistical study that quantifies the influence of uncertain rate constants thereby determining the key reaction pathways. A 0-D chemical kinetics solver in the OpenFOAM suite is used to perform a series of simulations to propagate the uncertainty in rate constants and the resulting mean and standard deviation of outcomes.

  4. Hydrogen in drinking water attenuates noise-induced hearing loss in guinea pigs.

    PubMed

    Lin, Ying; Kashio, Akinori; Sakamoto, Takashi; Suzukawa, Keigo; Kakigi, Akinobu; Yamasoba, Tatsuya

    2011-01-03

    It has been shown that molecular hydrogen acts as a therapeutic and preventive antioxidant by selectively reducing the hydroxyl radical, the most cytotoxic of the reactive oxygen species. In the present study, we tested the hypothesis that acoustic damage in guinea pigs can be attenuated by the consumption of molecular hydrogen. Guinea pigs received normal water or hydrogen-rich water for 14 days before they were exposed to 115 dB SPL 4-kHz octave band noise for 3h. Animals in each group underwent measurements for auditory brainstem response (ABR) or distortion-product otoacoustic emissions (DPOAEs) before the treatment (baseline) and immediately, 1, 3, 7, and 14 days after noise exposure. The ABR thresholds at 2 and 4 kHz were significantly better on post-noise days 1, 3, and 14 in hydrogen-treated animals when compared to the normal water-treated controls. Compared to the controls, the hydrogen-treated animals showed greater amplitude of DPOAE input/output growth functions during the recovery process, with statistical significance detected on post-noise days 3 and 7. These findings suggest that hydrogen can facilitate the recovery of hair cell function and attenuate noise-induced temporary hearing loss.

  5. Hydrogen Bonding between Solutes in Solvents Octan-1-ol and Water

    PubMed Central

    Abraham, Michael H.; Gola, Joelle M. R.; Cometto-Muñiz, J. Enrique; Acree, William E.

    2010-01-01

    1:1 Equilibrium constants, K, for the association of hydrogen bond bases and hydrogen bond acids have been determined using solvent octan-1-ol at 298 K for 30 acid-base combinations. The values of K are much smaller than those found for aprotic, rather non-polar solvents. It is shown that the log K values can satisfactorily be correlated against αH2*βH2, where αH2 and βH2 are the 1:1 hydrogen bond acidities and basicities of solutes. The slope of the plot, 2.938, is much smaller than those for log K values in the non-polar organic solvents previously studied. An analysis of literature data on 1:1 hydrogen bonding in water yields a negative slope for a plot of log K against αH2*βH2, thus showing how the use of very strong hydrogen bond acids and bases does not lead to larger values of log K for 1:1 hydrogen bonding in water. It is suggested that for simple 1:1 association between mono-functional solutes in water, log K cannot be larger than about −0.1 log units. Descriptors have been obtained for the complex between 2,2,2-trifluoroethanol and propanone, and used to analyze solvent effects on the two reactants, the complex, and the complexation constant. PMID:20954704

  6. Polarization Effects for Hydrogen-Bonded Complexes of Substituted Phenols with Water and Chloride Ion.

    PubMed

    Jorgensen, William L; Jensen, Kasper P; Alexandrova, Anastassia N

    2007-11-01

    Variations in hydrogen-bond strengths are investigated for complexes of nine para-substituted phenols (XPhOH) with a water molecule and chloride ion. Results from ab initio HF/6-311+G(d, p) and MP2/6-311+G(d, p)//HF/6-311+G(d, p) calculations are compared with those from the OPLS-AA and OPLS/CM1A force fields. In the OPLS-AA model, the partial charges on the hydroxyl group of phenol are not affected by the choice of para substituent, while the use of CM1A charges in the OPLS/CM1A approach does provide charge redistribution. The ab initio calculations reveal a 2.0-kcal/mol range in hydrogen-bond strengths for the XPhOH⋯OH(2) complexes in the order X = NO(2) > CN > CF(3) > Cl > F > H >OH >CH(3) > NH(2). The pattern is not well-reproduced with OPLS-AA, which also compresses the variation to 0.7 kcal/mol. However, the OPLS/CM1A results are in good accord with the ab initio findings for both the ordering and range, 2.3 kcal/mol. The hydrogen bonding is, of course, weaker with XPhOH as acceptor, the order for X is largely inverted, and the range is reduced to ca. 1.0 kcal/mol. The substituent effects are found to be much greater for the chloride ion complexes with a range of 11 kcal/mol. For quantitative treatment of such strong ion-molecule interactions the need for fully polarizable force fields is demonstrated.

  7. A reaction-diffusion model of cytosolic hydrogen peroxide.

    PubMed

    Lim, Joseph B; Langford, Troy F; Huang, Beijing K; Deen, William M; Sikes, Hadley D

    2016-01-01

    As a signaling molecule in mammalian cells, hydrogen peroxide (H2O2) determines the thiol/disulfide oxidation state of several key proteins in the cytosol. Localization is a key concept in redox signaling; the concentrations of signaling molecules within the cell are expected to vary in time and in space in manner that is essential for function. However, as a simplification, all theoretical studies of intracellular hydrogen peroxide and many experimental studies to date have treated the cytosol as a well-mixed compartment. In this work, we incorporate our previously reported reduced kinetic model of the network of reactions that metabolize hydrogen peroxide in the cytosol into a model that explicitly treats diffusion along with reaction. We modeled a bolus addition experiment, solved the model analytically, and used the resulting equations to quantify the spatiotemporal variations in intracellular H2O2 that result from this kind of perturbation to the extracellular H2O2 concentration. We predict that micromolar bolus additions of H2O2 to suspensions of HeLa cells (0.8 × 10(9)cells/l) result in increases in the intracellular concentration that are localized near the membrane. These findings challenge the assumption that intracellular concentrations of H2O2 are increased uniformly throughout the cell during bolus addition experiments and provide a theoretical basis for differing phenotypic responses of cells to intracellular versus extracellular perturbations to H2O2 levels.

  8. Raman spectra from Symmetric Hydrogen Bonds in Water by High-intensity Laser-induced Breakdown

    PubMed Central

    Men, Zhiwei; Fang, Wenhui; Li, Dongfei; Li, Zhanlong; Sun, Chenglin

    2014-01-01

    Raman spectra of ice VII and X were investigated using strong plasma shockwave generated by laser-induced breakdown (LIB) in liquid water. Simultaneously, the occurrence of the hydrogen emission lines of 656 nm (Hα), 486 nm (Hβ), 434 nm (Hγ) and 410 nm (Hδ) was observed. At 5 × 1012 W/cm2 optical power density, the O-H symmetric stretching, translational and librational modes of ice VII and a single peak at 785 cm−1 appeared in the spectra. The band was assigned to the Raman-active O-O mode of the monomolecular phase, which was the symmetric hydrogen bond of cuprite ice X. The spectra indicated that ice VII and X structure were formed, as the trajectory of the strong plasma shockwave passes through the stable Pressure-Temperature range of ice VII and X. The shockwave temperature and pressure were calculated by the Grüneisen model. PMID:24709652

  9. Hydrogen-rich water improves neurological functional recovery in experimental autoimmune encephalomyelitis mice.

    PubMed

    Zhao, Ming; Liu, Ming-Dong; Pu, Ying-Yan; Wang, Dan; Xie, Yu; Xue, Gai-Ci; Jiang, Yong; Yang, Qian-Qian; Sun, Xue-Jun; Cao, Li

    2016-05-15

    Multiple sclerosis (MS) is a chronic autoimmune demyelinating disease of the central nervous system (CNS). The high costs, inconvenient administration, and side effects of current Food and Drug Administration (FDA)-approved drugs often lead to poor adherence to the long-term treatment of MS. Molecular hydrogen (H2) has been reported to exhibit anti-oxidant, anti-apoptotic, anti-inflammatory, anti-allergy, and anti-cancer effects. In the present study, we explored the prophylactic and therapeutic effects of hydrogen-rich water (HRW) on the progress of experimental autoimmune encephalomyelitis (EAE), the animal model for MS. We found that prophylactic administration of both 0.36mM and 0.89mM HRW was able to delay EAE onset and reduce maximum clinical scores. Moreover, 0.89mM HRW also reduced disease severity, CNS infiltration, and demyelination when administered after the onset of disease. Furthermore, HRW treatment prevented infiltration of CD4(+) T lymphocytes into the CNS and inhibited Th17 cell development without affecting Th1 cell populations. Because HRW is non-toxic, inexpensive, easily administered, and can readily cross the blood-brain barrier, our experiments suggest that HRW may have great potential in the treatment of MS.

  10. Rapid water transportation through narrow one-dimensional channels by restricted hydrogen bonds.

    PubMed

    Ohba, Tomonori; Kaneko, Katsumi; Endo, Morinobu; Hata, Kenji; Kanoh, Hirofumi

    2013-01-29

    Water plays an important role in controlling chemical reactions and bioactivities. For example, water transportation through water channels in a biomembrane is a key factor in bioactivities. However, molecular-level mechanisms of water transportation are as yet unknown. Here, we investigate water transportation through narrow and wide one-dimensional (1D) channels on the basis of water-vapor adsorption rates and those determined by molecular dynamics simulations. We observed that water in narrow 1D channels was transported 3-5 times faster than that in wide 1D channels, although the narrow 1D channels provide fewer free nanospaces for water transportation. This rapid transportation is attributed to the formation of fewer hydrogen bonds between water molecules adsorbed in narrow 1D channels. The water-transportation mechanism provides the possibility of rapid communication through 1D channels and will be useful in controlling reactions and activities in water systems.

  11. Exploring the activity of a novel Au/TiC(001) model catalyst towards CO and CO2 hydrogenation

    NASA Astrophysics Data System (ADS)

    Asara, Gian Giacomo; Ricart, Josep M.; Rodriguez, Jose A.; Illas, Francesc

    2015-10-01

    Small metallic nanoparticles supported on transition metal carbides exhibit an unexpected high activity towards a series of chemical reactions. In particular, the Au/TiC system has proven to be an excellent catalyst for SO2 decomposition, thiophene hydrodesulfurization, O2 and H2 dissociation and the water gas shift reaction. Recent studies have shown that Au/TiC is a very good catalyst for the reverse water-gas shift (CO2 + H2 → CO + H2O) and CO2 hydrogenation to methanol. The present work further expands the range of applicability of this novel type of systems by exploring the catalytic activity of Au/TiC towards the hydrogenation of CO or CO2 with periodic density functional theory (DFT) calculations on model systems. Hydrogen dissociates easily on Au/TiC but direct hydrogenation of CO to methanol is hindered by very high activation barriers implying that, on this model catalyst, methanol production from CO2 involves the hydrogenation of a HOCO-like intermediate. When dealing with mixtures of syngas (CO/CO2/H2/H2O), CO could be transformed into CO2 through the water gas shift reaction with subsequent hydrogenation of CO2 to methanol.

  12. Effect of Hydrogen Plasma on Model Corrosion Layers of Bronze

    NASA Astrophysics Data System (ADS)

    Fojtíková, P.; Sázavská, V.; Mika, F.; Krčma, F.

    2016-05-01

    Our work is about plasmachemical reduction of model corrosion layers. The model corrosion layers were produced on bronze samples with size of 10 × 10 × 5 mm3, containing Cu and Sn. Concentrated hydrochloric acid was used as a corrosive environment. The application of reduction process in low-pressure low-temperature hydrogen plasma followed. A quartz cylindrical reactor with two outer copper electrodes was used. Plasma discharge was generated in pure hydrogen by a RF generator. Each corroded sample was treated in different conditions (supplied power and a continual or pulsed regime with a variable duty cycle mode). Process monitoring was ensured by optical emission spectroscopy. After treatment, samples were analyzed by SEM and EDX.

  13. Semirelativistic model for ionization of atomic hydrogen by electron impact

    NASA Astrophysics Data System (ADS)

    Attaourti, Y.; Taj, S.; Manaut, B.

    2005-06-01

    We present a semirelativistic model for the description of the ionization process of atomic hydrogen by electron impact in the first Born approximation by using the Darwin wave function to describe the bound state of atomic hydrogen and the Sommerfeld-Maue wave function to describe the ejected electron. This model, accurate to first order in Z/c in the relativistic correction, shows that, even at low kinetic energies of the incident electron, spin effects are small but not negligible. These effects become noticeable with increasing incident electron energies. All analytical calculations are exact and our semirelativistic results are compared with the results obtained in the nonrelativistic Coulomb Born approximation both for the coplanar asymmetric and the binary coplanar geometries.

  14. Semirelativistic model for ionization of atomic hydrogen by electron impact

    SciTech Connect

    Attaourti, Y.; Taj, S.; Manaut, B.

    2005-06-15

    We present a semirelativistic model for the description of the ionization process of atomic hydrogen by electron impact in the first Born approximation by using the Darwin wave function to describe the bound state of atomic hydrogen and the Sommerfeld-Maue wave function to describe the ejected electron. This model, accurate to first order in Z/c in the relativistic correction, shows that, even at low kinetic energies of the incident electron, spin effects are small but not negligible. These effects become noticeable with increasing incident electron energies. All analytical calculations are exact and our semirelativistic results are compared with the results obtained in the nonrelativistic Coulomb Born approximation both for the coplanar asymmetric and the binary coplanar geometries.

  15. Hydrogen and oxygen in brine shrimp chitin reflect environmental water and dietary isotopic composition

    NASA Astrophysics Data System (ADS)

    Nielson, Kristine E.; Bowen, Gabriel J.

    2010-03-01

    Hydrogen and oxygen isotope ratios of the common structural biopolymer chitin are a potential recorder of ecological and environmental information, but our understanding of the mechanisms of incorporation of H and O from environmental substrates into chitin is limited. We report the results of a set of experiments in which the isotopic compositions of environmental water and diet were varied independently in order to assess the contribution of these variables to the H and O isotopic composition of Artemia franciscana chitin. Hydrogen isotope ratios of chitin were strongly linearly correlated with both food and water, with approximately 26% of the hydrogen signal reflecting food and approximately 38% reflecting water. Oxygen isotopes were also strongly correlated with the isotopic composition of water and food, but whereas 69% of oxygen in chitin exchanged with environmental water, only 10% was derived from food. We propose that these observations reflect the position-specific, partial exchange of H and O atoms with brine shrimp body water during the processes of digestion and chitin biosynthesis. Comparison of culture experiments with a set of natural samples collected from the Great Salt Lake, UT in 2006 shows that, with some exceptions, oxygen isotope compositions of chitin track those of water, whereas hydrogen isotopes vary inversely with those of lake water. The different behavior of the two isotopic systems can be explained in terms of a dietary shift from allochthonous particulate matter with relatively higher δ 2H values in the early spring to autochthonous particulate matter with significantly lower δ 2H values in the late summer to autumn. These results suggest oxygen in chitin may be a valuable proxy for the oxygen isotopic composition of environmental water, whereas hydrogen isotope values from the same molecule may reveal ecological and biogeochemical changes within lakes.

  16. The hydrogenation of metals upon interaction with water

    NASA Technical Reports Server (NTRS)

    Andreyev, L. A.; Gelman, B. G.; Zhukhovitskiy, A. A.; Polosina, Y. Y.

    1979-01-01

    Hydrogen evolution at 600 deg and 5 x 10 to the 7th power - 10 to the 6th power torr from AVOOO Al samples, which were pickled in 10 percent NaOH, is discussed. An H evolution kinetic equation is derived for samples of equal vol. and different surfaces (5 and 20 sq cm). The values of the H evolution coefficient K indicated an agreement with considered H diffusion mechanism through an oxide layer. The activation energy for the H evolution process, obtained from the K-temp. relation, was 13,000 2000 cal/g-atom.

  17. Hydrogen and oxygen isotope exchange reactions between clay minerals and water

    USGS Publications Warehouse

    O'Neil, J.R.; Kharaka, Y.K.

    1976-01-01

    The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100-350?? for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100??. Exchange rates were 3-5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure. Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O18 exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O18 exchange. At 350?? kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O18 exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor. ?? 1976.

  18. Metal-encapsulated organolead halide perovskite photocathode for solar-driven hydrogen evolution in water

    NASA Astrophysics Data System (ADS)

    Crespo-Quesada, Micaela; Pazos-Outón, Luis M.; Warnan, Julien; Kuehnel, Moritz F.; Friend, Richard H.; Reisner, Erwin

    2016-09-01

    Lead-halide perovskites have triggered the latest breakthrough in photovoltaic technology. Despite the great promise shown by these materials, their instability towards water even in the presence of low amounts of moisture makes them, a priori, unsuitable for their direct use as light harvesters in aqueous solution for the production of hydrogen through water splitting. Here, we present a simple method that enables their use in photoelectrocatalytic hydrogen evolution while immersed in an aqueous solution. Field's metal, a fusible InBiSn alloy, is used to efficiently protect the perovskite from water while simultaneously allowing the photogenerated electrons to reach a Pt hydrogen evolution catalyst. A record photocurrent density of -9.8 mA cm-2 at 0 V versus RHE with an onset potential as positive as 0.95+/-0.03 V versus RHE is obtained. The photoelectrodes show remarkable stability retaining more than 80% of their initial photocurrent for ~1 h under continuous illumination.

  19. Hydrogen-water mixtures in giant planet interiors studied with ab initio simulations

    NASA Astrophysics Data System (ADS)

    Soubiran, F.; Militzer, B.

    2015-12-01

    We study water-hydrogen mixtures under planetary interior conditions using ab initio molecular dynamics simulations. We determine the thermodynamic properties of various water-hydrogen mixing ratios at temperatures of 2000 and 6000 K for pressures of a few tens of GPa. These conditions are relevant for ice giant planets and for the outer envelope of the gas giants. We find that at 2000 K the mixture is in a molecular regime, while at 6000 K the dissociation of hydrogen and water is important and affects the thermodynamic properties. We study the structure of the liquid and analyze the radial distribution function. We provide estimates for the transport properties, diffusion and viscosity, based on autocorrelation functions. We obtained viscosity estimates of the order of a few tenths of mPa s for the conditions under consideration. These results are relevant for dynamo simulations of ice giant planets.

  20. Hydrogen Mobility and Protein-Water Interactions in Proteins in the Solid State.

    PubMed

    Tompa, Kálmán; Bokor, Mónika; Ágner, Dorina; Iván, Dávid; Kovács, Dénes; Verebélyi, Tamás; Tompa, Péter

    2017-03-17

    In this work the groundwork is laid for characterizing the mobility of hydrogen-hydrogen pairs (proton-proton radial vectors) in proteins in the solid state that contain only residual water. In this novel approach, we introduce new ways of analyzing and interpreting data: 1) by representing hydrogen mobility (HM) and melting diagram (MD) data recorded by wide-line (1) H NMR spectroscopic analysis as a function of fundamental temperature (thermal excitation energy); 2) by suggesting a novel mode of interpretation of these parameters that sheds light on details of protein-water interactions, such as the exact amount of water molecules and the distribution of barrier potentials pertaining to their rotational and surface translational mobility; 3) by relying on directly determined physical observables. We illustrate the power of this approach by studying the behavior of two proteins, the structured enzyme lysozyme and the intrinsically disordered ERD14.

  1. Classification of hydrogen bond flips in small water polyhedra applied to concerted proton tunneling.

    PubMed

    Kirov, M V

    2016-10-05

    Recently a new mechanism of proton tunneling in a prism-like water hexamer was revealed [Richardson et al., Science, 2016, 351, 1310]. The tunneling motion involves the concerted breaking of two hydrogen bonds and rotations of two nearest water molecules. Eventually, this structural transformation means flipping one of the hydrogen bonds without the creation of defects in the hydrogen bond network. On the surface of polyhedral water clusters, there are five essentially different types of hydrogen bonds, and only two of them can be changed in this manner. In this article, the topological classification of such transformations for five small water polyhedra: triangular, pentagonal, and hexagonal prisms as well as cube and polyhedron 4(4)5(4), consisting of four square and four pentagonal faces, is presented. Our classification includes the enumeration of all possible one-bond-flips with consideration of the types of hydrogen bonds on the polyhedral surface. Attention is paid to the most stable proton configurations which can be studied in experiments. It was established that a number of one-bond-flip transitions between the low energy configurations are possible in clusters in the shape of triangular and pentagonal prisms.

  2. Variational transition state theory calculations of tunneling effects on concerted hydrogen motion in water clusters and formaldehyde/water clusters

    SciTech Connect

    Garrett, B.C. ); Melius, C.F. )

    1990-08-01

    The direct participation of water molecules in aqueous phase reaction processes has been postulated to occur via both single-step mechanisms as well as concerted hydrogen atom or proton shifts. In the present work, simple prototypes of concerted hydrogen atom transfer processes are examined for small hydrogen-bonded water clusters -- cyclic trimers and tetramers -- and hydrogen-bonded clusters of formaldehyde with one and two water molecules. Rate constants for the rearrangement processes are computed using variational transition state theory, accounting for quantum mechanical tunneling effects by semiclassical ground-state adiabatic transmission coefficients. The variational transition state theory calculations directly utilize selected information about the potential energy surface along the minimum energy path as parameters of the reaction path Hamiltonian. The potential energy information is obtained from ab ignite electronic structure calculations with an empirical bond additivity correction (the BAC-MP4 method). Tunneling is found to be very important for these concerted rearrangement processes -- the semiclassical ground-state adiabatic transmission coefficients are estimated to be as high as four order of magnitude at room temperature. Effects of the size of the cluster (number of water molecules in the cyclic complex) are also dramatic -- addition of a water molecule is seen to change the calculated rates by orders of magnitude. 36 refs., 10 figs.

  3. Water co-catalyzed selective dehydrogenation of methanol to formaldehyde and hydrogen

    NASA Astrophysics Data System (ADS)

    Shan, Junjun; Lucci, Felicia R.; Liu, Jilei; El-Soda, Mostafa; Marcinkowski, Matthew D.; Allard, Lawrence F.; Sykes, E. Charles H.; Flytzani-Stephanopoulos, Maria

    2016-08-01

    The non-oxidative dehydrogenation of methanol to formaldehyde is considered a promising method to produce formaldehyde and clean hydrogen gas. Although Cu-based catalysts have an excellent catalytic activity in the oxidative dehydrogenation of methanol, metallic Cu is commonly believed to be unreactive for the dehydrogenation of methanol in the absence of oxygen adatoms or oxidized copper. Herein we show that metallic Cu can catalyze the dehydrogenation of methanol in the absence of oxygen adatoms by using water as a co-catalyst both under realistic reaction conditions using silica-supported PtCu nanoparticles in a flow reactor system at temperatures below 250 °C, and in ultra-high vacuum using model PtCu(111) catalysts. Adding small amounts of isolated Pt atoms into the Cu surface to form PtCu single atom alloys (SAAs) greatly enhances the dehydrogenation activity of Cu. Under the same reaction conditions, the yields of formaldehyde from PtCu SAA nanoparticles are more than one order of magnitude higher than on the Cu nanoparticles, indicating a significant promotional effect of individual, isolated Pt atoms. Moreover, this study also shows the unexpected role of water in the activation of methanol. Water, a catalyst for methanol dehydrogenation at low temperatures, becomes a reactant in the methanol steam reforming reactions only at higher temperatures over the same metal catalyst.

  4. UO2 surface oxidation by mixtures of water vapor and hydrogen as a function of temperature

    NASA Astrophysics Data System (ADS)

    Espriu-Gascon, A.; Llorca, J.; Domínguez, M.; Giménez, J.; Casas, I.; de Pablo, J.

    2015-12-01

    In the present work, X-Ray Photoelectron Spectroscopy (XPS) was used to study the effect of water vapor on the UO2 surface as a function of temperature. The experiments were performed in situ inside a high pressure chamber attached to the XPS instrument. UO2 samples were put in contact with either hydrogen or argon streams, saturated with water at room temperature, and the sample surface evolution was analyzed by XPS. In the case of the water vapor/argon experiments, one experiment at 350 °C was performed and, in the case of the water vapor/hydrogen experiments, the temperatures used inside the reactor were 60, 120, 200 and 350 °C. On one hand, in presence of argon, the results obtained showed that the water vapor in the argon stream oxidized 93% of the U(IV) in the sample surface. On the other hand, the degree of UO2 surface oxidation showed a different dependence on the temperature in the experiments performed in the presence of hydrogen: the maximum surface oxidation occurred at 120 °C, where 65.4% of U(IV) in the sample surface was oxidized, while at higher temperatures, the surface oxidation decreased. This observation is attributed to the increase of hydrogen reducing effect when temperature increases which prevents part of the oxidation of the UO2 surface by the water vapor.

  5. Dynamic Modeling of Hydrogen Sulfide within Enclosed Environments in Biosolids Recovery Facilities.

    PubMed

    Matos, Rita Ventura; Matias, Natércia; Ferreira, Filipa; Matos, José Saldanha

    2016-12-01

    Hydrogen sulfide emissions from wastewater affect human health and equipment durability, thus presenting a complex issue for utilities. Several VOC emission models have been used before to predict H2S in collection systems and water resources recovery operations, even if with restrictions. By contrast, fewer studies focus on biosolids emissions and modelling. This paper presents a dynamic modelling approach to predict H2S concentration in a tank headspace of a wastewater biosolids recovery facility. Data from one of the largest Portuguese water resources recovery facilities was collected under different facility operating modes. The developed model adequately predicted H2S concentration, with R2 values of 0.89 and 0.78, for different periods of the year, thus showing how modelling may reliably contribute to utility operation decisions.

  6. Assessment of shock effects on amphibole water contents and hydrogen isotope compositions: 1. Amphibolite experiments

    NASA Astrophysics Data System (ADS)

    Minitti, Michelle E.; Rutherford, Malcolm J.; Taylor, Bruce E.; Dyar, M. Darby; Schultz, Peter H.

    2008-02-01

    Kaersutitic amphiboles found within a subset of the Martian meteorites have low water contents and variably heavy hydrogen isotope compositions. In order to assess if impact shock-induced devolatilization and hydrogen isotope fractionation were determining factors in these water and isotopic characteristics of the Martian kaersutites, we conducted impact shock experiments on samples of Gore Mountain amphibolite in the Ames Vertical Gun Range (AVGR). A parallel shock experiment conducted on an anorthosite sample indicated that contamination of shocked samples by the AVGR hydrogen propellant was unlikely. Petrographic study of the experimental amphibolite shock products indicates that only ˜ 10% of the shock products experienced levels of damage equivalent to those found in the most highly shocked kaersutite-bearing Martian meteorites (30-35 GPa). Ion microprobe studies of highly shocked hornblende from the amphibolite exhibited elevated water contents (ΔH 2O ˜ 0.1 wt.%) and enriched hydrogen isotope compositions (Δ D ˜ + 10‰) relative to unshocked hornblende. Water and hydrogen isotope analyses of tens of milligrams of unshocked, moderately shocked, and highly shocked hornblende samples by vacuum extraction/uranium reduction and isotope ratio mass spectrometry (IRMS), respectively, are largely consistent with analyses of single grains from the ion microprobe. The mechanisms thought to have produced the excess water in most of the shocked hornblendes are shock-induced reduction of hornblende Fe and/or irreversible adsorption of hydrogen. Addition of the isotopically enriched Martian atmosphere to the Martian meteorite kaersutites via these mechanisms could explain their enriched and variable isotopic compositions. Alternatively, regrouping the water extraction and IRMS analyses on the basis of isotopic composition reveals a small, but consistent, degree of impact-induced devolatilization (˜ 0.1 wt.% H 2O) and H isotope enrichment (Δ D ˜ + 10

  7. Resource recovery from used water: the manufacturing abilities of hydrogen-oxidizing bacteria.

    PubMed

    Matassa, Silvio; Boon, Nico; Verstraete, Willy

    2015-01-01

    Resources in used water are at present mainly destroyed rather than reused. Recovered nutrients can serve as raw material for the sustainable production of high value bio-products. The concept of using hydrogen and oxygen, produced by green or off-peak energy by electrolysis, as well as the unique capability of autotrophic hydrogen oxidizing bacteria to upgrade nitrogen and minerals into valuable microbial biomass, is proposed. Both axenic and mixed microbial cultures can thus be of value to implement re-synthesis of recovered nutrients in biomolecules. This process can become a major line in the sustainable "water factory" of the future.

  8. Oral ‘hydrogen water' induces neuroprotective ghrelin secretion in mice

    PubMed Central

    Matsumoto, Akio; Yamafuji, Megumi; Tachibana, Tomoko; Nakabeppu, Yusaku; Noda, Mami; Nakaya, Haruaki

    2013-01-01

    The therapeutic potential of molecular hydrogen (H2) is emerging in a number of human diseases and in their animal models, including in particular Parkinson's disease (PD). H2 supplementation of drinking water has been shown to exert disease-modifying effects in PD patients and neuroprotective effects in experimental PD model mice. However, H2 supplementation does not result in detectable changes in striatal H2 levels, indicating an indirect effect. Here we show that H2 supplementation increases gastric expression of mRNA encoding ghrelin, a growth hormone secretagogue, and ghrelin secretion, which are antagonized by the β1-adrenoceptor blocker, atenolol. Strikingly, the neuroprotective effect of H2 water was abolished by either administration of the ghrelin receptor-antagonist, D-Lys3 GHRP-6, or atenolol. Thus, the neuroprotective effect of H2 in PD is mediated by enhanced production of ghrelin. Our findings point to potential, novel strategies for ameliorating pathophysiology in which a protective effect of H2 supplementation has been demonstrated. PMID:24253616

  9. Synechocystis sp. PCC6803 metabolic models for the enhanced production of hydrogen.

    PubMed

    Montagud, Arnau; Gamermann, Daniel; Fernández de Córdoba, Pedro; Urchueguía, Javier F

    2015-06-01

    In the present economy, difficulties to access energy sources are real drawbacks to maintain our current lifestyle. In fact, increasing interests have been gathered around efficient strategies to use energy sources that do not generate high CO2 titers. Thus, science-funding agencies have invested more resources into research on hydrogen among other biofuels as interesting energy vectors. This article reviews present energy challenges and frames it into the present fuel usage landscape. Different strategies for hydrogen production are explained and evaluated. Focus is on biological hydrogen production; fermentation and photon-fuelled hydrogen production are compared. Mathematical models in biology can be used to assess, explore and design production strategies for industrially relevant metabolites, such as biofuels. We assess the diverse construction and uses of genome-scale metabolic models of cyanobacterium Synechocystis sp. PCC6803 to efficiently obtain biofuels. This organism has been studied as a potential photon-fuelled production platform for its ability to grow from carbon dioxide, water and photons, on simple culture media. Finally, we review studies that propose production strategies to weigh this organism's viability as a biofuel production platform. Overall, the work presented in this review unveils the industrial capabilities of cyanobacterium Synechocystis sp. PCC6803 to evolve interesting metabolites as a clean biofuel production platform.

  10. Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts.

    PubMed

    Lin, Lili; Zhou, Wu; Gao, Rui; Yao, Siyu; Zhang, Xiao; Xu, Wenqian; Zheng, Shijian; Jiang, Zheng; Yu, Qiaolin; Li, Yong-Wang; Shi, Chuan; Wen, Xiao-Dong; Ma, Ding

    2017-03-22

    Polymer electrolyte membrane fuel cells (PEMFCs) running on hydrogen are attractive alternative power supplies for a range of applications, with in situ release of the required hydrogen from a stable liquid offering one way of ensuring its safe storage and transportation before use. The use of methanol is particularly interesting in this regard, because it is inexpensive and can reform itself with water to release hydrogen with a high gravimetric density of 18.8 per cent by weight. But traditional reforming of methanol steam operates at relatively high temperatures (200-350 degrees Celsius), so the focus for vehicle and portable PEMFC applications has been on aqueous-phase reforming of methanol (APRM). This method requires less energy, and the simpler and more compact device design allows direct integration into PEMFC stacks. There remains, however, the need for an efficient APRM catalyst. Here we report that platinum (Pt) atomically dispersed on α-molybdenum carbide (α-MoC) enables low-temperature (150-190 degrees Celsius), base-free hydrogen production through APRM, with an average turnover frequency reaching 18,046 moles of hydrogen per mole of platinum per hour. We attribute this exceptional hydrogen production-which far exceeds that of previously reported low-temperature APRM catalysts-to the outstanding ability of α-MoC to induce water dissociation, and to the fact that platinum and α-MoC act in synergy to activate methanol and then to reform it.

  11. Spontaneous high-yield hydrogen production from cellulosic materials and water catalyzed by enzyme cocktail

    SciTech Connect

    Ye, Xinhao; Wang, Yiran; Hopkins, Robert C.; Adams, Michael W. W.; Evans, Barbara R; Mielenz, Jonathan R; Zhang, Y.-H. Percival

    2009-01-01

    Carbon-neutral hydrogen gas is a compelling energy carrier, especially for the transportation section. Low-cost hydrogen can be produced from abundant renewable lignocellulosic biomass through a number of methods employing chemical catalysis, biocatalysis or a combination of both, but these technologies suffer from low hydrogen yields (well below the theoretical yield of 12 H2 per glucose), undesired side-products and/or required severe reaction conditions. Here we present a novel in vitro synthetic biology approach for producing near theoretical hydrogen yields from cellulosic materials (cellodextrins) and water at 32oC and 1 atm. These non-natural catabolic pathways containing up to 14 enzymes and one coenzyme degrade cellodextrins initially to glucose-1-phosphate and eventually to CO2, split water and finally release the chemical energy in the form of hydrogen gas. Up to 11.2 H2 per anhydroglucose was produced in a batch reaction. This spontaneous endothermic reaction is driven by entropy gain, suggesting that the thermal energy is adsorbed for generating more chemical energy (hydrogen gas) than that in cellodextrins, i.e., output/input of chemical energy > 1, with an input of ambient-temperature thermal energy.

  12. Titanium Dioxide Nanorods with Hydrogenated Oxygen Vacancies for Enhanced Solar Water Splitting.

    PubMed

    Sun, Bo; Shi, Tielin; Tan, Xianhua; Liu, Zhiyong; Wu, Youni; Liao, Guanglan

    2016-06-01

    We demonstrate that moderate hydrogen annealing is a simple and effective approach to substantially improve the photocatalytic activity of TiO2 nanorods via increasing oxygen vacancies in outer layer. Hydrogenated TiO2 nanorods are obtained by annealing in hydrogen atmosphere at various temperatures ranging from 200 degrees C to 350 degrees C. TEM images directly illustrate the disordered layer on the surface of nanorods induced by hydrogen annealing. The photoelectrochemical measurements reveal that the photocurrent is improved first as the temperature increases and reaches to the maximum value at an appropriate temperature (250 degrees C), corresponding to about 50% enhancement compared to the pristine TiO2. Incident photon-to-electron conversion efficiency spectra reveal that the photocurrent improvement is mainly attributed to the enhanced photocatalytic activity of TiO2 in ultraviolet region. Mott-Schottky plots further betray that hydrogen annealing can significantly enhance the electric conductivity, via increasing the oxygen vacancies density in the outer layer. In addition, time-dependent measurements indicate the hydrogenated TiO2 nanorods possess excellent chemical stability. Thus, we believe the hydrogenated TiO2 nanorods would be a promising candidate for photoanode in solar water splitting.

  13. A Comprehensive Study of Hydrogen Adsorbing to Amorphous Water ice: Defining Adsorption in Classical Molecular Dynamics

    NASA Astrophysics Data System (ADS)

    Dupuy, John L.; Lewis, Steven P.; Stancil, P. C.

    2016-11-01

    Gas-grain and gas-phase reactions dominate the formation of molecules in the interstellar medium (ISM). Gas-grain reactions require a substrate (e.g., a dust or ice grain) on which the reaction is able to occur. The formation of molecular hydrogen (H2) in the ISM is the prototypical example of a gas-grain reaction. In these reactions, an atom of hydrogen will strike a surface, stick to it, and diffuse across it. When it encounters another adsorbed hydrogen atom, the two can react to form molecular hydrogen and then be ejected from the surface by the energy released in the reaction. We perform in-depth classical molecular dynamics simulations of hydrogen atoms interacting with an amorphous water-ice surface. This study focuses on the first step in the formation process; the sticking of the hydrogen atom to the substrate. We find that careful attention must be paid in dealing with the ambiguities in defining a sticking event. The technical definition of a sticking event will affect the computed sticking probabilities and coefficients. Here, using our new definition of a sticking event, we report sticking probabilities and sticking coefficients for nine different incident kinetic energies of hydrogen atoms [5-400 K] across seven different temperatures of dust grains [10-70 K]. We find that probabilities and coefficients vary both as a function of grain temperature and incident kinetic energy over the range of 0.99-0.22.

  14. Dependence of molecular hydrogen formation in water on scavengers of the precursor to the hydrated electron

    SciTech Connect

    Pastina, B. |; LaVerne, J.A.; Pimblott, S.M.

    1999-07-22

    Early studies on the radiolysis of water suggested a wide variety of precursors, and mechanisms, for the formation of the observed yield of molecular hydrogen. Molecular hydrogen yields have been measured in the {gamma} radiolysis of aqueous solutions with a wide variety of scavengers of the hydrated electron and its precursors. A decrease in molecular hydrogen yield with increasing scavenging capacity of the hydrated electron is found with all solutes. Scavengers with particularly high rate coefficients for reaction with the precursors to the hydrated electron compared to the hydrated electron, such as selenate and to a lesser extent molybdate, show a more rapid decrease in hydrogen yields with increasing scavenging capacity than is observed with the other solutes. The yield of molecular hydrogen is better parameterized by the scavenging capacity for the precursors to the hydrated electron than by the scavenging capacity for the hydrated electron. Good scavengers of precursors to the hydrated electrons do not exhibit a nonscavengable hydrogen yield in the high scavenging capacity limit. These results suggest that the previously accepted nonscavengable yield of molecular hydrogen is due to precursors of the hydrated electron and it can be lowered with appropriate scavengers.

  15. Herschel Legacy Survey of Hydrogen Fluoride and Water Towards Nearby Galaxies

    NASA Astrophysics Data System (ADS)

    Rodriguez Monje, Raquel

    Hydride molecules, molecules containing just one heavy element atom with one or more hydrogen atoms, play an importance role in interstellar chemistry, as they are often stable end points of chemical reactions, or represent important intermediate stages of the reaction chains theorized to form gas phase molecules. This makes hydride molecules a sensitive test of these chemical models, as well as potential tracers of molecular hydrogen. Due to the low moment of inertia, hydrides have their fundamental rotational transitions in the submillimeter band, blocked by the Earth's atmosphere and in most cases, only accessible with the past NASA mission, Herschel Space Observatory. Two of the key results from Herschel observations are: the first detection of the fundamental J = 1 - 0 rotational transition of hydrogen fluoride (HF) at 1.232 THz (243 μm) and the discovery of HF's ubiquitous nature in the Milky Way. HF has not only been observed toward almost every bright continuum source in the Galactic plane, but also in some nearby ultra luminous galaxies, establishing its importance outside the Milky Way as well. Despite fluorine's (F) relative low abundance in the interstellar medium (ISM) (about four times lower than carbon), F plays an important role in the interstellar chemistry due to the unique thermochemistry of the reaction between F and molecular hydrogen (H2). F is the only atom that reacts exothermically with H2, to form the compound HF. Once formed, HF becomes the main reservoir of fluorine in the ISM, with a strong bond only destroyed by reactions with low abundance ions H3+, C+ and He+, or photodissociation. This unusual stability allows the build up of large amounts of HF in the ISM, which has now been confirmed by Herschel. Chemical model predicted that the ground state rotational transition line of HF J = 1 - 0 would yield an extremely sensitive probe of the diffuse molecular gas along the line-of-sight to background far-infrared continuum sources and a

  16. Performance model of a recirculating stack nickel hydrogen cell

    NASA Technical Reports Server (NTRS)

    Zimmerman, Albert H.

    1994-01-01

    A theoretical model of the nickel hydrogen battery cell has been utilized to describe the chemical and physical changes during charge and overcharge in a recirculating stack nickel hydrogen cell. In particular, the movement of gas and electrolyte have been examined as a function of the amount of electrolyte put into the cell stack during cell activation, and as a function of flooding in regions of the gas screen in this cell design. Additionally, a two-dimensional variation on this model has been utilized to describe the effects of non-uniform loading in the nickel-electrode on the movement of gas and electrolyte within the recirculating stack nickel hydrogen cell. The type of nonuniform loading that has been examined here is that associated with higher than average loading near the surface of the sintered nickel electrode, a condition present to some degree in many nickel electrodes made by electrochemical impregnation methods. The effects of high surface loading were examined primarily under conditions of overcharge, since the movement of gas and electrolyte in the overcharging condition was typically where the greatest effects of non-uniform loading were found. The results indicate that significant changes in the capillary forces between cell components occur as the percentage of free volume in the stack filled by electrolyte becomes very high. These changes create large gradients in gas-filled space and oxygen concentrations near the boundary between the separator and the hydrogen electrode when the electrolyte fill is much greater than about 95 percent of the stack free volume. At lower electrolyte fill levels, these gaseous and electrolyte gradients become less extreme, and shift through the separator towards the nickel electrode. Similarly, flooding of areas in the gas screen cause higher concentrations of oxygen gas to approach the platinum/hydrogen electrode that is opposite the back side of the nickel electrode. These results illustrate the need for

  17. Lewis acid-water/alcohol complexes as hydrogen atom donors in radical reactions.

    PubMed

    Povie, Guillaume; Renaud, Philippe

    2013-01-01

    Water or low molecular weight alcohols are, due to their availability, low price and low toxicity ideal reagents for organic synthesis. Recently, it was reported that, despite the very strong BDE of the O-H bond, they can be used as hydrogen atom donors in place of expensive and/or toxic group 14 metal hydrides when boron and titanium(III) Lewis acids are present. This finding represents a considerable innovation and uncovers a new perspective on the paradigm of hydrogen atom transfers to radicals. We discuss here the influence of complex formation and other association processes on the efficacy of the hydrogen transfer step. A delicate balance between activation by complex formation and deactivation by further hydrogen bonding is operative.

  18. Simple thermodynamic model for the hydrogen phase diagram

    NASA Astrophysics Data System (ADS)

    Magdǎu, Ioan B.; Marqués, Miriam; Borgulya, Balint; Ackland, Graeme J.

    2017-03-01

    We describe a classical thermodynamic model that reproduces the main features of the solid hydrogen phase diagram. In particular, we show how the general structure types, which are found by electronic structure calculations and the quantum nature of the protons, can also be understood from a classical viewpoint. The model provides a picture not only of crystal structure, but also for the anomalous melting curve and insights into isotope effects, liquid metallisation, and infrared activity. The existence of a classical picture for this most quantum of condensed matter systems provides a surprising extension of the correspondence principle of quantum mechanics, in particular the equivalent effects of classical and quantum uncertainty.

  19. HYDROGEN-DEUTERIUM EXCHANGE IN PHOTOLYZED METHANE-WATER ICES

    SciTech Connect

    Weber, Amanda S.; Hodyss, Robert; Johnson, Paul V.; Willacy, Karen; Kanik, Isik

    2009-09-20

    Previous work has concluded that H-D exchange occurs readily in polycyclic aromatic hydrocarbons frozen in deuterated water (D{sub 2}O) irradiated with ultraviolet light. Here, we examine H-D exchange in methane-water ices following exposure to ultraviolet radiation and analyze the products formed as a result. We find that H-D exchange also occurs in methane-water ices by means of ultraviolet photolysis. Exchange proceeds through a radical mechanism that implies that almost all organic species will undergo significant H-D exchange with the matrix in water ices exposed to ultraviolet radiation. Given sufficient energetic processing of the ice, the H/D ratio of an ice matrix may be transferred to the organic species in the ice.

  20. Proton transfer dependence on hydrogen-bonding of solvent to the water wire: a theoretical study.

    PubMed

    Mai, Binh Khanh; Park, Kisoo; Duong, My Phu Thi; Kim, Yongho

    2013-01-10

    The mechanism and dynamics of double proton transfer dependence on hydrogen-bonding of solvent molecules to the bridging water in a water wire were studied by a direct ab initio dynamics approach with variational transition-state theory including multidimensional tunneling. Long-range proton transfers in solution and within enzymes may have very different mechanisms depending on the pK(a) values of participating groups and their electrostatic interactions with their environment. For end groups that have acidic or basic pK(a) values, proton transfers by the classical Grotthuss and "proton-hole" transfer mechanisms, respectively, are energetically favorable. This study shows that these processes are facilitated by hydrogen-bond accepting and donating solvent molecule interactions with the water wire in the transition state (TS), respectively. Tunneling also depends very much on the hydrogen bonding to the water wire. All molecules hydrogen bonded to the water wire, even if they raised and narrowed energy barriers, reduced the tunneling coefficients of double proton transfer, which was attributed to the increased effective mass of transferring protons near the TS. The theoretical HH/DD KIE, including tunneling, was in good agreement with experimental KIE values. These results suggest that the classical Grotthuss and proton-hole transfer mechanisms require quite different solvent (or protein) environments near the TS for the most efficient processes.

  1. Hydrogen bonding changes of internal water molecules in rhodopsin during metarhodopsin I and metarhodopsin II formation.

    PubMed Central

    Rath, P; Delange, F; Degrip, W J; Rothschild, K J

    1998-01-01

    Rhodopsin is a 7-helix, integral membrane protein found in the rod outer segments, which serves as the light receptor in vision. Light absorption by the retinylidene chromophore of rhodopsin triggers an 11-cis-->all-trans isomerization, followed by a series of protein conformational changes, which culminate in the binding and activation of the G-protein transducin by the metarhodopsin II (Meta II) intermediate. Fourier transform IR difference spectroscopy has been used to investigate the structural changes that water, as well as other OH- and NH-containing groups, undergo during the formation of the metarhodopsin I (Meta I) and Meta II intermediates. Bands associated with the OH stretch modes of water are identified by characteristic downshifts upon substitution of H2(18)O for H2O. Compared with earlier work, several negative bands associated with water molecules in unphotolysed rhodopsin were detected, which shift to lower frequencies upon formation of the Meta I and Meta II intermediates. These data indicate that at least one water molecule undergoes an increase in hydrogen bonding upon formation of the Meta I intermediate, while at least one other increases its hydrogen bonding during Meta II formation. Amino acid residue Asp-83, which undergoes a change in its hydrogen bonding during Meta II formation, does not appear to interact with any of the structurally active water molecules. Several NH and/or OH groups, which are inaccessible to hydrogen/deuterium exchange, also undergo alterations during Meta I and Meta II formation. PMID:9445403

  2. Small-scale, hydrogen-oxidizing-denitrifying bioreactor for treatment of nitrate-contaminated drinking water.

    PubMed

    Smith, Richard L; Buckwalter, Seanne P; Repert, Deborah A; Miller, Daniel N

    2005-05-01

    Nitrate removal by hydrogen-coupled denitrification was examined using flow-through, packed-bed bioreactors to develop a small-scale, cost effective system for treating nitrate-contaminated drinking-water supplies. Nitrate removal was accomplished using a Rhodocyclus sp., strain HOD 5, isolated from a sole-source drinking-water aquifer. The autotrophic capacity of the purple non-sulfur photosynthetic bacterium made it particularly adept for this purpose. Initial tests used a commercial bioreactor filled with glass beads and countercurrent, non-sterile flow of an autotrophic, air-saturated, growth medium and hydrogen gas. Complete removal of 2 mM nitrate was achieved for more than 300 days of operation at a 2-h retention time. A low-cost hydrogen generator/bioreactor system was then constructed from readily available materials as a water treatment approach using the Rhodocyclus strain. After initial tests with the growth medium, the constructed system was tested using nitrate-amended drinking water obtained from fractured granite and sandstone aquifers, with moderate and low TDS loads, respectively. Incomplete nitrate removal was evident in both water types, with high-nitrite concentrations in the bioreactor output, due to a pH increase, which inhibited nitrite reduction. This was rectified by including carbon dioxide in the hydrogen stream. Additionally, complete nitrate removal was accomplished with wastewater-impacted surface water, with a concurrent decrease in dissolved organic carbon. The results of this study using three chemically distinct water supplies demonstrate that hydrogen-coupled denitrification can serve as the basis for small-scale remediation and that pilot-scale testing might be the next logical step.

  3. Small-scale, hydrogen-oxidizing-denitrifying bioreactor for treatment of nitrate-contaminated drinking water

    USGS Publications Warehouse

    Smith, R.L.; Buckwalter, S.P.; Repert, D.A.; Miller, D.N.

    2005-01-01

    Nitrate removal by hydrogen-coupled denitrification was examined using flow-through, packed-bed bioreactors to develop a small-scale, cost effective system for treating nitrate-contaminated drinking-water supplies. Nitrate removal was accomplished using a Rhodocyclus sp., strain HOD 5, isolated from a sole-source drinking-water aquifer. The autotrophic capacity of the purple non-sulfur photosynthetic bacterium made it particularly adept for this purpose. Initial tests used a commercial bioreactor filled with glass beads and countercurrent, non-sterile flow of an autotrophic, air-saturated, growth medium and hydrogen gas. Complete removal of 2 mM nitrate was achieved for more than 300 days of operation at a 2-h retention time. A low-cost hydrogen generator/bioreactor system was then constructed from readily available materials as a water treatment approach using the Rhodocyclus strain. After initial tests with the growth medium, the constructed system was tested using nitrate-amended drinking water obtained from fractured granite and sandstone aquifers, with moderate and low TDS loads, respectively. Incomplete nitrate removal was evident in both water types, with high-nitrite concentrations in the bioreactor output, due to a pH increase, which inhibited nitrite reduction. This was rectified by including carbon dioxide in the hydrogen stream. Additionally, complete nitrate removal was accomplished with wastewater-impacted surface water, with a concurrent decrease in dissolved organic carbon. The results of this study using three chemically distinct water supplies demonstrate that hydrogen-coupled denitrification can serve as the basis for small-scale remediation and that pilot-scale testing might be the next logical step.

  4. A new perspective on hydrogen production by photosynthetic water-splitting

    SciTech Connect

    Lee, J.W.; Greenbaum, E.

    1996-05-01

    Present energy systems are heavily dependent on fossil fuels. This will eventually lead to the foreseeable depletion of fossil energy resources and, according to some reports, global climate changes due to the emission of carbon dioxide. In principle, hydrogen production by biophotolysis of water can be an ideal solar energy conversion system for sustainable development of human activities in harmony with the global environment. In photosynthetic hydrogen production research, there are currently two main efforts: (1) Direct photoevolution of hydrogen and oxygen by photosynthetic water splitting using the ferredoxin/hydrogenase pathway; (2) Dark hydrogen production by fermentation of organic reserves such as starch that are generated by photosynthesis during the light period. In this chapter, the advantages and challenges of the two approaches for hydrogen production will be discussed, in relation to a new opportunity brought by our recent discovery of a new photosynthetic water-splitting reaction which, potentially, has twice the energy efficiency of conventional watersplitting via the two light reaction Z-scheme of photosynthesis.

  5. Hydrogen Macro System Model User Guide, Version 1.2.1

    SciTech Connect

    Ruth, M.; Diakov, V.; Sa, T.; Goldsby, M.; Genung, K.; Hoseley, R.; Smith, A.; Yuzugullu, E.

    2009-07-01

    The Hydrogen Macro System Model (MSM) is a simulation tool that links existing and emerging hydrogen-related models to perform rapid, cross-cutting analysis. It allows analysis of the economics, primary energy-source requirements, and emissions of hydrogen production and delivery pathways.

  6. Macro-System Model for Hydrogen Energy Systems Analysis in Transportation: Preprint

    SciTech Connect

    Diakov, V.; Ruth, M.; Sa, T. J.; Goldsby, M. E.

    2012-06-01

    The Hydrogen Macro System Model (MSM) is a simulation tool that links existing and emerging hydrogen-related models to perform rapid, cross-cutting analysis. It allows analysis of the economics, primary energy-source requirements, and emissions of hydrogen production and delivery pathways.

  7. Constraining a halo model for cosmological neutral hydrogen

    NASA Astrophysics Data System (ADS)

    Padmanabhan, Hamsa; Refregier, Alexandre

    2017-02-01

    We describe a combined halo model to constrain the distribution of neutral hydrogen (H I) in the post-reionization universe. We combine constraints from the various probes of H I at different redshifts: the low-redshift 21-cm emission line surveys, intensity mapping experiments at intermediate redshifts, and the Damped Lyman-Alpha (DLA) observations at higher redshifts. We use a Markov Chain Monte Carlo approach to combine the observations and place constraints on the free parameters in the model. Our best-fitting model involves a relation between neutral hydrogen mass M_{H I} and halo mass M with a non-unit slope, and an upper and a lower cutoff. We find that the model fits all the observables but leads to an underprediction of the bias parameter of DLAs at z ˜ 2.3. We also find indications of a possible tension between the H I column density distribution and the mass function of H I-selected galaxies at z ˜ 0. We provide the central values of the parameters of the best-fitting model so derived. We also provide a fitting form for the derived evolution of the concentration parameter of H I in dark matter haloes, and discuss the implications for the redshift evolution of the H I-halo mass relation.

  8. Modeling the Spectra of Dense Hydrogen Plasmas: Beyond Occupation Probability

    NASA Astrophysics Data System (ADS)

    Gomez, T. A.; Montgomery, M. H.; Nagayama, T.; Kilcrease, D. P.; Winget, D. E.

    2017-03-01

    Accurately measuring the masses of white dwarf stars is crucial in many astrophysical contexts (e.g., asteroseismology and cosmochronology). These masses are most commonly determined by fitting a model atmosphere to an observed spectrum; this is known as the spectroscopic method. However, for cases in which more than one method may be employed, there are well known discrepancies between masses determined by the spectroscopic method and those determined by astrometric, dynamical, and/or gravitational-redshift methods. In an effort to resolve these discrepancies, we are developing a new model of hydrogen in a dense plasma that is a significant departure from previous models. Experiments at Sandia National Laboratories are currently underway to validate these new models, and we have begun modifications to incorporate these models into stellar-atmosphere codes.

  9. Development of Efficient Flowsheet and Transient Modeling for Nuclear Heat Coupled Sulfur Iodine Cyclefor Hydrogen Production

    SciTech Connect

    Shripad T. Revankar; Nicholas R. Brown; Cheikhou Kane; Seungmin Oh

    2010-05-01

    The realization of the hydrogen as an energy carrier for future power sources relies on a practical method of producing hydrogen in large scale with no emission of green house gases. Hydrogen is an energy carrier which can be produced by a thermochemical water splitting process. The Sulfur-Iodine (SI) process is an example of a water splitting method using iodine and sulfur as recycling agents.

  10. Exploring the activity of a novel Au/TiC(001) model catalyst towards CO and CO2 hydrogenation

    DOE PAGES

    Asara, Gian Giacomo; Ricart, Josep M.; Rodriguez, Jose A.; ...

    2015-02-02

    Small metallic nanoparticles supported on transition metal carbides exhibit an unexpected high activity towards a series of chemical reactions. In particular, the Au/TiC system has proven to be an excellent catalyst for SO2 decomposition, thiophene hydrodesulfurization, O2 and H2 dissociation and the water gas shift reaction. Recent studies have shown that Au/TiC is a very good catalyst for the reverse water–gas shift (CO2 + H2 → CO + H2O) and CO2 hydrogenation to methanol. The present work further expands the range of applicability of this novel type of systems by exploring the catalytic activity of Au/TiC towards the hydrogenation ofmore » CO or CO2 with periodic density functional theory (DFT) calculations on model systems. Hydrogen dissociates easily on Au/TiC but direct hydrogenation of CO to methanol is hindered by very high activation barriers implying that, on this model catalyst, methanol production from CO2 involves the hydrogenation of a HOCO-like intermediate. Thus, when dealing with mixtures of syngas (CO/CO2/H2/H2O), CO could be transformed into CO2 through the water gas shift reaction with subsequent hydrogenation of CO2 to methanol.« less

  11. Hydrogen-Bonding-Induced Fluorescence: Water-Soluble and Polarity-Independent Solvatochromic Fluorophores.

    PubMed

    Okada, Yohei; Sugai, Masae; Chiba, Kazuhiro

    2016-11-18

    Fluorophores with emission wavelengths that shift depending on their hydrogen-bonding microenvironment in water would be fascinating tools for the study of biological events. Herein we describe the design and synthesis of a series of water-soluble solvatochromic fluorophores, 2,5-bis(oligoethylene glycol)oxybenzaldehydes (8-11) and 2,5-bis(oligoethylene glycol)oxy-1,4-dibenzaldehydes (14-17), based on a push-pull strategy. Unlike typical examples in this class of fluorophores, the fluorescence properties of these compounds are independent of solvent polarity and become fluorescent upon intermolecular hydrogen-bonding, exhibiting high quantum yields (up to ϕ = 0.55) and large Stokes shifts (up to 134 nm). Furthermore, their emission wavelengths change depending on their hydrogen-bonding environment. The described fluorophores provide a starting point for unprecedented applications in the fields of chemical biology and medicinal chemistry.

  12. Control of Electrons’ Spin Eliminates Hydrogen Peroxide Formation During Water Splitting

    PubMed Central

    2017-01-01

    The production of hydrogen through water splitting in a photoelectrochemical cell suffers from an overpotential that limits the efficiencies. In addition, hydrogen-peroxide formation is identified as a competing process affecting the oxidative stability of photoelectrodes. We impose spin-selectivity by coating the anode with chiral organic semiconductors from helically aggregated dyes as sensitizers; Zn-porphyrins and triarylamines. Hydrogen peroxide formation is dramatically suppressed, while the overall current through the cell, correlating with the water splitting process, is enhanced. Evidence for a strong spin-selection in the chiral semiconductors is presented by magnetic conducting (mc-)AFM measurements, in which chiral and achiral Zn-porphyrins are compared. These findings contribute to our understanding of the underlying mechanism of spin selectivity in multiple electron-transfer reactions and pave the way toward better chiral dye-sensitized photoelectrochemical cells. PMID:28132505

  13. [Continuous Generation of Hydrogen Peroxide in Water Containing Very Low Concentrations of Unsymmetrical Dimethylhydrazine].

    PubMed

    Bruskov, V I; Yaguzhinsky, L S; Masalimov, Z K; Chernikov, A V; Emelyanenko, V I; Gudkov, S V

    2015-01-01

    Continuous generation of hydrogen peroxide catalyzed by low concentrations of 1,1-dimethylhydrazine (heptyl)--a rocket fuel component--in air saturated water was shown by the method of enhanced chemiluminescence in the system of luminol-p-iodophenol-peroxidase. The concentration dependence and the influence of heat and light on the formation of hydrogen peroxide in the water under the influence of dimethylhydrazine at concentrations considerably lower than maximum allowable concentrations were studied, and the physical-chemical mechanism of this process was considered. It is supposed that dimethylhydrazine at ultra-low concentrations is associated with air nanobubbles and represents a long-lived complex performing catalysis of hydrogen peroxide formation under the influence of heat and light. We put forward the new concept of.toxicity of dimethylhydrazine at very low concentrations due to violation of homeostasis of reactive oxygen species formation in aqueous solutions entering the body of humans and animals.

  14. Water-Soluble Iridium-NHC-Phosphine Complexes as Catalysts for Chemical Hydrogen Batteries Based on Formate.

    PubMed

    Horváth, Henrietta; Papp, Gábor; Szabolcsi, Roland; Kathó, Ágnes; Joó, Ferenc

    2015-09-21

    Molecular hydrogen, obtained by water electrolysis or photocatalytic water splitting, can be used to store energy obtained from intermittent sources such as wind and solar power. The storage and safe transportation of H2 , however, is an open and central question in such a hydrogen economy. Easy-to-synthesize, water-soluble iridium-N-heterocyclic carbene-phosphine (Ir(I) -NHC-phosphine) catalysts show unprecedented high catalytic activity in dehydrogenation of aqueous sodium formate. Fast reversible generation and storage of hydrogen can be achieved with these catalysts by a simple decrease or increase in the hydrogen pressure, respectively.

  15. Hydrogen production from water using copper and barium hydroxide

    DOEpatents

    Bamberger, Carlos E.; Richardson, deceased, Donald M.

    1979-01-01

    A process for producing hydrogen comprises the step of reacting metallic Cu with Ba(OH).sub.2 in the presence of steam to produce hydrogen and BaCu.sub.2 O.sub.2. The BaCu.sub.2 O.sub.2 is reacted with H.sub.2 O to form Cu.sub.2 O and a Ba(OH).sub.2 product for recycle to the initial reaction step. Cu can be obtained from the Cu.sub.2 O product by several methods. In one embodiment the Cu.sub.2 O is reacted with HF solution to provide CuF.sub.2 and Cu. The CuF.sub.2 is reacted with H.sub.2 O to provide CuO and HF. CuO is decomposed to Cu.sub.2 O and O.sub.2. The HF, Cu and Cu.sub.2 O are recycled. In another embodiment the Cu.sub.2 O is reacted with aqueous H.sub.2 SO.sub.4 solution to provide CuSO.sub.4 solution and Cu. The CuSO.sub.4 is decomposed to CuO and SO.sub.3. The CuO is decomposed to form Cu.sub.2 O and O.sub.2. The SO.sub.3 is dissolved to form H.sub.2 SO.sub.4. H.sub.2 SO.sub.4, Cu and Cu.sub.2 O are recycled. In another embodiment Cu.sub.2 O is decomposed electrolytically to Cu and O.sub.2. In another aspect of the invention, Cu is recovered from CuO by the steps of decomposing CuO to Cu.sub.2 O and O.sub.2, reacting the Cu.sub.2 O with aqueous HF solution to produce Cu and CuF.sub.2, reacting the CuF.sub.2 with H.sub.2 O to form CuO and HF, and recycling the CuO and HF to previous reaction steps.

  16. Kinetics Study of Solid Ammonia Borane Hydrogen Release – Modeling and Experimental Validation for Chemical Hydrogen Storage

    SciTech Connect

    Choi, Yong-Joon; Ronnebro, Ewa; Rassat, Scot D.; Karkamkar, Abhijeet J.; Maupin, Gary D.; Holladay, Jamelyn D.; Simmons, Kevin L.; Brooks, Kriston P.

    2014-02-24

    Ammonia borane (AB), NH3BH3, is a promising material for chemical hydrogen storage with 19.6 wt% gravimetric hydrogen capacity of which 16.2 wt% hydrogen can be utilized below 200°C. We have investigated the kinetics of hydrogen release from AB and from an AB-methyl cellulose (AB/MC) composite at temperatures of 160-300°C using both experiments and modeling. The purpose of our study was to show safe hydrogen release without thermal runaway effects and to validate system model kinetics. AB/MC released hydrogen at ~20°C lower than neat AB and at a rate that is two times faster. Based on the experimental results, the kinetics equations were revised to better represent the growth and nucleation process during decomposition of AB. We explored two different reactor concepts; Auger and fixed bed. The current Auger reactor concept turned out to not be appropriate, however, we demonstrated safe self-propagation of the hydrogen release reaction of solid AB/MC in a fixed bed reactor.

  17. Modeling Water Filtration

    ERIC Educational Resources Information Center

    Parks, Melissa

    2014-01-01

    Model-eliciting activities (MEAs) are not new to those in engineering or mathematics, but they were new to Melissa Parks. Model-eliciting activities are simulated real-world problems that integrate engineering, mathematical, and scientific thinking as students find solutions for specific scenarios. During this process, students generate solutions…

  18. Modeled ground water age distributions

    USGS Publications Warehouse

    Woolfenden, Linda R.; Ginn, Timothy R.

    2009-01-01

    The age of ground water in any given sample is a distributed quantity representing distributed provenance (in space and time) of the water. Conventional analysis of tracers such as unstable isotopes or anthropogenic chemical species gives discrete or binary measures of the presence of water of a given age. Modeled ground water age distributions provide a continuous measure of contributions from different recharge sources to aquifers. A numerical solution of the ground water age equation of Ginn (1999) was tested both on a hypothetical simplified one-dimensional flow system and under real world conditions. Results from these simulations yield the first continuous distributions of ground water age using this model. Complete age distributions as a function of one and two space dimensions were obtained from both numerical experiments. Simulations in the test problem produced mean ages that were consistent with the expected value at the end of the model domain for all dispersivity values tested, although the mean ages for the two highest dispersivity values deviated slightly from the expected value. Mean ages in the dispersionless case also were consistent with the expected mean ages throughout the physical model domain. Simulations under real world conditions for three dispersivity values resulted in decreasing mean age with increasing dispersivity. This likely is a consequence of an edge effect. However, simulations for all three dispersivity values tested were mass balanced and stable demonstrating that the solution of the ground water age equation can provide estimates of water mass density distributions over age under real world conditions.

  19. Modeled ground water age distributions.

    PubMed

    Woolfenden, Linda R; Ginn, Timothy R

    2009-01-01

    The age of ground water in any given sample is a distributed quantity representing distributed provenance (in space and time) of the water. Conventional analysis of tracers such as unstable isotopes or anthropogenic chemical species gives discrete or binary measures of the presence of water of a given age. Modeled ground water age distributions provide a continuous measure of contributions from different recharge sources to aquifers. A numerical solution of the ground water age equation of Ginn (1999) was tested both on a hypothetical simplified one-dimensional flow system and under real world conditions. Results from these simulations yield the first continuous distributions of ground water age using this model. Complete age distributions as a function of one and two space dimensions were obtained from both numerical experiments. Simulations in the test problem produced mean ages that were consistent with the expected value at the end of the model domain for all dispersivity values tested, although the mean ages for the two highest dispersivity values deviated slightly from the expected value. Mean ages in the dispersionless case also were consistent with the expected mean ages throughout the physical model domain. Simulations under real world conditions for three dispersivity values resulted in decreasing mean age with increasing dispersivity. This likely is a consequence of an edge effect. However, simulations for all three dispersivity values tested were mass balanced and stable demonstrating that the solution of the ground water age equation can provide estimates of water mass density distributions over age under real world conditions.

  20. Permeability of Molecular Hydrogen and Water Vapor Through Butyl Rubber at Ambient Temperature

    SciTech Connect

    Zeigler, K.

    1992-04-09

    The preparation of the Safety Analysis Report for the 233-H Replacement Tritium Facility (RTF) requires permeation constants of hydrogen isotopes through butyl rubber, to estimate possible worker exposure given a certain level of tritium in the confinement gloveboxes. Literature values of the permeability constants for hydrogen isotopes and water vapor through butyl rubber at ambient temperature (22-25 C) have been converted to common units and are tabulated (Tables I and II). Permeation rates of tritiated species are the same as that of protium species, within experimental error. Thus, molecular protium and normal water vapor data serve to estimate tritium permeation rates. Because of vendor to vendor variability of permeability, especially of water vapor, vendor measurements of water vapor permeability should continue to be used to estimate permeation in SRS processes.

  1. Permeability of Molecular Hydrogen and Water Vapor Through Butyl Rubber at Ambient Temperature

    SciTech Connect

    Clark, Elliot A.

    1992-04-09

    The preparation of the Safety Analysis Report for the 233-H Replacement Tritium Facility (RTF) requires permeation constants of hydrogen isotopes through butyl rubber, to estimate possible worker exposure given a certain level of tritium in the confinement gloveboxes. Literature values of the permeability constants for hydrogen isotopes and water vapor through butyl rubber at ambient temperature (22-25 C) have been converted to common units and are tabulated (Tables I and II). Permeation rates of tritiated species are the same as that of protium species, within experimental error. Thus, molecular protium and normal water vapor data serve to estimate tritium permeation rates. Because of vendor-to-vendor variability of permeability, especially of water vapor, vendor measurements of water vapor permeability should continue to be used to estimate permeation in SRS processes.

  2. Estimation of Solvation Entropy and Enthalpy via Analysis of Water Oxygen-Hydrogen Correlations.

    PubMed

    Velez-Vega, Camilo; McKay, Daniel J J; Kurtzman, Tom; Aravamuthan, Vibhas; Pearlstein, Robert A; Duca, José S

    2015-11-10

    A statistical-mechanical framework for estimation of solvation entropies and enthalpies is proposed, which is based on the analysis of water as a mixture of correlated water oxygens and water hydrogens. Entropic contributions of increasing order are cast in terms of a Mutual Information Expansion that is evaluated to pairwise interactions. In turn, the enthalpy is computed directly from a distance-based hydrogen bonding energy algorithm. The resulting expressions are employed for grid-based analyses of Molecular Dynamics simulations. In this first assessment of the methodology, we obtained global estimates of the excess entropy and enthalpy of water that are in good agreement with experiment and examined the method's ability to enable detailed elucidation of solvation thermodynamic structures, which can provide valuable knowledge toward molecular design.

  3. A molecular molybdenum-oxo catalyst for generating hydrogen from water.

    PubMed

    Karunadasa, Hemamala I; Chang, Christopher J; Long, Jeffrey R

    2010-04-29

    A growing awareness of issues related to anthropogenic climate change and an increase in global energy demand have made the search for viable carbon-neutral sources of renewable energy one of the most important challenges in science today. The chemical community is therefore seeking efficient and inexpensive catalysts that can produce large quantities of hydrogen gas from water. Here we identify a molybdenum-oxo complex that can catalytically generate gaseous hydrogen either from water at neutral pH or from sea water. This work shows that high-valency metal-oxo species can be used to create reduction catalysts that are robust and functional in water, a concept that has broad implications for the design of 'green' and sustainable chemistry cycles.

  4. Modeling the hydrothermal circulation and the hydrogen production at the Rainbow site with Cast3M

    NASA Astrophysics Data System (ADS)

    Perez, F.; Mügler, C.; Charlou, J.; Jean-baptiste, P.

    2012-12-01

    On the Mid-Atlantic Ridge, the Rainbow venting site is described as an ultramafic-hosted active hydrothermal site and releases high fluxes of methane and hydrogen [1, 2]. This behavior has first been interpreted as the result of serpentinization processes. But geochemical reactions involving olivine and plagioclase assemblages, and leading to chlorite, tremolite, talc and magnetite assemblages, could contribute to the observed characteristics of the exiting fluid [2]. The predominance of one of these geochemical reactions or their coexistence strongly depend on the hydrothermal fluid circulation. We developed and validated a 2D/3D numerical model using a Finite Volume method to simulate heat driven fluid flows in the framework of the Cast3M code [3, 4]. We also developed a numerical model for hydrogen production and transport that is based on experimental studies of the serpentinization processes [5-6]. This geochemical model takes into account the exothermic and water-consuming behavior of the serpentinization reaction and it can be coupled to our thermo-hydrogeological model. Our simulations provide temperatures, mass fluxes and venting surface areas very close to those estimated in-situ [7]. We showed that a single-path model [8] was necessary to simulate high values such as the in-situ measured temperatures and estimated water mass fluxes of the Rainbow site [7]. This single-path model will be used to model the production and transport of hydrogen at the Rainbow hydrothermal site. References [1]Charlou et al. (2010) AGU Monograph series. [2]Seyfried et al. (2011) Geochim. Cosmochim. Acta 75, 1574-1593. [3]http://www-cast3m.cea.fr. [4]Martin & Fyfe (1970) Chem. Geol. 6, 185-202. [5] Marcaillou et al. (2011) Earth and Planet. Sci. Lett. 303, 281-290. [6]Malvoisin et al. (2012) JGR, 117, B01104. [7]Perez et al. (2012) submited to Computational Geosciences. [8]Lowell & Germanovich (2004) AGU, Washington DC, USA.

  5. BUBBLE STRIPPING TO DETERMINE HYDROGEN CONCENTRATIONS IN GROUND WATER: A PRACTICAL APPLICATION OF HENRY'S LAW

    EPA Science Inventory

    The Bubble Stripping Method is a chemical testing method that operates on the principle of Henry's Law. It is useful for determining concentrations of hydrogen in well water, and it is capable of detecting concentrations on the order of nanomoles per liter. The method provides ...

  6. Hydrogen peroxide treatments for channel catfish eggs infected with water molds

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fungi, or water molds Saprolegnia spp., on channel catfish Ictalurus punctatus eggs can lower fry production. This requires the producer to spawn more catfish or face fingerling shortages. Few treatments have been tested against channel catfish eggs infested with an identified fungus. Hydrogen pe...

  7. Storm Water Management Model (SWMM)

    EPA Pesticide Factsheets

    EPA's Storm Water Management Model (SWMM) is used throughout the world for planning, analysis and design related to stormwater runoff, combined and sanitary sewers, and other drainage systems in urban areas.

  8. Hydrogen production from high-moisture content biomass in supercritical water

    SciTech Connect

    Antal, M.J. Jr.; Matsumura, Y.; Onuma, M.T.

    1995-09-01

    Wet biomass (water hyacinth, banana trees, cattails, green algae, kelp, etc.) grows rapidly and abundantly around the world. However, wet biomass is not regarded as a promising feedstock for conventional thermochemical conversion processes because the cost of drying the material is too high. Prior work has shown that low concentrations of glucose (a model compound for whole biomass) and various wet biomass species (water hyacinth, algae) can be completely gasified in supercritical water at 600{degrees}C and 34.5 MPa after a 30 s residence time. But higher concentrations of glucose evidenced incomplete conversion. For this reason, flow reactors were fabricated which could accommodate packed beds of catalyst, and studies were initiated of the steam reforming (gasification) reactions in the presence of various candidate heterogeneous catalysts. The goal is to identify active catalysts for steam reforming biomass slurries in supercritical water. Soon after tests began, a suitable class of carbon-based catalysts was discovered. These catalysts effect complete (>99%) conversion of high-concentration glucose (up to 22% by weight) to a hydrogen-rich synthesis gas. High space velocities are realized [>20 (g/hr)/g], and the catalyst is stable over a period of several hours. The carbon catalyst is not expensive, and exists in a wide variety of forms and compositions. After this discovery, work has focused on four interrelated tasks: (1) tests to identify the most active form and composition of the catalyst; (2) tests employing the preferred catalyst to study the effect of feedstock composition on carbon conversion and gas composition; (3) studies of catalyst deactivation and subsequent reactivation, including the in-house synthesis of bifunctional catalysts which incorporate promoters and stabilizers; and (4) the design and fabrication of a larger, new reactor with a slurry feeder intended to handle high-concentration, wet biomass feeds.

  9. Hydrogen sulphide release to surface waters at the Precambrian/Cambrian boundary.

    PubMed

    Wille, Martin; Nägler, Thomas F; Lehmann, Bernd; Schröder, Stefan; Kramers, Jan D

    2008-06-05

    Animal-like multicellular fossils appeared towards the end of the Precambrian, followed by a rapid increase in the abundance and diversity of fossils during the Early Cambrian period, an event also known as the 'Cambrian explosion'. Changes in the environmental conditions at the Precambrian/Cambrian transition (about 542 Myr ago) have been suggested as a possible explanation for this event, but are still a matter of debate. Here we report molybdenum isotope signatures of black shales from two stratigraphically correlated sample sets with a depositional age of around 542 Myr. We find a transient molybdenum isotope signal immediately after the Precambrian/Cambrian transition. Using a box model of the oceanic molybdenum cycle, we find that intense upwelling of hydrogen sulphide-rich deep ocean water best explains the observed Early Cambrian molybdenum isotope signal. Our findings suggest that the Early Cambrian animal radiation may have been triggered by a major change in ocean circulation, terminating a long period during which the Proterozoic ocean was stratified, with sulphidic deep water.

  10. HIERARCHICAL METHODOLOGY FOR MODELING HYDROGEN STORAGE SYSTEMS. PART I: SCOPING MODELS

    SciTech Connect

    Hardy, B; Donald L. Anton, D

    2008-12-22

    Detailed models for hydrogen storage systems provide essential design information about flow and temperature distributions, as well as, the utilization of a hydrogen storage media. However, before constructing a detailed model it is necessary to know the geometry and length scales of the system, along with its heat transfer requirements, which depend on the limiting reaction kinetics. More fundamentally, before committing significant time and resources to the development of a detailed model, it is necessary to know whether a conceptual storage system design is viable. For this reason, a hierarchical system of models progressing from scoping models to detailed analyses was developed. This paper, which discusses the scoping models, is the first in a two part series that presents a collection of hierarchical models for the design and evaluation of hydrogen storage systems.

  11. An analysis of hydrogen production via closed-cycle schemes. [thermochemical processings from water

    NASA Technical Reports Server (NTRS)

    Chao, R. E.; Cox, K. E.

    1975-01-01

    A thermodynamic analysis and state-of-the-art review of three basic schemes for production of hydrogen from water: electrolysis, thermal water-splitting, and multi-step thermochemical closed cycles is presented. Criteria for work-saving thermochemical closed-cycle processes are established, and several schemes are reviewed in light of such criteria. An economic analysis is also presented in the context of energy costs.

  12. Characteristics of hydrogen ion transport in urinary bladder of water turtle.

    PubMed

    Steinmetz, P R

    1967-10-01

    The mechanism of acidification by the urinary bladder of the water turtle was studied in an in vitro system which permitted control and measurement of electrical and concentration driving forces. The rate of hydrogen ion secretion was measured by means of a pH stat technique in the absence of exogenous carbon dioxide and bicarbonate. Transport of hydrogen ion into the solution bathing the mucosal surface of the bladder was associated with the appearance of alkali in the serosal compartment. The mean rate of hydrogen ion secretion in the absence of electrical and concentration gradients across the bladder was 0.96 mumole/hr. The secretion rate was only slightly greater in the presence of the spontaneous potential difference. The maximal hydrogen ion gradient that could be generated by the bladder was 3.33 pH units in the presence of the spontaneous voltage and 3.02 pH units in the short-circuited state. Hydrogen ion secretion was markedly reduced by acetazolamide and anaerobiosis, which indicated that under our experimental conditions acidification depended on the production and enzymatic hydration of metabolic carbon dioxide. On the basis of the stoichiometry of the pH changes across the membrane under different conditions, it is suggested that the active transport mechanism for hydrogen ion is located near the mucosal surface of the epithelial cell and that the alkali generated in back of the pump moves passively into the serosal fluid along an electrochemical gradient.

  13. Nanocatalysts for Solar Water Splitting and a Perspective on Hydrogen Economy.

    PubMed

    Grewe, Tobias; Meggouh, Mariem; Tüysüz, Harun

    2016-01-01

    In this review article, nanocatalysts for solar hydrogen production are the focus of discussion as they can contribute to the development of sustainable hydrogen production in order to meet future energy demands. Achieving this task is subject of scientific aspirations in the field of photo- and photoelectrocatalysis for solar water splitting where systems of single catalysts or tandem configurations are being investigated. In search of a suitable catalyst, a number of crucial parameters are laid out which need to be considered for material design, in particular for nanostructured materials that provide exceptional physical and chemical properties in comparison to their bulk counterparts. Apart from synthetic approaches for nanocatalysts, key parameters and properties of nanostructured photocatalysts such as light absorption, charge carrier generation, charge transport, separation and recombination, and other events that affect nanoscale catalysts are discussed. To provide a deeper understanding of these key parameters and properties, their contribution towards existing catalyst systems is evaluated for photo- and photoelectrocatalytic solar hydrogen evolution. Finally, an insight into hydrogen production processes is given, stressing the current development of sustainable hydrogen sources and presenting a perspective towards a hydrogen-based economy.

  14. Electrochemically reduced water exerts superior reactive oxygen species scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water

    PubMed Central

    Hamasaki, Takeki; Harada, Gakuro; Nakamichi, Noboru; Kabayama, Shigeru; Teruya, Kiichiro; Fugetsu, Bunshi; Gong, Wei; Sakata, Ichiro; Shirahata, Sanetaka

    2017-01-01

    Electrochemically reduced water (ERW) is produced near a cathode during electrolysis and exhibits an alkaline pH, contains richly dissolved hydrogen, and contains a small amount of platinum nanoparticles. ERW has reactive oxygen species (ROS)-scavenging activity and recent studies demonstrated that hydrogen-dissolved water exhibits ROS-scavenging activity. Thus, the antioxidative capacity of ERW is postulated to be dependent on the presence of hydrogen levels; however, there is no report verifying the role of dissolved hydrogen in ERW. In this report, we clarify whether the responsive factor for antioxidative activity in ERW is dissolved hydrogen. The intracellular ROS scavenging activity of ERW and hydrogen-dissolved water was tested by both fluorescent stain method and immuno spin trapping assay. We confirm that ERW possessed electrolysis intensity-dependent intracellular ROS-scavenging activity, and ERW exerts significantly superior ROS-scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water. ERW retained its ROS-scavenging activity after removal of dissolved hydrogen, but lost its activity when autoclaved. An oxygen radical absorbance capacity assay, the 2,2-diphenyl-1-picrylhydrazyl assay and chemiluminescence assay could not detect radical-scavenging activity in both ERW and hydrogen-dissolved water. These results indicate that ERW contains electrolysis-dependent hydrogen and an additional antioxidative factor predicted to be platinum nanoparticles. PMID:28182635

  15. Electrochemically reduced water exerts superior reactive oxygen species scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water.

    PubMed

    Hamasaki, Takeki; Harada, Gakuro; Nakamichi, Noboru; Kabayama, Shigeru; Teruya, Kiichiro; Fugetsu, Bunshi; Gong, Wei; Sakata, Ichiro; Shirahata, Sanetaka

    2017-01-01

    Electrochemically reduced water (ERW) is produced near a cathode during electrolysis and exhibits an alkaline pH, contains richly dissolved hydrogen, and contains a small amount of platinum nanoparticles. ERW has reactive oxygen species (ROS)-scavenging activity and recent studies demonstrated that hydrogen-dissolved water exhibits ROS-scavenging activity. Thus, the antioxidative capacity of ERW is postulated to be dependent on the presence of hydrogen levels; however, there is no report verifying the role of dissolved hydrogen in ERW. In this report, we clarify whether the responsive factor for antioxidative activity in ERW is dissolved hydrogen. The intracellular ROS scavenging activity of ERW and hydrogen-dissolved water was tested by both fluorescent stain method and immuno spin trapping assay. We confirm that ERW possessed electrolysis intensity-dependent intracellular ROS-scavenging activity, and ERW exerts significantly superior ROS-scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water. ERW retained its ROS-scavenging activity after removal of dissolved hydrogen, but lost its activity when autoclaved. An oxygen radical absorbance capacity assay, the 2,2-diphenyl-1-picrylhydrazyl assay and chemiluminescence assay could not detect radical-scavenging activity in both ERW and hydrogen-dissolved water. These results indicate that ERW contains electrolysis-dependent hydrogen and an additional antioxidative factor predicted to be platinum nanoparticles.

  16. Modulating memristive performance of hexagonal WO3 nanowire by water-oxidized hydrogen ion implantation

    PubMed Central

    Zhou, Yong; Peng, Yuehua; Yin, Yanling; Zhou, Fang; Liu, Chang; Ling, Jing; Lei, Le; Zhou, Weichang; Tang, Dongsheng

    2016-01-01

    In a two-terminal Au/hexagonal WO3 nanowire/Au device, ions drifting or carriers self-trapping under external electrical field will modulate the Schottky barriers between the nanowire and electrodes, and then result in memristive effect. When there are water molecules adsorbed on the surface of WO3 nanowire, hydrogen ions will generate near the positively-charged electrode and transport in the condensed water film, which will enhance the memristive performance characterized by analogic resistive switching remarkably. When the bias voltage is swept repeatedly under high relative humidity level, hydrogen ions will accumulate on the surface and then implant into the lattice of the WO3 nanowire, which leads to a transition from semiconducting WO3 nanowire to metallic HxWO3 nanowire. This insulator-metal transition can be realized more easily after enough electron-hole pairs being excited by laser illumination. The concentration of hydrogen ions in HxWO3 nanowire will decrease when the device is exposed to oxygen atmosphere or the bias voltage is swept in atmosphere with low relative humidity. By modulating the concentration of hydrogen ions, conductive hydrogen tungsten bronze filament might form or rupture near electrodes when the polarity of applied voltage changes, which will endow the device with memristive performance characterized by digital resistive switching. PMID:27600368

  17. Modulating memristive performance of hexagonal WO3 nanowire by water-oxidized hydrogen ion implantation.

    PubMed

    Zhou, Yong; Peng, Yuehua; Yin, Yanling; Zhou, Fang; Liu, Chang; Ling, Jing; Lei, Le; Zhou, Weichang; Tang, Dongsheng

    2016-09-07

    In a two-terminal Au/hexagonal WO3 nanowire/Au device, ions drifting or carriers self-trapping under external electrical field will modulate the Schottky barriers between the nanowire and electrodes, and then result in memristive effect. When there are water molecules adsorbed on the surface of WO3 nanowire, hydrogen ions will generate near the positively-charged electrode and transport in the condensed water film, which will enhance the memristive performance characterized by analogic resistive switching remarkably. When the bias voltage is swept repeatedly under high relative humidity level, hydrogen ions will accumulate on the surface and then implant into the lattice of the WO3 nanowire, which leads to a transition from semiconducting WO3 nanowire to metallic HxWO3 nanowire. This insulator-metal transition can be realized more easily after enough electron-hole pairs being excited by laser illumination. The concentration of hydrogen ions in HxWO3 nanowire will decrease when the device is exposed to oxygen atmosphere or the bias voltage is swept in atmosphere with low relative humidity. By modulating the concentration of hydrogen ions, conductive hydrogen tungsten bronze filament might form or rupture near electrodes when the polarity of applied voltage changes, which will endow the device with memristive performance characterized by digital resistive switching.

  18. Modulating memristive performance of hexagonal WO3 nanowire by water-oxidized hydrogen ion implantation

    NASA Astrophysics Data System (ADS)

    Zhou, Yong; Peng, Yuehua; Yin, Yanling; Zhou, Fang; Liu, Chang; Ling, Jing; Lei, Le; Zhou, Weichang; Tang, Dongsheng

    2016-09-01

    In a two-terminal Au/hexagonal WO3 nanowire/Au device, ions drifting or carriers self-trapping under external electrical field will modulate the Schottky barriers between the nanowire and electrodes, and then result in memristive effect. When there are water molecules adsorbed on the surface of WO3 nanowire, hydrogen ions will generate near the positively-charged electrode and transport in the condensed water film, which will enhance the memristive performance characterized by analogic resistive switching remarkably. When the bias voltage is swept repeatedly under high relative humidity level, hydrogen ions will accumulate on the surface and then implant into the lattice of the WO3 nanowire, which leads to a transition from semiconducting WO3 nanowire to metallic HxWO3 nanowire. This insulator-metal transition can be realized more easily after enough electron-hole pairs being excited by laser illumination. The concentration of hydrogen ions in HxWO3 nanowire will decrease when the device is exposed to oxygen atmosphere or the bias voltage is swept in atmosphere with low relative humidity. By modulating the concentration of hydrogen ions, conductive hydrogen tungsten bronze filament might form or rupture near electrodes when the polarity of applied voltage changes, which will endow the device with memristive performance characterized by digital resistive switching.

  19. The Role of Water in the Storage of Hydrogen in Metals

    NASA Technical Reports Server (NTRS)

    Hampton, Michael D.; Lomness, Janice K.; Giannuzzi, Lucille A.

    2001-01-01

    One major problem with the use of hydrogen is safe and efficient storage. In the pure form, bulky and heavy containers are required greatly reducing the efficiency of its use. Safety is also a great concern. Storage of hydrogen in the form of a metal hydride offers distinct advantages both in terms of volumetric efficiency and in terms of safety. As a result, an enormous amount of research is currently being done on metal-hydrogen systems. Practical application of these systems to storage of hydrogen can only occur when they are very well understood. In this paper, the preliminary results of a study of the surfaces of magnesium nickel alloys will be presented. Alloys that have been rendered totally unreactive with hydrogen as well as those that have been activated with liquid water and with water vapor were studied. Data obtained from XPS (X-ray Photoelectron Spectrometer) analysis, with samples held in vacuum for the shortest possible time to minimize the hydroxide degradation will be presented. Furthermore, TEM data on samples prepared in a new way that largely protects the surface from the high vacuum will be discussed.

  20. Geospatial analysis and seasonal changes in water-equivalent hydrogen in eastern equatorial Mars

    NASA Astrophysics Data System (ADS)

    Clevy, June Renee

    2014-10-01

    This dissertation describes the relationship between hydrogen abundance, as measured through epithermal neutron counts, and the topographic, geologic, and surficial features in the equatorial region of eastern Mars. In Chapter 1, I present an alternative method for resampling the epithermal neutron count data collected by the neutron spectrometer from Mars Odyssey's Gamma Ray Spectrometer suite. Chapter 2 provides a seasonal break down of mean and median epithermal neutron count rates and examines areas of static, seasonal, and episodic hydrogen enrichment. Armed with new maps of mean epithermal neutron count rates and derivative maps of weight percent water equivalent hydrogen, I examine the spatial relationships between equatorial hydrogen concentrations and satellite-measured surface properties such as elevation, its derivatives slope and aspect, albedo, dust cover, geologic units, and valley networks in Chapter 3. The chapters in this dissertation represent a workflow from the development of the Water Equivalent Hydrogen dataset used in this research (Chapter 1), to an analysis of seasonal changes in the hydrogen signal (Chapter 2), and the relationships between this data and measurements of elevation, crustal thickness, surface composition, and geomorphology (Chapter 3). These investigations were made possible by the application of terrestrial geographic information science to planetary geology through Geographic Information Systems (GIS). Neighborhood processing allowed me to refine the spatial resolution of the epithermal neutron count in the first chapter. Class frequency tables permitted the identification of changes over time in chapter two and facilitated the identification of high and low variability areas. Finally, a quantitative process known as the Location Quotient, which builds upon frequency tables, was applied to identify more frequent than expected combinations of hydrogen abundance and other martian data (e.g., elevation) for the purpose of

  1. Hydrogen isotopic composition of the water in CR chondrites

    NASA Astrophysics Data System (ADS)

    Bonal, L.; Alexander, C. M. O.'D.; Huss, G. R.; Nagashima, K.; Quirico, E.; Beck, P.

    2013-04-01

    The thermal and aqueous alteration experienced by QUE 99177, MET 00426, EET 92042, GRA 95229, Renazzo and Al Rais CR chondrites was assessed through multi-technique characterization of their the carbonaceous matter and hydrated mineral phases. Each of the chondrites escaped long duration thermal metamorphism as reflected by the low structural order of the polyaromatic carbonaceous matter assessed by Raman spectroscopy. The infrared spectra of the matrix grains clearly reveal the presence of hydrated minerals in each of the CR chondrites. In particular, the extent of aqueous alteration experienced by QUE 99177 and MET 00426 may have been previously underestimated. The H isotopic compositions of the altering fluids were measured in situ in fine-grained phyllosilicates and individual coarse-grained hydrated silicates. In the analyzed CR chondrites, the main observations are that (i) the water is systematically enriched in D, and the enrichments (δDwater up to 1600‰) can be even higher than the highest D-enrichments reported for cometary water; (ii) the isotopic composition of the water is highly variable at the micrometer scale; (iii) there is no clear trend observed in the isotopic composition of the water (maximum D-enrichment, range of variation) along the aqueous alteration sequence. The D-enrichments and spatial variability are easier to explain as secondary signatures acquired through parent body processes, rather than as being due to the accretion of at least two ices with distinct isotopic compositions and sources that did not fully mix when they melted at the start of the aqueous alteration process.

  2. Constitutive and damage material modeling in a high pressure hydrogen environment

    NASA Technical Reports Server (NTRS)

    Russell, D. A.; Fritzemeier, L. G.

    1991-01-01

    Numerous components in reusable space propulsion systems such as the SSME are exposed to high pressure gaseous hydrogen environments. Flow areas and passages in the fuel turbopump, fuel and oxidizer preburners, main combustion chamber, and injector assembly contain high pressure hydrogen either high in purity or as hydrogen rich steam. Accurate constitutive and damage material models applicable to high pressure hydrogen environments are therefore needed for engine design and analysis. Existing constitutive and cyclic crack initiation models were evaluated only for conditions of oxidizing environments. The main objective is to evaluate these models for applicability to high pressure hydrogen environments.

  3. Hydrogen bond donors accelerate vibrational cooling of hot purine derivatives in heavy water.

    PubMed

    Zhang, Yuyuan; Chen, Jinquan; Kohler, Bern

    2013-08-08

    Natural nucleobases and many of their derivatives have ultrashort excited state lifetimes that make them excellent model systems for studying intermolecular energy flow from a hot solute molecule to the solvent. UV-pump/broadband-mid-IR-probe transient absorption spectra of canonical purine nucleobases and several xanthine derivatives were acquired in D2O and acetonitrile in the probe frequency range of 1500-1750 cm(-1). The spectra reveal that vibrationally hot ground state molecules created by ultrafast internal conversion return to thermal equilibrium in several picoseconds by dissipating their excess energy to solvent molecules. In acetonitrile solution, where hydrogen bonding is minimal, vibrational cooling (VC) occurs with the same time constant of 10 ± 3 ps for paraxanthine, theophylline, and caffeine within experimental uncertainty. In D2O, VC by these molecules occurs more rapidly and at different rates that are correlated with the number of N-D bonds. Hypoxanthine has a VC time constant of 3 ± 1 ps, while similar lifetimes of 2.3 ± 0.8 ps and 3.1 ± 0.3 ps are seen for 5'-adenosine monophosphate and 5'-guanosine monophosphate, respectively. All three molecules have at least two N-D bonds. Slightly slower VC time constants are measured for paraxanthine (4 ± 1 ps) and theophylline (5.1 ± 0.8 ps), dimethylated xanthines that have only one N-D bond. Caffeine, a trimethylated xanthine with no N-D bonds, has a VC time constant of 7.7 ± 0.9 ps, the longest ever observed for any nucleobase in aqueous solution. Hydrogen bond donation by solute molecules is proposed to enable rapid energy disposal to water via direct coupling of high frequency solute-solvent modes.

  4. Protein structural dynamics at the gas/water interface examined by hydrogen exchange mass spectrometry.

    PubMed

    Xiao, Yiming; Konermann, Lars

    2015-08-01

    Gas/water interfaces (such as air bubbles or foam) are detrimental to the stability of proteins, often causing aggregation. This represents a potential problem for industrial processes, for example, the production and handling of protein drugs. Proteins possess surfactant-like properties, resulting in a high affinity for gas/water interfaces. The tendency of previously buried nonpolar residues to maximize contact with the gas phase can cause significant structural distortion. Most earlier studies in this area employed spectroscopic tools that could only provide limited information. Here we use hydrogen/deuterium exchange (HDX) mass spectrometry (MS) for probing the conformational dynamics of the model protein myoglobin (Mb) in the presence of N(2) bubbles. HDX/MS relies on the principle that unfolded and/or highly dynamic regions undergo faster deuteration than tightly folded segments. In bubble-free solution Mb displays EX2 behavior, reflecting the occurrence of short-lived excursions to partially unfolded conformers. A dramatically different behavior is seen in the presence of N(2) bubbles; EX2 dynamics still take place, but in addition the protein shows EX1 behavior. The latter results from interconversion of the native state with conformers that are globally unfolded and long-lived. These unfolded species likely correspond to Mb that is adsorbed to the surface of gas bubbles. N(2) sparging also induces aggregation. To explain the observed behavior we propose a simple model, that is, "semi-unfolded" ↔ "native" ↔ "globally unfolded" → "aggregated". This model quantitatively reproduces the experimentally observed kinetics. To the best of our knowledge, the current study marks the first exploration of surface denaturation phenomena by HDX/MS.

  5. Protein structural dynamics at the gas/water interface examined by hydrogen exchange mass spectrometry

    PubMed Central

    Xiao, Yiming; Konermann, Lars

    2015-01-01

    Gas/water interfaces (such as air bubbles or foam) are detrimental to the stability of proteins, often causing aggregation. This represents a potential problem for industrial processes, for example, the production and handling of protein drugs. Proteins possess surfactant-like properties, resulting in a high affinity for gas/water interfaces. The tendency of previously buried nonpolar residues to maximize contact with the gas phase can cause significant structural distortion. Most earlier studies in this area employed spectroscopic tools that could only provide limited information. Here we use hydrogen/deuterium exchange (HDX) mass spectrometry (MS) for probing the conformational dynamics of the model protein myoglobin (Mb) in the presence of N2 bubbles. HDX/MS relies on the principle that unfolded and/or highly dynamic regions undergo faster deuteration than tightly folded segments. In bubble-free solution Mb displays EX2 behavior, reflecting the occurrence of short-lived excursions to partially unfolded conformers. A dramatically different behavior is seen in the presence of N2 bubbles; EX2 dynamics still take place, but in addition the protein shows EX1 behavior. The latter results from interconversion of the native state with conformers that are globally unfolded and long-lived. These unfolded species likely correspond to Mb that is adsorbed to the surface of gas bubbles. N2 sparging also induces aggregation. To explain the observed behavior we propose a simple model, that is, “semi-unfolded” ↔ “native” ↔ “globally unfolded” → “aggregated”. This model quantitatively reproduces the experimentally observed kinetics. To the best of our knowledge, the current study marks the first exploration of surface denaturation phenomena by HDX/MS. PMID:25761782

  6. Improvements in the gaseous hydrogen-water equilibration technique for hydrogen isotope ratio analysis

    USGS Publications Warehouse

    Coplen, T.B.; Wildman, J.D.; Chen, J.

    1991-01-01

    Improved precision in the H2-H2O equilibration method for ??D analysis has been achieved in an automated system. Reduction in 1-?? standard deviation of a single mass-spectrometer analysis to 1.3??? is achieved by (1) bonding catalyst to glass rods and assigning use to specific equilibration chambers to monitor performance of catalyst, (2) improving the apparatus design, and (3) reducing the H3+ contribution of the mass-spectrometer ion source. For replicate analysis of a water sample, the standard deviation improved to 0.8???. H2S-bearing samples and samples as small as 0.1 mL can be analyzed routinely with this method.

  7. Physics Beyond the Standard Model from Molecular Hydrogen Spectroscopy

    NASA Astrophysics Data System (ADS)

    Ubachs, Wim; Salumbides, Edcel John; Bagdonaite, Julija

    2015-06-01

    The spectrum of molecular hydrogen can be measured in the laboratory to very high precision using advanced laser and molecular beam techniques, as well as frequency-comb based calibration [1,2]. The quantum level structure of this smallest neutral molecule can now be calculated to very high precision, based on a very accurate (10-15 precision) Born-Oppenheimer potential [3] and including subtle non-adiabatic, relativistic and quantum electrodynamic effects [4]. Comparison between theory and experiment yields a test of QED, and in fact of the Standard Model of Physics, since the weak, strong and gravitational forces have a negligible effect. Even fifth forces beyond the Standard Model can be searched for [5]. Astronomical observation of molecular hydrogen spectra, using the largest telescopes on Earth and in space, may reveal possible variations of fundamental constants on a cosmological time scale [6]. A study has been performed at a 'look-back' time of 12.5 billion years [7]. In addition the possible dependence of a fundamental constant on a gravitational field has been investigated from observation of molecular hydrogen in the photospheres of white dwarfs [8]. The latter involves a test of the Einsteins equivalence principle. [1] E.J. Salumbides et al., Phys. Rev. Lett. 107, 143005 (2011). [2] G. Dickenson et al., Phys. Rev. Lett. 110, 193601 (2013). [3] K. Pachucki, Phys. Rev. A82, 032509 (2010). [4] J. Komasa et al., J. Chem. Theory Comp. 7, 3105 (2011). [5] E.J. Salumbides et al., Phys. Rev. D87, 112008 (2013). [6] F. van Weerdenburg et al., Phys. Rev. Lett. 106, 180802 (2011). [7] J. Badonaite et al., Phys. Rev. Lett. 114, 071301 (2015). [8] J. Bagdonaite et al., Phys. Rev. Lett. 113, 123002 (2014).

  8. Hydrogen isotope composition of dry season atmospheric water vapor on Quelccaya Ice Cap, Peru

    NASA Astrophysics Data System (ADS)

    Samuels-Crow, K. E.; Galewsky, J.; Hardy, D. R.; Braun, C.

    2011-12-01

    In-situ measurements of modern meteorological conditions at Quelccaya Ice Cap's summit, including the isotopic composition of atmospheric water vapor, may aid in the interpretation of the 1500-year, annually resolved ice-core record available from the site (Thompson et al., 2003). Betweeen July 7 and July 9, 2011, we collected 11 samples of atmospheric water vapor from the summit of Quelccaya and analyzed the hydrogen isotopic composition on a Finnegan MAT-252 mass spectrometer using the method of Strong et al 2007. δD values ranged from -134% to -168%, and specific humidity ranged from 1.5 to 3 g/kg. The isotopic composition of tropical Andean ice cores has been variously interpreted in terms of simple Rayleigh distillation models, in which water evaporates from the tropical Atlantic and condenses as it moves upslope (Grootes et al., 1989; Pierrehumbert, 1999), or in terms of the condensation temperature (Thompson et al., 2003). The joint distribution of water vapor concentrations and δD values in our dataset cannot be explained by a simple upslope Rayleigh distillation model. Such a model predicts higher water-vapor concentrations and lower δD values than those measured during the sampling period. We hypothesize that the joint distribution of water vapor mixing ratio and isotopic composition can be explained by large-scale mixing of air parcels that were last saturated in the upper tropical troposphere. Such mixing necessarily leads to parcels that have higher delta values than would be expected for the simple Rayleigh distillation to the observed mixing ratio. Local effects of snow sublimation may exert additional controls over the water-vapor mixing ratio and delta values. Further monitoring during both the wet and dry seasons may clarify the relationship between large-scale water-vapor transport and the snow and ice preserved on Quelccaya. References Friedman, I. (1953) Deuterium content of natural waters and other substances, Geoch. et Cosmochim. Acta, 4

  9. Intermolecular potential and second virial coefficient of the water-hydrogen complex

    SciTech Connect

    Hodges, Matthew P.; Wheatley, Richard J.; Schenter, Gregory K.; Harvey, Allen H.

    2004-01-08

    We construct a rigid-body (5-dimensional) potential-energy surface for the water-hydrogen complex using scaled perturbation theory (SPT). An analytic fit of this surface is obtained, and using this, two minima are found: the global minimum has C{sub 2v} symmetry, with the hydrogen molecule acting as a proton donor to the oxygen atom on water; a local minimum with C{sub s} symmetry has the hydrogen molecule acting as a proton acceptor to one of the hydrogen atoms on water, where the OH bond and H{sub 2} are in a T-shaped configuration. The SPT global and local minima are bound by 1097 {micro}E{sub h} (E{sub h} {approx} 4.359 744 x 10{sup -18} J). Our best estimate of the binding energy, from a complete basis set extrapolation of coupled-cluster calculations, is 1076.1 {micro}E{sub h}. The fitted surface is used to calculate the second cross virial coefficient over a wide temperature range (100-3000 K). Three complementary methods are used to quantify quantum statistical mechanical effects that become significant at low temperatures. We compare our results with experimental data, which are available over a smaller temperature range (230-700 K). Generally good agreement is found, but the experimental data are subject to larger uncertainties.

  10. Intermolecular potential and second virial coefficient of the water-hydrogen complex.

    PubMed

    Hodges, Matthew P; Wheatley, Richard J; Schenter, Gregory K; Harvey, Allan H

    2004-01-08

    We construct a rigid-body (five-dimensional) potential-energy surface for the water-hydrogen complex using scaled perturbation theory (SPT). An analytic fit of this surface is obtained, and, using this, two minima are found. The global minimum has C2v symmetry, with the hydrogen molecule acting as a proton donor to the oxygen atom on water. A local minimum with Cs symmetry has the hydrogen molecule acting as a proton acceptor to one of the hydrogen atoms on water, where the OH bond and H2 are in a T-shaped configuration. The SPT global minimum is bound by 1097 microEh (Eh approximately 4.359744 x 10(-18) J). Our best estimate of the binding energy, from a complete basis set extrapolation of coupled-cluster calculations, is 1076.1 microEh. The fitted surface is used to calculate the second cross virial coefficient over a wide temperature range (100-3000 K). Three complementary methods are used to quantify quantum statistical mechanical effects that become significant at low temperatures. We compare our results with experimental data, which are available over a smaller temperature range (230-700 K). Generally good agreement is found, but the experimental data are subject to larger uncertainties.

  11. Hierarchical formation of helical supramolecular polymers via stacking of hydrogen-bonded pairs in water.

    PubMed

    Brunsveld, L; Vekemans, J A J M; Hirschberg, J H K K; Sijbesma, R P; Meijer, E W

    2002-04-16

    Bifunctional ureido-s-triazines provided with penta(ethylene oxide) side chains are able to self assemble in water, leading to helical columns via cooperative stacking of the hydrogen-bonded pairs (DADA array). Monofunctional ureido-s-triazines do not form such helical architectures. The presence of a linker, covalently connecting the two ureido-s-triazine units, is essential as it generates a high local concentration of aromatic units, favorable for stacking interactions. This hydrophobic stacking of the aromatic units occurs at concentrations as low as 5 x 10(-6) M and can be visualized by using fluorescence spectroscopy. The stacking generates a hydrophobic microenvironment that allows intermolecular hydrogen bonding to occur at higher concentrations because the hydrogen bonds are shielded from competitive hydrogen bonding with water. This hierarchical process results in the formation of a helical self-assembled polymer in water at concentrations above 10(-4) M. Chiral side chains attached to the ureido-s-triazine units bias the helicity of these columns as concluded from CD spectroscopy and "Sergeants and Soldiers" experiments.

  12. Spectroscopic identification of ethanol-water conformers by large-amplitude hydrogen bond librational modes

    SciTech Connect

    Andersen, J.; Wugt Larsen, R.; Heimdal, J.

    2015-12-14

    The far-infrared absorption spectra have been recorded for hydrogen-bonded complexes of water with ethanol embedded in cryogenic neon matrices at 2.8 K. The partial isotopic H/D-substitution of the ethanol subunit enabled by a dual inlet deposition procedure enables the observation and unambiguous assignment of the intermolecular high-frequency out-of-plane and the low-frequency in-plane donor OH librational modes for two different conformations of the mixed binary ethanol/water complex. The resolved donor OH librational bands confirm directly previous experimental evidence that ethanol acts as the O⋯HO hydrogen bond acceptor in the two most stable conformations. In the most stable conformation, the water subunit forces the ethanol molecule into its less stable gauche configuration upon dimerization owing to a cooperative secondary weak O⋯HC hydrogen bond interaction evidenced by a significantly blue-shift of the low-frequency in-plane donor OH librational band origin. The strong correlation between the low-frequency in-plane donor OH librational motion and the secondary intermolecular O⋯HC hydrogen bond is demonstrated by electronic structure calculations. The experimental findings are further supported by CCSD(T)-F12/aug-cc-pVQZ calculations of the conformational energy differences together with second-order vibrational perturbation theory calculations of the large-amplitude donor OH librational band origins.

  13. Slow dielectric response of Debye-type in water and other hydrogen bonded liquids

    NASA Astrophysics Data System (ADS)

    Jansson, Helén; Bergman, Rikard; Swenson, Jan

    2010-05-01

    The slow dynamics of some hydrogen bonded glass-forming liquids has been investigated by broadband dielectric spectroscopy. We show that the polyalcohols glycerol, xylitol, and sorbitol, and mixtures of glycerol and water, and in fact, even pure water exhibit a process of Debye character at longer time-scales than the glass transition and viscosity related α-relaxation. Even if it is less pronounced, this process displays many similarities to the well-studied Debye-like process in monoalcohols. It can be observed in both the negative derivative of the real part of the permittivity or in the imaginary part of the permittivity, if the conductivity contribution is reduced. In the present study the conductivity contribution has been suppressed by use of a thin Teflon film placed between the sample and one of the electrodes. The new findings might have important implications for the structure and dynamics of hydrogen bonded liquids in general, and for water in particular.

  14. A metal-free polymeric photocatalyst for hydrogen production from water under visible light.

    PubMed

    Wang, Xinchen; Maeda, Kazuhiko; Thomas, Arne; Takanabe, Kazuhiro; Xin, Gang; Carlsson, Johan M; Domen, Kazunari; Antonietti, Markus

    2009-01-01

    The production of hydrogen from water using a catalyst and solar energy is an ideal future energy source, independent of fossil reserves. For an economical use of water and solar energy, catalysts that are sufficiently efficient, stable, inexpensive and capable of harvesting light are required. Here, we show that an abundant material, polymeric carbon nitride, can produce hydrogen from water under visible-light irradiation in the presence of a sacrificial donor. Contrary to other conducting polymer semiconductors, carbon nitride is chemically and thermally stable and does not rely on complicated device manufacturing. The results represent an important first step towards photosynthesis in general where artificial conjugated polymer semiconductors can be used as energy transducers.

  15. Generation of Hydrogen by Visible Light-Induced Water Splitting with the Use of Semiconductors and Dyes.

    PubMed

    Rao, C N R; Lingampalli, Srinivasa Rao

    2016-01-06

    Photosynthesis that occurs in plants involves both the oxidation of water and the reduction of carbon dioxide. Plants carry out these reactions with ease, by involving electron-transport chains. In this article, hydrogen generation by the reduction of water in the laboratory by using semiconductor nanostructures through artificial photosynthesis is examined. Dye-sensitized photochemical generation of hydrogen from water is also discussed. Hydrogen generation by these means has great technological relevance, since it is an environmentally friendly fuel. The way in which oxygen can be generated by the oxidation of water using metal oxide catalysts is also shown.

  16. Towards a unified description of the hydrogen bond network of liquid water: A dynamics based approach

    SciTech Connect

    Ozkanlar, Abdullah Zhou, Tiecheng; Clark, Aurora E.

    2014-12-07

    The definition of a hydrogen bond (H-bond) is intimately related to the topological and dynamic properties of the hydrogen bond network within liquid water. The development of a universal H-bond definition for water is an active area of research as it would remove many ambiguities in the network properties that derive from the fixed definition employed to assign whether a water dimer is hydrogen bonded. This work investigates the impact that an electronic-structure based definition, an energetic, and a geometric definition of the H-bond has upon both topological and dynamic network behavior of simulated water. In each definition, the use of a cutoff (either geometric or energetic) to assign the presence of a H-bond leads to the formation of transiently bonded or broken dimers, which have been quantified within the simulation data. The relative concentration of transient species, and their duration, results in two of the three definitions sharing similarities in either topological or dynamic features (H-bond distribution, H-bond lifetime, etc.), however no two definitions exhibit similar behavior for both classes of network properties. In fact, two networks with similar local network topology (as indicated by similar average H-bonds) can have dramatically different global network topology (as indicated by the defect state distributions) and altered H-bond lifetimes. A dynamics based correction scheme is then used to remove artificially transient H-bonds and to repair artificially broken bonds within the network such that the corrected network exhibits the same structural and dynamic properties for two H-bond definitions (the properties of the third definition being significantly improved). The algorithm described represents a significant step forward in the development of a unified hydrogen bond network whose properties are independent of the original hydrogen bond definition that is employed.

  17. Photocatalytic hydrogen generation from water under visible light using core/shell nano-catalysts.

    PubMed

    Wang, X; Shih, K; Li, X Y

    2010-01-01

    A microemulsion technique was employed to synthesize nano-sized photocatalysts with a core (CdS)/shell (ZnS) structure. The primary particles of the photocatalysts were around 10 nm, and the mean size of the catalyst clusters in water was about 100 nm. The band gaps of the catalysts ranged from 2.25 to 2.46 eV. The experiments of photocatalytic H(2) generation showed that the catalysts (CdS)(x)/(ZnS)(1-x) with x ranging from 0.1 to 1 were able to produce hydrogen from water photolysis under visible light. The catalyst with x=0.9 had the highest rate of hydrogen production. The catalyst loading density also influenced the photo-hydrogen production rate, and the best catalyst concentration in water was 1 g L(-1). The stability of the nano-catalysts in terms of size, morphology and activity was satisfactory during an extended test period for a specific hydrogen production rate of 2.38 mmol g(-1) L(-1) h(-1) and a quantum yield of 16.1% under visible light (165 W Xe lamp, lambda>420 nm). The results demonstrate that the (CdS)/(ZnS) core/shell nano-particles are a novel photo-catalyst for renewable hydrogen generation from water under visible light. This is attributable to the large band-gap ZnS shell that separates the electron/hole pairs generated by the CdS core and hence reduces their recombinations.

  18. Advanced alkaline water electrolysis. Task 2 summary report. Model for alkaline water electrolysis systems

    SciTech Connect

    Yaffe, M.R.; Murray, J.N.

    1980-04-01

    Task 2 involved the establishment of an engineering and economic model for the evaluation of various options in water electrolysis. The mode, verification of the specific coding and four case studies are described. The model was tested by evaluation of a nearly commercial technology, i.e., an 80-kW alkaline electrolyte system, operating at 60/sup 0/C, which delivers approximately 255 SLM, hydrogen for applications such as electrical generation cooling or semiconductor manufacturing. The calculated cost of hydrogen from this installed non-optimized case system with an initial cost to the customer of $87,000 was $6.99/Kg H/sub 2/ ($1.67/100 SCF) on a 20-yr levelized basis using 2.5 cents/kWh power costs. This compares favorably to a levelized average merchant hydrogen cost value of $9.11/Kg H/sub 2/ ($2.17/100 SCF) calculated using the same program.

  19. Validation of hydrogen gas stratification and mixing models

    SciTech Connect

    Wu, Hsingtzu; Zhao, Haihua

    2015-05-26

    Two validation benchmarks confirm that the BMIX++ code is capable of simulating unintended hydrogen release scenarios efficiently. The BMIX++ (UC Berkeley mechanistic MIXing code in C++) code has been developed to accurately and efficiently predict the fluid mixture distribution and heat transfer in large stratified enclosures for accident analyses and design optimizations. The BMIX++ code uses a scaling based one-dimensional method to achieve large reduction in computational effort compared to a 3-D computational fluid dynamics (CFD) simulation. Two BMIX++ benchmark models have been developed. One is for a single buoyant jet in an open space and another is for a large sealed enclosure with both a jet source and a vent near the floor. Both of them have been validated by comparisons with experimental data. Excellent agreements are observed. The entrainment coefficients of 0.09 and 0.08 are found to fit the experimental data for hydrogen leaks with the Froude number of 99 and 268 best, respectively. In addition, the BIX++ simulation results of the average helium concentration for an enclosure with a vent and a single jet agree with the experimental data within a margin of about 10% for jet flow rates ranging from 1.21 × 10⁻⁴ to 3.29 × 10⁻⁴ m³/s. In conclusion, computing time for each BMIX++ model with a normal desktop computer is less than 5 min.

  20. Validation of hydrogen gas stratification and mixing models

    DOE PAGES

    Wu, Hsingtzu; Zhao, Haihua

    2015-05-26

    Two validation benchmarks confirm that the BMIX++ code is capable of simulating unintended hydrogen release scenarios efficiently. The BMIX++ (UC Berkeley mechanistic MIXing code in C++) code has been developed to accurately and efficiently predict the fluid mixture distribution and heat transfer in large stratified enclosures for accident analyses and design optimizations. The BMIX++ code uses a scaling based one-dimensional method to achieve large reduction in computational effort compared to a 3-D computational fluid dynamics (CFD) simulation. Two BMIX++ benchmark models have been developed. One is for a single buoyant jet in an open space and another is for amore » large sealed enclosure with both a jet source and a vent near the floor. Both of them have been validated by comparisons with experimental data. Excellent agreements are observed. The entrainment coefficients of 0.09 and 0.08 are found to fit the experimental data for hydrogen leaks with the Froude number of 99 and 268 best, respectively. In addition, the BIX++ simulation results of the average helium concentration for an enclosure with a vent and a single jet agree with the experimental data within a margin of about 10% for jet flow rates ranging from 1.21 × 10⁻⁴ to 3.29 × 10⁻⁴ m³/s. In conclusion, computing time for each BMIX++ model with a normal desktop computer is less than 5 min.« less

  1. Hydrogen from renewable energy - Photovoltaic/water electrolysis as an exemplary approach

    NASA Astrophysics Data System (ADS)

    Sprafka, R. J.; Tison, R. R.; Escher, W. J. D.

    A feasibility study has been conducted for a NASA Kennedy Space Center liquid hydrogen/liquid oxygen production facility using solar cell arrays as the power source for electrolysis. The 100 MW output of the facility would be split into 67.6 and 32 MW portions for electrolysis and liquefaction, respectively. The solar cell array would cover 1.65 sq miles, and would be made up of 249 modular 400-kW arrays. Hydrogen and oxygen are generated at either dispersed or centralized water electrolyzers. The yearly hydrogen output is projected to be 5.76 million lbs, with 8 times that much oxygen; these fuel volumes can support approximately 18 Space Shuttle launches/year.

  2. Hydrogen from renewable energy - Photovoltaic/water electrolysis as an exemplary approach

    NASA Technical Reports Server (NTRS)

    Sprafka, R. J.; Tison, R. R.; Escher, W. J. D.

    1984-01-01

    A feasibility study has been conducted for a NASA Kennedy Space Center liquid hydrogen/liquid oxygen production facility using solar cell arrays as the power source for electrolysis. The 100 MW output of the facility would be split into 67.6 and 32 MW portions for electrolysis and liquefaction, respectively. The solar cell array would cover 1.65 sq miles, and would be made up of 249 modular 400-kW arrays. Hydrogen and oxygen are generated at either dispersed or centralized water electrolyzers. The yearly hydrogen output is projected to be 5.76 million lbs, with 8 times that much oxygen; these fuel volumes can support approximately 18 Space Shuttle launches/year.

  3. Oral intake of hydrogen-rich water ameliorated chlorpyrifos-induced neurotoxicity in rats

    SciTech Connect

    Wang, Tingting; Zhao, Ling; Liu, Mengyu; Xie, Fei; Ma, Xuemei Zhao, Pengxiang; Liu, Yunqi; Li, Jiala; Wang, Minglian; Yang, Zhaona; Zhang, Yutong

    2014-10-01

    Chronic exposure to low-levels of organophosphate (OP) compounds, such as chlorpyrifos (CPF), induces oxidative stress and could be related to neurological disorders. Hydrogen has been identified as a novel antioxidant which could selectively scavenge hydroxyl radicals. We explore whether intake of hydrogen-rich water (HRW) can protect Wistar rats from CPF-induced neurotoxicity. Rats were gavaged daily with 6.75 mg/kg body weight (1/20 LD{sub 50}) of CPF and given HRW by oral intake. Nissl staining and electron microscopy results indicated that HRW intake had protective effects on the CPF-induced damage of hippocampal neurons and neuronal mitochondria. Immunostaining results showed that the increased glial fibrillary acidic protein (GFAP) expression in astrocytes induced by CPF exposure can be ameliorated by HRW intake. Moreover, HRW intake also attenuated CPF-induced oxidative stress as evidenced by enhanced level of MDA, accompanied by an increase in GSH level and SOD and CAT activity. Acetylcholinesterase (AChE) activity tests showed significant decrease in brain AChE activity after CPF exposure, and this effect can be ameliorated by HRW intake. An in vitro study demonstrated that AChE activity was more intense in HRW than in normal water with or without chlorpyrifos-oxon (CPO), the metabolically-activated form of CPF. These observations suggest that HRW intake can protect rats from CPF-induced neurotoxicity, and the protective effects of hydrogen may be mediated by regulating the oxidant and antioxidant status of rats. Furthermore, this work defines a novel mechanism of biological activity of hydrogen by directly increasing the AChE activity. - Highlights: • Hydrogen molecules protect rats from CPF-induced damage of hippocampal neurons. • The increased GFAP expression induced by CPF can also be ameliorated by hydrogen. • Hydrogen molecules attenuated the increase in CPF-induced oxidative stress. • Hydrogen molecules attenuated AChE inhibition in vivo

  4. Unusual hydrogen bonding behavior in binary complexes of coinage metal anions with water

    NASA Astrophysics Data System (ADS)

    Schneider, Holger; Boese, A. Daniel; Weber, J. Mathias

    2005-08-01

    We have studied the interaction of atomic coinage metal anions with water molecules by infrared photodissociation spectroscopy of M-•H2O•Arn clusters (M =Cu, Ag, Au; n =1, 2). We compare our observations with calculations on density-functional and coupled cluster levels of theory. The gold anion is bound to the water molecule by a single ionic hydrogen bond, similar to the halide-water complexes. In contrast, zero-point motion in the silver and copper complexes leads to a deviation from this motif.

  5. Silicon based multilayer photoelectrodes for photoelectrolysis of water to produce hydrogen from the sun

    NASA Astrophysics Data System (ADS)

    Faruque, Faisal

    The main objective of this work is to study different materials for the direct photosynthesis of hydrogen from water. A variety of photocatalysts such as titanium dioxide, titanium oxy-nitride, silicon carbide, and gallium nitride are being investigated by others for the clean production of hydrogen for fuel cells and hydrogen economy. Our approach was to deposit suitable metallic regions on photocatalyst nanoparticles to direct the efficient synthesis of hydrogen to a particular site for convenient collection. We studied different electrode metals such as gold, platinum, titanium, palladium, and tungsten. We also studied different solar cell materials such as silicon (p- and n-types), silicon carbide and titanium dioxide semiconductors in order to efficiently generate electrons under illumination. We introduced a novel silicon-based multilayer photosynthesis device to take advantage of suitable properties of silicon and tungsten to efficiently produce hydrogen. The device consisted of a silicon (0.5mm) substrate, a deposited atomic layer of Al2O 3 (1nm), a doped polysilicon (0.1microm), and finally a tungsten nanoporous (5-10nm) layer acting as an interface electrode with water. The Al2O 3 layer was introduced to reduce leakage current and to prevent the spreading of the diffused p-n junction layer between the silicon and doped polysilicon layers. The surface of the photoelectrode was coated with nanotextured tungsten nanopores (TNP), which increased the surface area of the electrodes to the electrolyte, assisting in electron-hole mobility, and acting as a photocatalyst. The reported device exhibited a fill factor (%FF) of 27.22% and solar-to-hydrogen conversion efficiency of 0.03174%. This thesis describes the structures of the device, and offers a characterization and comparison between different photoelectrodes.

  6. [Accelerated senescence of fresh-cut Chinese water chestnut tissues in relation to hydrogen peroxide accumulation].

    PubMed

    Peng, Li-Tao; Jiang, Yue-Ming; Yang, Shu-Zhen; Pan, Si-Yi

    2005-10-01

    Accelerated senescence of fresh-cut Chinese water chestnut (CWC) tissues in relation to active oxygen species (AOS) metabolism was investigated. Fresh-cut CWC (2 mm thick) and intact CWC were stored at 4 degrees C in trays wrapped with plastic films. Changes in superoxide anion production rate, activities of superoxide dismutase (SOD), catalase (CAT) and ascorbate peroxidase (APX) were monitored, while contents of hydrogen peroxide, ascorbic acid, MDA as well as electrolyte leakage were measured. Fresh-cutting of CWC induced activities of SOD, CAT and APX to a certain extent (Fig. 2B and Fig. 3), but simultaneously stimulated superoxide anion production markedly (Fig. 2A), enhanced hydrogen peroxide accumulation and accelerated loss in ascorbic acid (Figs. 4 and 5), which resulted in increased lipid peroxidation indicated by malondialdehyde (MDA) content and electrolyte leakage (Fig. 1). Statistics analysis indicated that there was a significantly positive correlation among hydrogen peroxide accumulation, MDA content and electrolyte leakage (Table 1). Histochemical detection with 3, 3'-diaminobenzidine further demonstrated that hydrogen peroxide accumulation increased in fresh-cut CWC during storage (Fig. 5). AOS production rate and activities of SOD, CAT and APX changed little while no obvious hydrogen peroxide accumulation was observed, in intact CWC during storage.

  7. Kinetic modelling of molecular hydrogen transport in microporous carbon materials.

    SciTech Connect

    Hankel, M.; Zhang, H.; Nguyen, T. X.; Bhatia, S. K.; Gray, S. K.; Smith, S. C.

    2011-01-01

    The proposal of kinetic molecular sieving of hydrogen isotopes is explored by employing statistical rate theory methods to describe the kinetics of molecular hydrogen transport in model microporous carbon structures. A Lennard-Jones atom-atom interaction potential is utilized for the description of the interactions between H{sub 2}/D{sub 2} and the carbon framework, while the requisite partition functions describing the thermal flux of molecules through the transition state are calculated quantum mechanically in view of the low temperatures involved in the proposed kinetic molecular sieving application. Predicted kinetic isotope effects for initial passage from the gas phase into the first pore mouth are consistent with expectations from previous modeling studies, namely, that at sufficiently low temperatures and for sufficiently narrow pore mouths D{sub 2} transport is dramatically favored over H{sub 2}. However, in contrast to expectations from previous modeling, the absence of any potential barrier along the minimum energy pathway from the gas phase into the first pore mouth yields a negative temperature dependence in the predicted absolute rate coefficients - implying a negative activation energy. In pursuit of the effective activation barrier, we find that the minimum potential in the cavity is significantly higher than in the pore mouth for nanotube-shaped models, throwing into question the common assumption that passage through the pore mouths should be the rate-determining step. Our results suggest a new mechanism that, depending on the size and shape of the cavity, the thermal activation barrier may lie in the cavity rather than at the pore mouth. As a consequence, design strategies for achieving quantum-mediated kinetic molecular sieving of H{sub 2}/D{sub 2} in a microporous membrane will need, at the very least, to take careful account of cavity shape and size in addition to pore-mouth size in order to ensure that the selective step, namely passage

  8. Functional interactions in bacteriorhodopsin: a theoretical analysis of retinal hydrogen bonding with water.

    PubMed Central

    Nina, M; Roux, B; Smith, J C

    1995-01-01

    The light-driven proton pump, bacteriorhodopsin (bR) contains a retinal molecule with a Schiff base moiety that can participate in hydrogen-bonding interactions in an internal, water-containing channel. Here we combine quantum chemistry and molecular mechanics techniques to determine the geometries and energetics of retinal Schiff base-water interactions. Ab initio molecular orbital calculations are used to determine potential surfaces for water-Schiff base hydrogen-bonding and to characterize the energetics of rotation of the C-C single bond distal and adjacent to the Schiff base NH group. The ab initio results are combined with semiempirical quantum chemistry calculations to produce a data set used for the parameterization of a molecular mechanics energy function for retinal. Using the molecular mechanics force field the hydrated retinal and associated bR protein environment are energy-minimized and the resulting geometries examined. Two distinct sites are found in which water molecules can have hydrogen-bonding interactions with the Schiff base: one near the NH group of the Schiff base in a polar region directed towards the extracellular side, and the other near a retinal CH group in a relatively nonpolar region, directed towards the cytoplasmic side. Images FIGURE 1 FIGURE 2 FIGURE 6 FIGURE 8 PMID:7711248

  9. Accelerated Stress Corrosion Crack Initiation of Alloys 600 and 690 in Hydrogenated Supercritical Water

    NASA Astrophysics Data System (ADS)

    Moss, Tyler; Was, Gary S.

    2017-01-01

    The objective of this study is to determine whether stress corrosion crack initiation of Alloys 600 and 690 occurs by the same mechanism in subcritical and supercritical water. Tensile bars of Alloys 690 and 600 were strained in constant extension rate tensile experiments in hydrogenated subcritical and supercritical water from 593 K to 723 K (320 °C to 450 °C), and the crack initiation behavior was characterized by high-resolution electron microscopy. Intergranular cracking was observed across the entire temperature range, and the morphology, structure, composition, and temperature dependence of initiated cracks in Alloy 690 were consistent between hydrogenated subcritical and supercritical water. Crack initiation of Alloy 600 followed an Arrhenius relationship and did not exhibit a discontinuity or change in slope after crossing the critical temperature. The measured activation energy was 121 ± 13 kJ/mol. Stress corrosion crack initiation in Alloy 690 was fit with a single activation energy of 92 ± 12 kJ/mol across the entire temperature range. Cracks were observed to propagate along grain boundaries adjacent to chromium-depleted metal, with Cr2O3 observed ahead of crack tips. All measures of the SCC behavior indicate that the mechanism for stress corrosion crack initiation of Alloy 600 and Alloy 690 is consistent between hydrogenated subcritical and supercritical water.

  10. Accelerated Stress Corrosion Crack Initiation of Alloys 600 and 690 in Hydrogenated Supercritical Water

    NASA Astrophysics Data System (ADS)

    Moss, Tyler; Was, Gary S.

    2017-04-01

    The objective of this study is to determine whether stress corrosion crack initiation of Alloys 600 and 690 occurs by the same mechanism in subcritical and supercritical water. Tensile bars of Alloys 690 and 600 were strained in constant extension rate tensile experiments in hydrogenated subcritical and supercritical water from 593 K to 723 K (320 °C to 450 °C), and the crack initiation behavior was characterized by high-resolution electron microscopy. Intergranular cracking was observed across the entire temperature range, and the morphology, structure, composition, and temperature dependence of initiated cracks in Alloy 690 were consistent between hydrogenated subcritical and supercritical water. Crack initiation of Alloy 600 followed an Arrhenius relationship and did not exhibit a discontinuity or change in slope after crossing the critical temperature. The measured activation energy was 121 ± 13 kJ/mol. Stress corrosion crack initiation in Alloy 690 was fit with a single activation energy of 92 ± 12 kJ/mol across the entire temperature range. Cracks were observed to propagate along grain boundaries adjacent to chromium-depleted metal, with Cr2O3 observed ahead of crack tips. All measures of the SCC behavior indicate that the mechanism for stress corrosion crack initiation of Alloy 600 and Alloy 690 is consistent between hydrogenated subcritical and supercritical water.

  11. The effect of plutonium dioxide water surface coverage on the generation of hydrogen and oxygen

    SciTech Connect

    Veirs, Douglas K.; Berg, John M.; Crowder, Mark L.

    2012-06-20

    The conditions for the production of oxygen during radiolysis of water adsorbed onto plutonium dioxide powder are discussed. Studies in the literature investigating the radiolysis of water show that both oxygen and hydrogen can be generated from water adsorbed on high-purity plutonium dioxide powder. These studies indicate that there is a threshold in the amount of water below which oxygen is not generated. The threshold is associated with the number of monolayers of adsorbed water and is shown to occur at approximately two monolayers of molecularly adsorbed water. Material in equilibrium with 50% relative humidity (RH) will be at the threshold for oxygen generation. Using two monolayers of molecularly adsorbed water as the threshold for oxygen production, the total pressure under various conditions is calculated assuming stoichiometric production of hydrogen and oxygen. The specific surface area of the oxide has a strong effect on the final partial pressure. The specific surface areas resulting in the highest pressures within a 3013 container are evaluated. The potential for oxygen generation is mitigated by reduced relative humidity, and hence moisture adsorption, at the oxide surface which occurs if the oxide is warmer than the ambient air. The potential for oxygen generation approaches zero as the temperature difference between the ambient air and the material approaches 6 C.

  12. Water-containing hydrogen-bonding network in the active center of channelrhodopsin.

    PubMed

    Ito, Shota; Kato, Hideaki E; Taniguchi, Reiya; Iwata, Tatsuya; Nureki, Osamu; Kandori, Hideki

    2014-03-05

    Channelrhodopsin (ChR) functions as a light-gated ion channel in Chlamydomonas reinhardtii. Passive transport of cations by ChR is fundamentally different from the active transport by light-driven ion pumps such as archaerhodopsin, bacteriorhodopsin, and halorhodopsin. These microbial rhodopsins are important tools for optogenetics, where ChR is used to activate neurons by light, while the ion pumps are used for neural silencing. Ion-transport functions by these rhodopsins strongly depend on the specific hydrogen-bonding networks containing water near the retinal chromophore. In this work, we measured protein-bound water molecules in a chimeric ChR protein of ChR1 (helices A to E) and ChR2 (helices F and G) of Chlamydomonas reinhardtii using low-temperature FTIR spectroscopy at 77 K. We found that the active center of ChR possesses more water molecules (9 water vibrations) than those of other microbial (2-6 water vibrations) and animal (6-8 water vibrations) rhodopsins. We conclude that the protonated retinal Schiff base interacts with the counterion (Glu162) directly, without the intervening water molecule found in proton-pumping microbial rhodopsins. The present FTIR results and the recent X-ray structure of ChR reveal a unique hydrogen-bonding network around the active center of this light-gated ion channel.

  13. An insight into liquid water networks through hydrogen bonding halide anion: Stimulated Raman scattering

    NASA Astrophysics Data System (ADS)

    Wang, Shenghan; Fang, Wenhui; Li, Tianyu; Li, Fangfang; Sun, Chenglin; Li, Zuowei; Huang, Yuxin; Men, Zhiwei

    2016-04-01

    We have studied the interaction between water molecules and halide anions and acquired the influence of concentration by the spontaneous Raman spectrum. The results agreed well with the previous researches. To explore further, the stimulated Raman scattering of a halide-water binary solution is measured to study the nature of the hydrogen bonding between water molecules and halogen anions. Under the effect of laser-induced plasma, the OH stretching vibration spectra of aqueous solutions of halogen ions pretty exhibit different trend compared with that of spontaneous Raman spectrum. The frequency shifts of water OH vibration show different values and directions with adding different halide anions. The red shift of F-- and Cl--water molecule clusters is due to the process of charge transfer, whereas the blue shift of Br-- and I--water molecule cluster is due to polarization effect without charge transfer. The results demonstrate that F- and Cl- slightly weaken the hydrogen bond (HB), whereas Br- and I- enhance HB in the water cluster. The decrease of concentration of halogen ions aqueous solution can weaken the effect on the HB.

  14. Hydrogen from water photolysis via SC-SEP cells

    SciTech Connect

    Ottova, A.L.; Tien, H.T.; Tan, Z.; Ren, P.; Luo, W.

    1997-12-31

    The use of semiconductor septum electrochemical photovoltaic (SC-SEP) cell, modeled after green plant photosynthesis, in an application of solar energy conversion,m is reported. A SC-SEP cell consists of a thin film of CdSe deposited on a metallic substrate (Ti, Ni, or stainless steel) as a bipolar septum electrode separating two aqueous solutions. It has been established that, upon irradiation of the septum electrode with visible light of the solar spectrum, photogenerated electron-hole pairs are separated under light.

  15. Revisited reaction-diffusion model of thermal desorption spectroscopy experiments on hydrogen retention in material

    SciTech Connect

    Guterl, Jerome Smirnov, R. D.; Krasheninnikov, S. I.

    2015-07-28

    Desorption phase of thermal desorption spectroscopy (TDS) experiments performed on tungsten samples exposed to flux of hydrogen isotopes in fusion relevant conditions is analyzed using a reaction-diffusion model describing hydrogen retention in material bulk. Two regimes of hydrogen desorption are identified depending on whether hydrogen trapping rate is faster than hydrogen diffusion rate in material during TDS experiments. In both regimes, a majority of hydrogen released from material defects is immediately outgassed instead of diffusing deeply in material bulk when the evolution of hydrogen concentration in material is quasi-static, which is the case during TDS experiments performed with tungsten samples exposed to flux of hydrogen isotopes in fusion related conditions. In this context, analytical expressions of the hydrogen outgassing flux as a function of the material temperature are obtained with sufficient accuracy to describe main features of thermal desorption spectra (TDSP). These expressions are then used to highlight how characteristic temperatures of TDSP depend on hydrogen retention parameters, such as trap concentration or activation energy of detrapping processes. The use of Arrhenius plots to characterize retention processes is then revisited when hydrogen trapping takes place during TDS experiments. Retention processes are also characterized using the shape of desorption peaks in TDSP, and it is shown that diffusion of hydrogen in material during TDS experiment can induce long desorption tails visible aside desorption peaks at high temperature in TDSP. These desorption tails can be used to estimate activation energy of diffusion of hydrogen in material.

  16. Muonium chemistry and spin dynamics in sulphur, modelling interstitial hydrogen.

    PubMed

    Cox, S F J; Lord, J S; McKenzie, I; Adjizian, J-J; Heggie, M I; Jayasooriya, U A; Grinter, R; Reid, I D

    2011-08-10

    The nature of the elusive muonium centre in sulphur is re-examined in the light of new data on its level-crossing resonance and spin-lattice relaxation. The aim is to provide a model for the solid-state chemistry of interstitial hydrogen in this element, which is as yet unknown, as well as to solve one of the longest standing puzzles in μSR spectroscopy, namely the surprisingly strong depolarization of muons mimicking ion-implanted protons in this innocuous non-magnetic material. The paramagnetic muonium (and by inference hydrogen) centre is confirmed to have the character of a molecular radical, but with huge anisotropy at cryogenic temperatures and a striking shift of the resonance at ordinary temperatures, the hyperfine parameters appearing to collapse and vanish towards the melting point. New density-functional supercell calculations identify a number of possible structures for the defect centre, including a novel form of bond-centred muonium in a closed-ring S(8)Mu complex. Simulations of the spin dynamics and fits to the spectra suggest a dynamical equilibrium or chemical exchange between several configurations, with occupancy of the bond-centre site falling from unity at low cryogenic temperatures to zero near the melting point.

  17. Synthesis, characterization, and modeling of hydrogen storage in carbon aerogels

    SciTech Connect

    Pekala, R.W.; Coronado, P.R.; Calef, D.F.

    1995-04-01

    Carbon aerogels are a special class of open-cell foams with an ultrafine cell/pore size (<50 nm), high surface area (600-800 m{sup 2}/g), and a solid matrix composed of interconnected colloidal-like particles or fibers with characteristic diameters of 10 nm. These materials are usually synthesized from the sol-gel polymerization of resorcinol-formaldehyde or phenolic-furfural, followed by supercritical extraction of the solvent and pyrolysis in an inert atmosphere. The resultant aerogel has a nanocrystalline structure with micropores (<2 nm diameter) located within the solid matrix. Carbon aerogel monoliths can be prepared at densities ranging from 0.05-1.0 g/cm{sup 3}, leading to volumetric surface areas (> 500 m{sup 2}/cm{sup 3}) that are much larger than commercially available materials. This research program is directed at optimization of the aerogel structure for maximum hydrogen adsorption over a wide range of temperatures and pressures. Computer modeling of hydrogen adsorption at carbon surfaces was also examined.

  18. Validation of a reduced-order jet model for subsonic and underexpanded hydrogen jets

    SciTech Connect

    Li, Xuefang; Hecht, Ethan S.; Christopher, David M.

    2016-01-01

    Much effort has been made to model hydrogen releases from leaks during potential failures of hydrogen storage systems. A reduced-order jet model can be used to quickly characterize these flows, with low computational cost. Notional nozzle models are often used to avoid modeling the complex shock structures produced by the underexpanded jets by determining an “effective” source to produce the observed downstream trends. In our work, the mean hydrogen concentration fields were measured in a series of subsonic and underexpanded jets using a planar laser Rayleigh scattering system. Furthermore, we compared the experimental data to a reduced order jet model for subsonic flows and a notional nozzle model coupled to the jet model for underexpanded jets. The values of some key model parameters were determined by comparisons with the experimental data. Finally, the coupled model was also validated against hydrogen concentrations measurements for 100 and 200 bar hydrogen jets with the predictions agreeing well with data in the literature.

  19. Hydrogen peroxide and peracetic acid determination in waste water using a reversible reagentless biosensor.

    PubMed

    Sanz, Vanesa; de Marcos, Susana; Galbán, Javier

    2007-02-05

    During the reversible reaction between peroxidase (HRP) and peroxides, several peroxidase intermediate species, showing different molecular absorption spectra, are formed which can be used for their determination. On this basis, a reversible reagentless optical biosensor based on HRP for hydrogen peroxide and peracetic acid determinations has been developed. The biosensor (which can be used for at least 3 months and/or more than 200 measurements) is prepared by HRP entrapment in a polyacrylamide gel matrix. A mathematical model (in which optical, kinetic and transport aspects are considered) relating the measured absorbance with the analyte concentration is also presented. Both peroxides show similar responses in the sensor film. Under the recommended working conditions, the biosensor shows linear response ranges from 6x10(-7) to 1.0x10(-4) M using FIA mode, and from 2x10(-7) to 1.5x10(-5) M using continuous mode for both peroxides; the precision, expressed as R.S.D., is about 4%. This biosensor has been applied for peroxide determination in waste water samples previously treated with peroxides.

  20. Water-Ammonia Ionic Ocean on Uranus and Neptune-Clue from Tropospheric Hydrogen Sulfide Clouds

    NASA Astrophysics Data System (ADS)

    Atreya, S. K.; Egeler, P. A.; Wong, A.

    2005-12-01

    Interior models of the ice-giants, Uranus and Neptune, predict a water-ammonia ionic ocean at tens of kilobar pressure [1,2]. If correct, its implication for planetary formation models is profound. In this presentation we demonstrate that the existence of an ionic ocean will manifest itself in the planets' tropospheric cloud structure, particularly in the form of a hydrogen sulfide, i.e. H2S-ice, cloud. In fact, an H2S cloud was introduced ad hoc in the 3-5 bar region to explain microwave absorption [3] and the methane [4] observations, but its presence cannot be proved in the absence of entry probes. Our equilibrium cloud condensation model (ECCM) shows that an H2S-ice cloud does not form when conventional enrichment factors (20-30× solar at Uranus, and 30-50× solar at Neptune) are employed for all heavy elements (mass >4) [5]. However, a deep ``cloud'' composed of a weak solution of ammonia and water forms, and its base is at 370 and 500 bars, respectively, for 30× solar and 50× solar enrichment factors. If an ionic ``ocean'' exists much deeper, water vapor, as well as ammonia dissolved in it, would be severely depleted at levels above this ocean. The consequences of such water vapor and ammonia depletions are that (1) clouds of water and ammonia, if present, are much less prominent; (2) only small amount of H2S vapor is removed by NH3, to form an NH4SH cloud; so that (3) a cloud of H2S-ice can now form; and (4) an H2O ``ocean'' in the 1-kilobar region [6] does not form. This scenario has important implications for the design of entry probe missions, as measurements to only 10-20 bars, rather than kilobar levels, will need to be made. The heavy elements, Ar, Kr, Xe, Ne, C, and S, as well as He, D/H, GeH4, AsH3, PH3, and CO can all be accessed at pressures less than 20 bars. These measurements are critical for constraining the formation models [5,7,8]. Measurement of water in the well-mixed region of Uranus and Neptune is technologically highly challenging

  1. Investigation of heat and mass transfer process in metal hydride hydrogen storage reactors, suitable for a solar powered water pump system

    NASA Astrophysics Data System (ADS)

    Coldea, I.; Popeneciu, G.; Lupu, D.; Misan, I.; Blanita, G.; Ardelean, O.

    2012-02-01

    The paper analyzes heat and mass transfer process in metal hydride hydrogen storage systems as key element in the development of a solar powered pump system. Hydrogen storage and compression performance of the developed reactors are investigated according to the type of metal alloys, the metal hydride bed parameters and system operating conditions. To reach the desired goal, some metal hydride from groups AB5 and AB2 were synthesized and characterized using elements substitution for tailoring their properties: reversible hydrogen absorption capacity between the hydrogen absorption and desorption pressures at equilibrium at small temperature differences. For the designed hydrogen storage reactors, a new technical solution which combines the effective increase of the thermal conductivity of MH bed and good permeability to hydrogen gas circulation, was implemented and tested. The results permitted us to develop a heat engine with metal hydride, the main element of the functional model of a heat operated metal hydride based water pumping system using solar energy. This is a free energy system able to deliver water, at a convenience flow and pressure, in remote places without conventional energy access.

  2. Water Distribution and Removal Model

    SciTech Connect

    Y. Deng; N. Chipman; E.L. Hardin

    2005-08-26

    The design of the Yucca Mountain high level radioactive waste repository depends on the performance of the engineered barrier system (EBS). To support the total system performance assessment (TSPA), the Engineered Barrier System Degradation, Flow, and Transport Process Model Report (EBS PMR) is developed to describe the thermal, mechanical, chemical, hydrological, biological, and radionuclide transport processes within the emplacement drifts, which includes the following major analysis/model reports (AMRs): (1) EBS Water Distribution and Removal (WD&R) Model; (2) EBS Physical and Chemical Environment (P&CE) Model; (3) EBS Radionuclide Transport (EBS RNT) Model; and (4) EBS Multiscale Thermohydrologic (TH) Model. Technical information, including data, analyses, models, software, and supporting documents will be provided to defend the applicability of these models for their intended purpose of evaluating the postclosure performance of the Yucca Mountain repository system. The WD&R model ARM is important to the site recommendation. Water distribution and removal represents one component of the overall EBS. Under some conditions, liquid water will seep into emplacement drifts through fractures in the host rock and move generally downward, potentially contacting waste packages. After waste packages are breached by corrosion, some of this seepage water will contact the waste, dissolve or suspend radionuclides, and ultimately carry radionuclides through the EBS to the near-field host rock. Lateral diversion of liquid water within the drift will occur at the inner drift surface, and more significantly from the operation of engineered structures such as drip shields and the outer surface of waste packages. If most of the seepage flux can be diverted laterally and removed from the drifts before contacting the wastes, the release of radionuclides from the EBS can be controlled, resulting in a proportional reduction in dose release at the accessible environment. The purposes

  3. Electrodeposited cobalt-sulfide catalyst for electrochemical and photoelectrochemical hydrogen generation from water.

    PubMed

    Sun, Yujie; Liu, Chong; Grauer, David C; Yano, Junko; Long, Jeffrey R; Yang, Peidong; Chang, Christopher J

    2013-11-27

    A cobalt-sulfide (Co-S) film prepared via electrochemical deposition on conductive substrates is shown to behave as an efficient and robust catalyst for electrochemical and photoelectrochemical hydrogen generation from neutral pH water. Electrochemical experiments demonstrate that the film exhibits a low catalytic onset overpotential (η) of 43 mV, a Tafel slope of 93 mV/dec, and near 100% Faradaic efficiency in pH 7 phosphate buffer. Catalytic current densities can approach 50 mA/cm(2) and activity is maintained for at least 40 h. The catalyst can also be electrochemically coated on silicon, rendering a water-compatible photoelectrochemical system for hydrogen production under simulated 1 sun illumination. The facile preparation of this Co-S film, along with its low overpotential, high activity, and long-term aqueous stability, offer promising features for potential use in solar energy applications.

  4. Case study of hydrogen water chemistry implementation at the Duane Arnold Energy Center

    SciTech Connect

    Leibel, T.A.; Turley, D.S. ); Steen, A. )

    1989-01-01

    This paper presents a case study of the hydrogen water chemistry (HWC) program implemented at Duane Arnold Energy Center (DAEC). In 1985 various reactor recirculation system piping weld repairs and safe end replacements were performed at the DAEC. These weld repairs and safe-end replacements were required as a result of inter-granular stress corrosion cracking (IGSCC). In 1986, the utility decided to implement a hydrogen water chemistry program as a means of suppressing IGSCC. The paper includes a discussion of the system design basis, a brief system description, and a discussion of plant system interactions. A description of methodology developed to verify and monitor the effectiveness of the HWC system is also included.

  5. Fast Interconversion of Hydrogen Bonding at the Hematite (001)–Liquid Water Interface

    SciTech Connect

    von Rudorff, Guido Falk; Jakobsen, Rasmus; Rosso, Kevin M.; Blumberger, Jochen

    2016-04-07

    The interface between transition-metal oxides and aqueous solutions plays an important role in biogeochemistry and photoelectrochemistry, but the atomistic structure is often elusive. Here we report on the surface geometry, solvation structure, and thermal fluctuations of the hydrogen bonding network at the hematite (001)–water interface as obtained from hybrid density functional theory-based molecular dynamics. We find that the protons terminating the surface form binary patterns by either pointing in-plane or out-of-plane. The patterns exist for about 1 ps and spontaneously interconvert in an ultrafast, solvent-driven process within 50 fs. This results in only about half of the terminating protons pointing toward the solvent and being acidic. The lifetimes of all hydrogen bonds formed at the interface are shorter than those in pure liquid water. The solvation structure reported herein forms the basis for a better fundamental understanding of electron transfer coupled to proton transfer reactions at this important interface.

  6. Do-It-Yourself: 3D Models of Hydrogenic Orbitals through 3D Printing

    ERIC Educational Resources Information Center

    Griffith, Kaitlyn M.; de Cataldo, Riccardo; Fogarty, Keir H.

    2016-01-01

    Introductory chemistry students often have difficulty visualizing the 3-dimensional shapes of the hydrogenic electron orbitals without the aid of physical 3D models. Unfortunately, commercially available models can be quite expensive. 3D printing offers a solution for producing models of hydrogenic orbitals. 3D printing technology is widely…

  7. Molecular simulation of diffusion of hydrogen, carbon monoxide, and water in heavy n-alkanes.

    PubMed

    Makrodimitri, Zoi A; Unruh, Dominik J M; Economou, Ioannis G

    2011-02-17

    The self-diffusion and mutual diffusion coefficients of hydrogen (H(2)), carbon monoxide (CO), and water (H(2)O) in n-alkanes were studied by molecular dynamics simulation. n-Alkane molecules were modeled based on the TraPPE united atom force field. NPT molecular dynamics (MD) simulations were performed for n-C(12) to n-C(96) at different temperature and pressure values to validate the accuracy of the force field. In all cases, good agreement was obtained between literature experimental data and model predictions for the density and structure properties of the n-alkanes. Subsequently, the self-diffusion coefficient of the three light components in the various n-alkanes was calculated at different temperatures. Model predictions were in very good agreement with limited experimental data. Furthermore, the Maxwell-Stefan diffusion coefficients of H(2) and CO in two n-alkanes, namely n-C(12) and n-C(28), were calculated based on long MD NVT simulations for different solute concentrations in the n-alkanes. Finally, the Fick diffusion coefficient of the components was calculated as a product of the Maxwell-Stefan diffusion coefficient and a thermodynamic factor. The latter was estimated from the statistical associating fluid theory (SAFT). The Fick diffusion coefficient was found to be higher than the Maxwell-Stefan diffusion coefficient for H(2) and CO in n-C(28). The empirical Darken equation was used to estimate the Maxwell-Stefan diffusion coefficient, and calculations were found to be in good agreement with simulation results.

  8. Rapid reduction of N-nitrosamine disinfection byproducts in water with hydrogen and porous nickel catalysts.

    PubMed

    Frierdich, Andrew J; Shapley, John R; Strathmann, Timothy J

    2008-01-01

    There is a need for new technologies to rapidly and economically treatwater contaminated with N-nitrosodimethylamine (NDMA) and related compounds because of their high toxicity and recent detection in drinking water sources as a consequence of industrial releases and chlorine disinfection of wastewater effluent Treatment of N-nitrosamines with H2 in conjunction with a high surface area porous nickel material, a model nonprecious metal catalyst, has been evaluated. Experiments show that NDMA is reduced rapidly and catalytically to dimethylamine and N2 (e.g., t1/2 = 1.5 min for 500 mg/L catalyst and PH2 = 1 atm), and kinetic trends are consistent with a surface-mediated mechanism involving scission of the N-nitrosamine N-N bond and subsequent reactions with adsorbed atomic hydrogen. The metal-loading-normalized pseudo-first-order rate constant (77.9 +/- 13.1 L g(Ni)(-1) h(-1)) exceeds values reported for Pd-based catalysts. Several related N-nitrosamines react at rates similar to those of NDMA, indicating a weak dependence on structure. The reaction rates for NDMA reduction are not significantly affected by changing pH, and the presence of high concentrations of many common water constituents (Na+, Ca2+, Mg2+, Cl-, SO4(2-), HCO(3-), and NOM) exerts only a small effect on reaction rates. Nitrate is also reduced by the Ni catalyst, and high nitrate concentrations competitively inhibit the reduction of NDMA. (Bi)sulfide poisons the catalyst by strong chemisorption to the Ni surface. Cost-normalized rate constants for the Ni catalyst are highly favorable compared to Pd-based catalysts, indicating that, with further development, Ni-based catalysts may become attractive alternatives to precious metal catalysts.

  9. Modelling of Impulsional pH Variations Using ChemFET-Based Microdevices: Application to Hydrogen Peroxide Detection

    PubMed Central

    Diallo, Abdou Karim; Djeghlaf, Lyes; Launay, Jerome; Temple-Boyer, Pierre

    2014-01-01

    This work presents the modelling of impulsional pH variations in microvolume related to water-based electrolysis and hydrogen peroxide electrochemical oxidation using an Electrochemical Field Effect Transistor (ElecFET) microdevice. This ElecFET device consists of a pH-Chemical FET (pH-ChemFET) with an integrated microelectrode around the dielectric gate area in order to trigger electrochemical reactions. Combining oxidation/reduction reactions on the microelectrode, water self-ionization and diffusion properties of associated chemical species, the model shows that the sensor response depends on the main influential parameters such as: (i) polarization parameters on the microelectrode, i.e., voltage (Vp) and time (tp); (ii) distance between the gate sensitive area and the microelectrode (d); and (iii) hydrogen peroxide concentration ([H2O2]). The model developed can predict the ElecFET response behaviour and creates new opportunities for H2O2-based enzymatic detection of biomolecules. PMID:24556666

  10. Characterization of the hydrogen-bond network of water around sucrose and trehalose: Microwave and terahertz spectroscopic study.

    PubMed

    Shiraga, Keiichiro; Adachi, Aya; Nakamura, Masahito; Tajima, Takuro; Ajito, Katsuhiro; Ogawa, Yuichi

    2017-03-14

    Modification of the water hydrogen bond network imposed by disaccharides is known to serve as a bioprotective agent in living organisms, though its comprehensive understanding is still yet to be reached. In this study, aiming to characterize the dynamical slowing down and destructuring effect of disaccharides, we performed broadband dielectric spectroscopy, ranging from 0.5 GHz to 12 THz, of sucrose and trehalose aqueous solutions. The destructuring effect was examined in two ways (the hydrogen bond fragmentation and disordering) and our result showed that both sucrose and trehalose exhibit an obvious destructuring effect with a similar strength, by fragmenting hydrogen bonds and distorting the tetrahedral-like structure of water. This observation strongly supports a chaotropic (structure-breaking) aspect of disaccharides on the water structure. At the same time, hydration water was found to exhibit slower dynamics and a greater reorientational cooperativity than bulk water because of the strengthened hydrogen bonds. These results lead to the conclusion that strong disaccharide-water hydrogen bonds structurally incompatible with native water-water bonds lead to the rigid but destructured hydrogen bond network around disaccharides. Another important finding in this study is that the greater dynamical slowing down of trehalose was found compared with that of sucrose, at variance with the destructuring effect where no solute dependent difference was observed. This discovery suggests that the exceptionally greater bioprotective impact especially of trehalose among disaccharides is mainly associated with the dynamical slowing down (rather than the destructuring effect).

  11. Characterization of the hydrogen-bond network of water around sucrose and trehalose: Microwave and terahertz spectroscopic study

    NASA Astrophysics Data System (ADS)

    Shiraga, Keiichiro; Adachi, Aya; Nakamura, Masahito; Tajima, Takuro; Ajito, Katsuhiro; Ogawa, Yuichi

    2017-03-01

    Modification of the water hydrogen bond network imposed by disaccharides is known to serve as a bioprotective agent in living organisms, though its comprehensive understanding is still yet to be reached. In this study, aiming to characterize the dynamical slowing down and destructuring effect of disaccharides, we performed broadband dielectric spectroscopy, ranging from 0.5 GHz to 12 THz, of sucrose and trehalose aqueous solutions. The destructuring effect was examined in two ways (the hydrogen bond fragmentation and disordering) and our result showed that both sucrose and trehalose exhibit an obvious destructuring effect with a similar strength, by fragmenting hydrogen bonds and distorting the tetrahedral-like structure of water. This observation strongly supports a chaotropic (structure-breaking) aspect of disaccharides on the water structure. At the same time, hydration water was found to exhibit slower dynamics and a greater reorientational cooperativity than bulk water because of the strengthened hydrogen bonds. These results lead to the conclusion that strong disaccharide-water hydrogen bonds structurally incompatible with native water-water bonds lead to the rigid but destructured hydrogen bond network around disaccharides. Another important finding in this study is that the greater dynamical slowing down of trehalose was found compared with that of sucrose, at variance with the destructuring effect where no solute dependent difference was observed. This discovery suggests that the exceptionally greater bioprotective impact especially of trehalose among disaccharides is mainly associated with the dynamical slowing down (rather than the destructuring effect).

  12. COMPILATION OF GROUND WATER MODELS

    EPA Science Inventory

    The full report presents an overview of currently available computer-based simulation models for ground-water flow, solute and heat transport, and hydrogeochemistry in both porous media and fractured rock. Separate sections address multiphase flow and related chemical species tra...

  13. Lake Louise Water (USGS47): A new isotopic reference water for stable hydrogen and oxygen isotope measurements

    USGS Publications Warehouse

    Qi, Haiping; Lorenz, Jennifer M.; Coplen, Tyler B.; Tarbox, Lauren V.; Mayer, Bernhard; Taylor, Steve

    2014-01-01

    RESULTS: The δ2H and δ18O values of this reference water are –150.2 ± 0.5 ‰ and –19.80 ± 0.02 ‰, respectively, relative to VSMOW on scales normalized such that the δ2H and δ18O values of SLAP reference water are, respectively, –428 and –55.5 ‰. Each uncertainty is an estimated expanded uncertainty (U = 2uc) about the reference value that provides an interval that has about a 95-percent probability of encompassing the true value. CONCLUSION: This isotopic reference material, designated as USGS47, is intended as one of two isotopic reference waters for daily normalization of stable hydrogen and stable oxygen isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. "

  14. Performance of wave function and density functional methods for water hydrogen bond spin-spin coupling constants.

    PubMed

    García de la Vega, J M; Omar, S; San Fabián, J

    2017-04-01

    Spin-spin coupling constants in water monomer and dimer have been calculated using several wave function and density functional-based methods. CCSD, MCSCF, and SOPPA wave functions methods yield similar results, specially when an additive approach is used with the MCSCF. Several functionals have been used to analyze their performance with the Jacob's ladder and a set of functionals with different HF exchange were tested. Functionals with large HF exchange appropriately predict (1) J O H , (2) J H H and (2h) J O O couplings, while (1h) J O H is better calculated with functionals that include a reduced fraction of HF exchange. Accurate functionals for (1) J O H and (2) J H H have been tested in a tetramer water model. The hydrogen bond effects on these intramolecular couplings are additive when they are calculated by SOPPA(CCSD) wave function and DFT methods. Graphical Abstract Evaluation of the additive effect of the hydrogen bond on spin-spin coupling constants of water using WF and DFT methods.

  15. Metal-encapsulated organolead halide perovskite photocathode for solar-driven hydrogen evolution in water.

    PubMed

    Crespo-Quesada, Micaela; Pazos-Outón, Luis M; Warnan, Julien; Kuehnel, Moritz F; Friend, Richard H; Reisner, Erwin

    2016-09-06

    Lead-halide perovskites have triggered the latest breakthrough in photovoltaic technology. Despite the great promise shown by these materials, their instability towards water even in the presence of low amounts of moisture makes them, a priori, unsuitable for their direct use as light harvesters in aqueous solution for the production of hydrogen through water splitting. Here, we present a simple method that enables their use in photoelectrocatalytic hydrogen evolution while immersed in an aqueous solution. Field's metal, a fusible InBiSn alloy, is used to efficiently protect the perovskite from water while simultaneously allowing the photogenerated electrons to reach a Pt hydrogen evolution catalyst. A record photocurrent density of -9.8 mA cm(-2) at 0 V versus RHE with an onset potential as positive as 0.95±0.03 V versus RHE is obtained. The photoelectrodes show remarkable stability retaining more than 80% of their initial photocurrent for ∼1 h under continuous illumination.

  16. Sulfur transformations at the hydrogen sulfide/oxygen interface in stratified waters and in cyanobacterial mats

    NASA Technical Reports Server (NTRS)

    Cohen, Y.

    1985-01-01

    Stratified water bodies allow the development of several microbial plates along the water column. The microbial plates develop in relation to nutrient availability, light penetration, and the distribution of oxygen and sulfide. Sulfide is initially produced in the sediment by sulfate-reducing bacteria. It diffuses along the water column creating a zone of hydrogen sulfide/oxygen interface. In the chemocline of Solar Lake oxygen and sulfide coexist in a 0 to 10 cm layer that moves up and down during a diurnal cycle. The microbial plate at the chemocline is exposed to oxygen and hydrogen sulfide, alternating on a diurnal basis. The cyanobacteria occupying the interface switch from anoxygenic photosynthesis in the morning to oxygenic photosynthesis during the rest of the day which results in a temporal build up of elemental sulfur during the day and disappears at night due to both oxidation to thiosulfate and sulfate by thiobacilli, and reduction to hydrogen sulfide by Desulfuromonas sp. and anaerobically respiring cyanobacteria. Sulfate reduction was enhanced in the light at the surface of the cyanobacterial mats. Microsulfate reduction measurements showed enhanced activity of sulfate reduction even under high oxygen concentrations of 300 to 800 micrometer. Apparent aerobic SO sub 4 reduction activity is explained by the co-occurrence of H sub 2. The physiology of this apparent sulfate reduction activity is studied.

  17. Metal-encapsulated organolead halide perovskite photocathode for solar-driven hydrogen evolution in water

    PubMed Central

    Crespo-Quesada, Micaela; Pazos-Outón, Luis M.; Warnan, Julien; Kuehnel, Moritz F.; Friend, Richard H.; Reisner, Erwin

    2016-01-01

    Lead-halide perovskites have triggered the latest breakthrough in photovoltaic technology. Despite the great promise shown by these materials, their instability towards water even in the presence of low amounts of moisture makes them, a priori, unsuitable for their direct use as light harvesters in aqueous solution for the production of hydrogen through water splitting. Here, we present a simple method that enables their use in photoelectrocatalytic hydrogen evolution while immersed in an aqueous solution. Field's metal, a fusible InBiSn alloy, is used to efficiently protect the perovskite from water while simultaneously allowing the photogenerated electrons to reach a Pt hydrogen evolution catalyst. A record photocurrent density of −9.8 mA cm−2 at 0 V versus RHE with an onset potential as positive as 0.95±0.03 V versus RHE is obtained. The photoelectrodes show remarkable stability retaining more than 80% of their initial photocurrent for ∼1 h under continuous illumination. PMID:27595974

  18. Hydrogen production by the naked active site of the di-iron hydrogenases in water.

    PubMed

    Zipoli, Federico; Car, Roberto; Cohen, Morrel H; Selloni, Annabella

    2009-10-01

    We explored the reactivity of the active center of the [FeFe]-hydrogenases detached from the enzyme and immersed in acidified water by first-principles Car-Parrinello molecular-dynamics simulations. We focused on the identification of the structures that are stable and metastable in acidified water and on their activity for hydrogen production. Our calculations revealed that the naked active center could be an efficient catalyst provided that electrons are transferred to the cluster. We found that both bridging and terminal isomers are present at equilibrium and that the bridging configuration is essential for efficient hydrogen production. The formation of the hydrogen molecule occurs via sequential protonations of the distal iron and of the N-atom of the S-CH(2)-NH-CH(2)-S chelating group. H(2) desorption does not involve a significant energy barrier, making the process very efficient at room temperature. We established that the bottleneck in the reaction is the direct proton transfer from water to the vacant site of the distal iron. Moreover, we found that even if the terminal isomer is present at the equilibrium, its strong local hydrophobicity prevents poisoning of the cluster.

  19. Oxygen tolerance of an in silico-designed bioinspired hydrogen-evolving catalyst in water.

    PubMed

    Sit, Patrick H-L; Car, Roberto; Cohen, Morrel H; Selloni, Annabella

    2013-02-05

    Certain bacterial enzymes, the diiron hydrogenases, have turnover numbers for hydrogen production from water as large as 10(4)/s. Their much smaller common active site, composed of earth-abundant materials, has a structure that is an attractive starting point for the design of a practical catalyst for electrocatalytic or solar photocatalytic hydrogen production from water. In earlier work, our group has reported the computational design of [FeFe](P)/FeS(2), a hydrogenase-inspired catalyst/electrode complex, which is efficient and stable throughout the production cycle. However, the diiron hydrogenases are highly sensitive to ambient oxygen by a mechanism not yet understood in detail. An issue critical for practical use of [FeFe](P)/FeS(2) is whether this catalyst/electrode complex is tolerant to the ambient oxygen. We report demonstration by ab initio simulations that the complex is indeed tolerant to dissolved oxygen over timescales long enough for practical application, reducing it efficiently. This promising hydrogen-producing catalyst, composed of earth-abundant materials and with a diffusion-limited rate in acidified water, is efficient as well as oxygen tolerant.

  20. Physics beyond the Standard Model from hydrogen spectroscopy

    NASA Astrophysics Data System (ADS)

    Ubachs, W.; Koelemeij, J. C. J.; Eikema, K. S. E.; Salumbides, E. J.

    2016-02-01

    Spectroscopy of hydrogen can be used for a search into physics beyond the Standard Model. Differences between the absorption spectra of the Lyman and Werner bands of H2 as observed at high redshift and those measured in the laboratory can be interpreted in terms of possible variations of the proton-electron mass ratio μ =mp /me over cosmological history. Investigation of ten such absorbers in the redshift range z = 2.0 -4.2 yields a constraint of | Δμ / μ | < 5 ×10-6 at 3σ. Observation of H2 from the photospheres of white dwarf stars inside our Galaxy delivers a constraint of similar magnitude on a dependence of μ on a gravitational potential 104 times as strong as on the Earth's surface. While such astronomical studies aim at finding quintessence in an indirect manner, laboratory precision measurements target such additional quantum fields in a direct manner. Laser-based precision measurements of dissociation energies, vibrational splittings and rotational level energies in H2 molecules and their deuterated isotopomers HD and D2 produce values for the rovibrational binding energies fully consistent with quantum ab initio calculations including relativistic and quantum electrodynamical (QED) effects. Similarly, precision measurements of high-overtone vibrational transitions of HD+ ions, captured in ion traps and sympathetically cooled to mK temperatures, also result in transition frequencies fully consistent with calculations including QED corrections. Precision measurements of inter-Rydberg transitions in H2 can be extrapolated to yield accurate values for level splittings in the H2+ -ion. These comprehensive results of laboratory precision measurements on neutral and ionic hydrogen molecules can be interpreted to set bounds on the existence of possible fifth forces and of higher dimensions, phenomena describing physics beyond the Standard Model.

  1. Hydrogen isotope exchange between n-alkanes and water under hydrothermal conditions

    NASA Astrophysics Data System (ADS)

    Reeves, Eoghan P.; Seewald, Jeffrey S.; Sylva, Sean P.

    2012-01-01

    To investigate the extent of hydrogen isotope (2H and 1H) exchange between hydrocarbons and water under hydrothermal conditions, we performed experiments heating C1-C5n-alkanes in aqueous solutions of varying initial 2H/1H ratios in the presence of a pyrite-pyrrhotite-magnetite redox buffer at 323 °C and 35-36 MPa. Extensive and reversible incorporation of water-derived hydrogen into C2-C5n-alkanes was observed on timescales of months. In contrast, comparatively minor exchange was observed for CH4. Isotopic exchange is facilitated by reversible equilibration of n-alkanes and their corresponding n-alkenes with H2 derived from the disproportionation of water. Rates of δ2H variation in C3+n-alkanes decreased with time, a trend that is consistent with an asymptotic approach to steady state isotopic compositions regulated by alkane-water isotopic equilibrium. Substantially slower δ2H variation was observed for ethane relative to C3-C5n-alkanes, suggesting that the greater stability of C3+ alkenes and isomerization reactions may dramatically enhance rates of 2H/1H exchange in C3+n-alkanes. Thus, in reducing aqueous environments, reversible reaction of alkanes and their corresponding alkenes facilitates rapid 2H/1H exchange between water and alkyl-bound hydrogen on relatively short geological timescales at elevated temperatures and pressures. The proximity of some thermogenic and purported abiogenic alkane δ2H values to those predicted for equilibrium 2H/1H fractionation with ambient water suggests that this process may regulate the δ2H signatures of some naturally occurring hydrocarbons.

  2. 2 W power source based on air-hydrogen polymer electrolyte membrane fuel cells and water-aluminum hydrogen micro-generator

    NASA Astrophysics Data System (ADS)

    Shkolnikov, Eugene; Vlaskin, Mikhail; Iljukhin, Alexey; Zhuk, Andrey; Sheindlin, Alexander

    The article presents an attempt to design the 2 W power source (PS) based on air-hydrogen fuel cells (FCs) and water-aluminium micro-generator as a hydrogen supply (WAHMG). Experiments concern FC's breathing in compact arrangement and combined performance of FC + WAHMG. It turned out to be necessary to build a fan into FC stack provided the rotation speed of fan depends on the FC current. The highest power density of FC at optimal speed of air blowing was 101 mW cm -2. Electrical energy produced by FC was about 1.2-1.8 Wh per gram of Al in micro-generator. This value depends on the total yield of hydrogen in WAHMG and hydrogen losses due to purges.

  3. Life cycle water footprint of hydrogenation-derived renewable diesel production from lignocellulosic biomass.

    PubMed

    Wong, Alain; Zhang, Hao; Kumar, Amit

    2016-10-01

    The conversion of lignocellulosic biomass to biofuel requires water. This study is focused on the production of hydrogenation-derived renewable diesel (HDRD) from lignocellulosic biomass. Although there has been considerable focus on the assessment of greenhouse gas (GHG) emissions, there is limited work on the assessment of the life cycle water footprint of HDRD production. This paper presents a life cycle water consumption study on lignocellulosic biomass to HDRD via pyrolysis and hydrothermal liquefaction (HTL) processes. The results of this study show that whole tree (i.e., tree chips) biomass has water requirements of 497.79 L/MJ HDRD and 376.16 L/MJ HDRD for production through fast pyrolysis and the HTL process, respectively. Forest residues (i.e., chips from branches and tops generated during logging operations) have water requirements of 338.58 L/MJ HDRD and 255.85 L/MJ HDRD for production through fast pyrolysis and the HTL process, respectively. Agricultural residues (i.e., straw from wheat, oats, and barley), which are more water efficient, have water requirements of 83.7 L/MJ HDRD and 59.1 L/MJ HDRD through fast pyrolysis and the HTL process, respectively. Differences in water use between feedstocks and conversion processes indicate that the choices of biomass feedstock and conversion pathway water efficiency are crucial factors affecting water use efficiency of HDRD production.

  4. Tracer study of oxygen and hydrogen uptake by Mg alloys in air with water vapor

    DOE PAGES

    Brady, M. P.; Fayek, M.; Meyer, H. M.; ...

    2015-05-15

    We studied the pure oxidation of Mg, Mg–3Al–1Zn (AZ31B), and Mg–1Zn–0.25Zr–<0.5Nd (ZE10A) at 85 °C in humid air using sequential exposures with H218O and D216O for water vapor. Incorporation of 18O in the hydroxide/oxide films indicated that oxygen from water vapor participated in the reaction. Moreover, penetration of hydrogen into the underlying metal was observed, particularly for the Zr- and Nd-containing ZE10A. Isotopic tracer profiles suggested a complex mixed inward/outward film growth mechanism.

  5. Occurrence and distribution of color and hydrogen sulfide in water of the principal artesian aquifers in the Valdosta area, Georgia

    USGS Publications Warehouse

    Krause, Richard E.

    1976-01-01

    Hydrogen sulfide and color occur in objectionable amounts in ground water from the principal artesian aquifer in the Valdosta , Ga., area. Generally, water from wells south of Valdosta is high in hydrogen sulfide; water from wells north of the city is high in color. Water with high sulfate is likely to be a problem in wells deeper than about 540 ft. Heavy pumpage concentrated in a small area may cause high-sulfate water to migrate vertically upward into shallower wells. (Woodard-USGS)

  6. Interaction of hydrogen chloride and water with oxide surfaces. III - Titanium dioxide

    NASA Technical Reports Server (NTRS)

    Siriwardane, R. V.; Wightman, J. P.

    1983-01-01

    The adsorption of hydrogen chloride and water vapors on five TiO2 powders in both the anatase and rutile crystalline forms was studied as a function of temperature, pressure, and outgas conditions. The adsorbents were characterized utilizing X-ray powder diffraction, scanning electron microscopy, surface area analysis, indicator method, microelectrophoresis, XPS, and infrared spectroscopy. It was found that both outgas temperature and adsorption temperature influenced the adsorption of water vapor on TiO2, while water vapor adsorption on TiO2 was completely reversible. It is argued that the number of hydroxyl groups present on the surface determines the adsorption capacity of water on the different titanium dioxides. It was found that heats of immersion in water were affected significantly by outgas temperature. Hydrogen chloride adsorption isotherms at 30 C measured on TiO2 after outgassing at 100-400 C showed that a part of the total HCl adsorbed was irreversibly adsorbed. The highest HCl adsorption capacity per unit area was exhibited by anatase, while pure rutile exhibited the lowest adsorption capacity.

  7. Effects of shock and Martian alteration on Tissint hydrogen isotope ratios and water content

    NASA Astrophysics Data System (ADS)

    Hallis, L. J.; Huss, G. R.; Nagashima, K.; Taylor, G. J.; Stöffler, D.; Smith, C. L.; Lee, M. R.

    2017-03-01

    The Tissint meteorite, a picritic shergottite, fell to Earth in Morocco on the 18th of July 2011, and is only the fifth Martian meteorite witnessed to fall. Hydrogen isotope ratios and water contents are variable within different minerals in Tissint. Ringwoodite and shock melt pockets contain elevated D/H ratios relative to terrestrial values (δD = 761-4224‰). These high ratios in recrystallized phases indicate significant implantation of hydrogen from the D-rich Martian atmosphere during shock. In contrast, although olivine has detectable water abundances (230-485 ppm), it exhibits much lower D/H ratios (δD = +88 to -150‰), suggesting this water was not implanted from the Martian atmosphere. The minimal terrestrial weathering experienced by Tissint gives confidence that the olivine-hosted water has a Martian origin, but its high concentration indicates direct inheritance from the parental melt is improbable, especially given the low pressure of olivine crystallisation. Incorporation of a low δD crustal fluid, or deuteric alteration during crystallisation, could explain the relatively high water contents and low D/H ratios in Tissint olivine.

  8. Formation and properties of water from quartz and hydrogen at high pressure and temperature

    NASA Astrophysics Data System (ADS)

    Futera, Zdenek; Yong, Xue; Pan, Yuanming; Tse, John S.; English, Niall J.

    2017-03-01

    Quartz, as the most stable low-pressure polymorph of silica (SiO2), is widely abundant in Earth's crust and mantle, exhibiting relatively high chemical stability. Although silica is only slightly soluble in water at ambient conditions, producing silicon-based weakly acidic compounds, Shinozaki et al. (2014) have shown recently that water itself can be formed by dissolution of SiO2 in H2 fluid under high- temperature and pressure conditions. Here, we have simulated this process via molecular-dynamics techniques based on a reactive force-field description of the Si O2 /H2 interface. Diffusion of the H2 fluid into the quartz crystal lattice was observed upon increasing temperature and pressure, followed by interaction of dissociated, atomic hydrogen with oxygen atoms in the SiO2 lattice, disrupting the lattice and leading to the formation of water. Interestingly, water is evolved in the subsurface region of the silica, and it remains confined there, isolated from the hydrogen fluid, which corresponds precisely to the ice-like spectroscopic patterns observed experimentally. The over-pressured water formed from quartz and H2 is a possible trigger for nucleating enigmatic deep earthquakes in the continental mantle lithosphere.

  9. Yield of Ozone, Nitrite Nitrogen and Hydrogen Peroxide Versus Discharge Parameter Using APPJ Under Water

    NASA Astrophysics Data System (ADS)

    Chen, Bingyan; Zhu, Changping; Fei, Juntao; He, Xiang; Yin, Cheng; Wang, Yuan; Gao, Ying; Jiang, Yongfeng; Wen, Wen; Chen, Longwei

    2016-03-01

    Discharge plasma in and in contact with water can be accompanied with ultraviolet radiation and electron impact, thus can generate hydroxyl radicals, ozone, nitrite nitrogen and hydrogen peroxide. In this paper, a non-equilibrium plasma processing system was established by means of an atmospheric pressure plasma jet immersed in water. The hydroxyl intensities and discharge energy waveforms were tested. The results show that the positive and negative discharge energy peaks were asymmetric, where the positive discharge energy peak was greater than the negative one. Meanwhile, the yield of ozone and nitrite nitrogen was enhanced with the increase of both the treatment time and the discharge energy. Moreover, the pH value of treated water was reduced rapidly and maintained at a lower level. The residual concentration of hydrogen peroxide in APPJ treated water was kept at a low level. Additionally, both the efficiency energy ratio of the yield of ozone and nitrite nitrogen and that of the removal of p-nitrophenol increased as a function of discharge energy and discharge voltage. The experimental results were fully analyzed and the chemical reaction equations and the physical processes of discharges in water were given. supported by National Natural Science Foundation of China (Nos. 11274092, 11404092, 61401146), the Nantong Science and Technology Project, Nantong, China (No. BK2014024), the Open Project of Jiangsu Province Key Laboratory of Environmental Engineering, Nanjing, China (No. KF2014001), and the Fundamental Research Funds for the Central Universities of China (No. 2014B11414)

  10. Hydrogen Sensors Boost Hybrids; Today's Models Losing Gas?

    NASA Technical Reports Server (NTRS)

    2005-01-01

    Advanced chemical sensors are used in aeronautic and space applications to provide safety monitoring, emission monitoring, and fire detection. In order to fully do their jobs, these sensors must be able to operate in a range of environments. NASA has developed sensor technologies addressing these needs with the intent of improving safety, optimizing combustion efficiencies, and controlling emissions. On the ground, the chemical sensors were developed by NASA engineers to detect potential hydrogen leaks during Space Shuttle launch operations. The Space Shuttle uses a combination of hydrogen and oxygen as fuel for its main engines. Liquid hydrogen is pumped to the external tank from a storage tank located several hundred feet away. Any hydrogen leak could potentially result in a hydrogen fire, which is invisible to the naked eye. It is important to detect the presence of a hydrogen fire in order to prevent a major accident. In the air, the same hydrogen-leak dangers are present. Stress and temperature changes can cause tiny cracks or holes to form in the tubes that line the Space Shuttle s main engine nozzle. Such defects could allow the hydrogen that is pumped through the nozzle during firing to escape. Responding to the challenges associated with pinpointing hydrogen leaks, NASA endeavored to improve propellant leak-detection capabilities during assembly, pre-launch operations, and flight. The objective was to reduce the operational cost of assembling and maintaining hydrogen delivery systems with automated detection systems. In particular, efforts have been focused on developing an automated hydrogen leak-detection system using multiple, networked hydrogen sensors that are operable in harsh conditions.

  11. SIC-BASED HYDROGEN SELECTIVE MEMBRANES FOR WATER-GAS-SHIFT REACTION

    SciTech Connect

    Paul K.T. Liu

    2003-12-01

    A hydrogen selective membrane as a membrane reactor (MR) can significantly improve the power generation efficiency with a reduced capital and operating cost for the waster-gas-shift reaction. Existing hydrogen selective ceramic membranes are not suitable for the proposed MR due to their poor hydrothermal stability. In this project we have focused on the development of innovative silicon carbide (SiC) based hydrogen selective membranes, which can potentially overcome this technical barrier. SiC macro-porous membranes have been successfully fabricated via extrusion of commercially available SiC powder. Also, an SiC hydrogen selective thin film was prepared via our CVD/I technique. This composite membrane demonstrated excellent hydrogen selectivity at high temperature ({approx}600 C). More importantly, this membrane also exhibited a much improved hydrothermal stability at 600 C with 50% steam (atmospheric pressure) for nearly 100 hours. In parallel, we have explored an alternative approach to develop a H{sub 2} selective SiC membrane via pyrolysis of selected pre-ceramic polymers and sol-gel techniques. Building upon the positive progress made in the membrane development study, we conducted an optimization study to develop an H{sub 2} selective SiC membrane with sufficient hydrothermal stability suitable for the WGS environment. In addition, mathematical simulation has been performed to compare the performance of the membrane reactor (MR) vs conventional packed bed reactor for WGS reaction. Our result demonstrates that >99.999% conversion can be accomplished via WGS-MR using the hydrogen selective membrane developed by us. Further, water/CO ratio can be reduced, and >97% hydrogen recovery and <200 ppm CO can be accomplished according to the mathematical simulation. Thus, we believe that the operating economics of WGS can be improved significantly based upon the proposed MR concept. In parallel, gas separations and hydrothermal and long-term-storage stability of the

  12. Hydrogen peroxide poisoning

    MedlinePlus

    Hydrogen peroxide is used in these products: Hydrogen peroxide Hair bleach Some contact lens cleaners Note: Household hydrogen peroxide has a 3% concentration. That means it contains 97% water and 3% hydrogen peroxide. Hair ...

  13. Modelling the post-reionization neutral hydrogen (H I ) bias

    NASA Astrophysics Data System (ADS)

    Sarkar, Debanjan; Bharadwaj, Somnath; Anathpindika, S.

    2016-08-01

    Observations of the neutral hydrogen (H I) 21-cm signal hold the potential of allowing us to map out the cosmological large-scale structures (LSS) across the entire post-reionization era (z ≤ 6). Several experiments are planned to map the LSS over a large range of redshifts and angular scales, many of these targeting the Baryon Acoustic Oscillations. It is important to model the H I distribution in order to correctly predict the expected signal, and more so to correctly interpret the results after the signal is detected. In this paper we have carried out semi-numerical simulations to model the H I distribution and study the H I power spectrum P_{H I}(k,z) across the redshift range 1 ≤ z ≤ 6. We have modelled the H I bias as a complex quantity tilde{b}(k,z) whose modulus squared b2(k, z) relates P_{H I}(k,z) to the matter power spectrum P(k, z), and whose real part br(k, z) quantifies the cross-correlation between the H I and the matter distribution. We study the z and k dependence of the bias, and present polynomial fits which can be used to predict the bias across 0 ≤ z ≤ 6 and 0.01 ≤ k ≤ 10 Mpc-1. We also present results for the stochasticity r = br/b which is important for cross-correlation studies.

  14. Conformational changes in the archaerhodopsin-3 proton pump: detection of conserved strongly hydrogen bonded water networks.

    PubMed

    Clair, Erica C Saint; Ogren, John I; Mamaev, Sergey; Kralj, Joel M; Rothschild, Kenneth J

    2012-01-01

    Archaerhodopsin-3 (AR3) is a light-driven proton pump from Halorubrum sodomense, but little is known about its photocycle. Recent interest has focused on AR3 because of its ability to serve both as a high-performance, genetically-targetable optical silencer of neuronal activity and as a membrane voltage sensor. We examined light-activated structural changes of the protein, retinal chromophore, and internal water molecules during the photocycle of AR3. Low-temperature and rapid-scan time-resolved FTIR-difference spectroscopy revealed that conformational changes during formation of the K, M, and N photocycle intermediates are similar, although not identical, to bacteriorhodopsin (BR). Positive/negative bands in the region above 3,600 cm( - 1), which have previously been assigned to structural changes of weakly hydrogen bonded internal water molecules, were substantially different between AR3 and BR. This included the absence of positive bands recently associated with a chain of proton transporting water molecules in the cytoplasmic channel and a weakly hydrogen bonded water (W401), which is part of a hydrogen-bonded pentagonal cluster located near the retinal Schiff base. However, many of the broad IR continuum absorption changes below 3,000 cm( - 1) assigned to networks of water molecules involved in proton transport through cytoplasmic and extracellular portions in BR were very similar in AR3. This work and subsequent studies comparing BR and AR3 structural changes will help identify conserved elements in BR-like proton pumps as well as bioengineer AR3 to optimize neural silencing and voltage sensing.

  15. Oral intake of hydrogen-rich water inhibits intimal hyperplasia in arterialized vein grafts in rats

    PubMed Central

    Sun, Qiang; Kawamura, Tomohiro; Masutani, Kosuke; Peng, Ximei; Sun, Qing; Stolz, Donna B.; Pribis, John P.; Billiar, Timothy R.; Sun, Xuejun; Bermudez, Christian A.; Toyoda, Yoshiya; Nakao, Atsunori

    2012-01-01

    Aims Arterialized vein grafts often fail due to intimal hyperplasia. Hydrogen potently protects organs and cells from many insults via its anti-inflammatory and antioxidant properties. We investigated the efficacy of oral administration of hydrogen-rich water (HW) for prevention of intimal hyperplasia. Methods and results The inferior vena cava was excised, stored in cold Ringer solution for 2 h, and placed as an interposition graft in the abdominal aorta of syngeneic Lewis rats. HW was generated by immersing a magnesium stick in tap water (Mg + 2H2O → Mg (OH)2 + H2). Beginning on the day of graft implantation, recipients were given tap water [regular water (RW)], HW or HW that had been subsequently degassed water (DW). Six weeks after grafting, the grafts in the rats given RW or DW had developed intimal hyperplasia, accompanied by increased oxidative injury. HW significantly suppressed intimal hyperplasia. One week after grafting, the grafts in HW-treated rats exhibited improved endothelial integrity with less platelet and white blood cell aggregation. Up-regulation of the mRNAs for intracellular adhesion molecules was attenuated in the vein grafts of the rats receiving HW. Activation of p38 mitogen-activated protein kinase, matrix metalloproteinase (MMP)-2, and MMP-9 was also significantly inhibited in grafts receiving HW. In rat smooth muscle cell (A7r5) cultures, hydrogen treatment for 24 h reduced smooth muscle cell migration. Conclusion Drinking HW significantly reduced neointima formation after vein grafting in rats. Drinking HW may have therapeutic value as a novel therapy for intimal hyperplasia and could easily be incorporated into daily life. PMID:22287575

  16. On the role of interfacial hydrogen bonds in "on-water" catalysis.

    PubMed

    Karhan, Kristof; Khaliullin, Rustam Z; Kühne, Thomas D

    2014-12-14

    Numerous experiments have demonstrated that many classes of organic reactions exhibit increased reaction rates when performed in heterogeneous water emulsions. Despite enormous practical importance of the observed "on-water" catalytic effect and several mechanistic studies, its microscopic origins remains unclear. In this work, the second generation Car-Parrinello molecular dynamics method is extended to self-consistent charge density-functional based tight-binding in order to study "on-water" catalysis of the Diels-Alder reaction between dimethyl azodicarboxylate and quadricyclane. We find that the stabilization of the transition state by dangling hydrogen bonds exposed at the aqueous interfaces plays a significantly smaller role in "on-water" catalysis than has been suggested previously.

  17. On the role of interfacial hydrogen bonds in "on-water" catalysis

    NASA Astrophysics Data System (ADS)

    Karhan, Kristof; Khaliullin, Rustam Z.; Kühne, Thomas D.

    2014-12-01

    Numerous experiments have demonstrated that many classes of organic reactions exhibit increased reaction rates when performed in heterogeneous water emulsions. Despite enormous practical importance of the observed "on-water" catalytic effect and several mechanistic studies, its microscopic origins remains unclear. In this work, the second generation Car-Parrinello molecular dynamics method is extended to self-consistent charge density-functional based tight-binding in order to study "on-water" catalysis of the Diels-Alder reaction between dimethyl azodicarboxylate and quadricyclane. We find that the stabilization of the transition state by dangling hydrogen bonds exposed at the aqueous interfaces plays a significantly smaller role in "on-water" catalysis than has been suggested previously.

  18. Geochemistry and origin of formation waters in the western Canada sedimentary basin-I. Stable isotopes of hydrogen and oxygen

    USGS Publications Warehouse

    Hitchon, B.; Friedman, I.

    1969-01-01

    Stable isotopes of hydrogen and oxygen, together with chemical analyses, were determined for 20 surface waters, 8 shallow potable formation waters, and 79 formation waters from oil fields and gas fields. The observed isotope ratios can be explained by mixing of surface water and diagenetically modified sea water, accompanied by a process which enriches the heavy oxygen isotope. Mass balances for deuterium and total dissolved solids in the western Canada sedimentary basin demonstrate that the present distribution of deuterium in formation waters of the basin can be derived through mixing of the diagenetically modified sea water with not more than 2.9 times as much fresh water at the same latitude, and that the movement of fresh water through the basin has redistributed the dissolved solids of the modified sea water into the observed salinity variations. Statistical analysis of the isotope data indicates that although exchange of deuterium between water and hydrogen sulphide takes place within the basin, the effect is minimized because of an insignificant mass of hydrogen sulphide compared to the mass of formation water. Conversely, exchange of oxygen isotopes between water and carbonate minerals causes a major oxygen-18 enrichment of formation waters, depending on the relative masses of water and carbonate. Qualitative evidence confirms the isotopic fractionation of deuterium on passage of water through micropores in shales. ?? 1969.

  19. Mitigation of Hydrogen Gas Generation from the Reaction of Water with Uranium Metal in K Basins Sludge

    SciTech Connect

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2010-01-29

    Means to decrease the rate of hydrogen gas generation from the chemical reaction of uranium metal with water were identified by surveying the technical literature. The underlying chemistry and potential side reactions were explored by conducting 61 principal experiments. Several methods achieved significant hydrogen gas generation rate mitigation. Gas-generating side reactions from interactions of organics or sludge constituents with mitigating agents were observed. Further testing is recommended to develop deeper knowledge of the underlying chemistry and to advance the technology aturation level. Uranium metal reacts with water in K Basin sludge to form uranium hydride (UH3), uranium dioxide or uraninite (UO2), and diatomic hydrogen (H2). Mechanistic studies show that hydrogen radicals (H·) and UH3 serve as intermediates in the reaction of uranium metal with water to produce H2 and UO2. Because H2 is flammable, its release into the gas phase above K Basin sludge during sludge storage, processing, immobilization, shipment, and disposal is a concern to the safety of those operations. Findings from the technical literature and from experimental investigations with simple chemical systems (including uranium metal in water), in the presence of individual sludge simulant components, with complete sludge simulants, and with actual K Basin sludge are presented in this report. Based on the literature review and intermediate lab test results, sodium nitrate, sodium nitrite, Nochar Acid Bond N960, disodium hydrogen phosphate, and hexavalent uranium [U(VI)] were tested for their effects in decreasing the rate of hydrogen generation from the reaction of uranium metal with water. Nitrate and nitrite each were effective, decreasing hydrogen generation rates in actual sludge by factors of about 100 to 1000 when used at 0.5 molar (M) concentrations. Higher attenuation factors were achieved in tests with aqueous solutions alone. Nochar N960, a water sorbent, decreased hydrogen

  20. A ’Hydrogen Partitioning’ Model for Hydrogen Assisted Crack Growth.

    DTIC Science & Technology

    1984-09-01

    number of sites/m 3), a is the lattice parameter of the metal, n is the number of atoms per unit cell, NA is Avogadro constant , and HB is the binding...remains constant at a given temper- ature and hydrogen pressure, and is independent of the stress intensity factor K. (ii) The rate of hydrogen...for the ith fracture mode (or micromechanism), (da/dt)i, is given by Eqn. (1). In the equation, Is the proportionality constant for the ith mode. -6

  1. Henry Cavendish (1731-1810): hydrogen, carbon dioxide, water, and weighing the world.

    PubMed

    West, John B

    2014-07-01

    Henry Cavendish (1731-1810) was an outstanding chemist and physicist. Although he was not a major figure in the history of respiratory physiology he made important discoveries concerning hydrogen, carbon dioxide, atmospheric air, and water. Hydrogen had been prepared earlier by Boyle but its properties had not been recognized; Cavendish described these in detail, including the density of the gas. Carbon dioxide had also previously been studied by Black, but Cavendish clarified its properties and measured its density. He was the first person to accurately analyze atmospheric air and reported an oxygen concentration very close to the currently accepted value. When he removed all the oxygen and nitrogen from an air sample, he found that there was a residual portion of about 0.8% that he could not characterize. Later this was shown to be argon. He produced large amounts of water by burning hydrogen in oxygen and recognized that these were its only constituents. Cavendish also worked on electricity and heat. However, his main contribution outside chemistry was an audacious experiment to measure the density of the earth, which he referred to as "weighing the world." This involved determining the gravitational attraction between lead spheres in a specially constructed building. Although this was a simple experiment in principle, there were numerous complexities that he overcame with meticulous attention to experimental details. His result was very close to the modern accepted value. The Cavendish Experiment, as it is called, assures his place in the history of science.

  2. Hydrogen embrittlement of duplex stainless steel and maraging steel in sea water: Effect of pressure

    SciTech Connect

    Pohjanne, P.; Festy, D.

    1994-12-31

    Hydrogen embrittlement behavior of cast super duplex stainless steel and cast maraging steel was examined as a function of electrode potential and hydrostatic pressure, i.e, the water depth, in synthetic sea water using fracture mechanics bolt-loaded wedge-opening (WOL) specimens. The experimental variables investigated included: (1) Electrode potential: free corrosion potential and cathodic protection; (2) Hydrostatic pressure: ambient and 10 MPa corresponding depth of 1,000 meters. The duplex stainless-,steel was not susceptible to hydrogen embrittlement with initial stress intensity values of 30 MPa{radical}m < K{sub i} < 45 MPa{radical}m at ambient pressure. However, at pressure of 10 MPa slight crack growth was observed at open circuit potential and the crack growth was enhanced by the cathodic protection. The maraging steel was susceptible to hydrogen embrittlement in all tests, with all examined initial stress intensity value