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Sample records for modeling hydrogen water

  1. Water's hydrogen bonds in the hydrophobic effect: a simple model.

    PubMed

    Xu, Huafeng; Dill, Ken A

    2005-12-15

    We propose a simple analytical model to account for water's hydrogen bonds in the hydrophobic effect. It is based on computing a mean-field partition function for a water molecule in the first solvation shell around a solute molecule. The model treats the orientational restrictions from hydrogen bonding, and utilizes quantities that can be obtained from bulk water simulations. We illustrate the principles in a 2-dimensional Mercedes-Benz-like model. Our model gives good predictions for the heat capacity of hydrophobic solvation, reproduces the solvation energies and entropies at different temperatures with only one fitting parameter, and accounts for the solute size dependence of the hydrophobic effect. Our model supports the view that water's hydrogen bonding propensity determines the temperature dependence of the hydrophobic effect. It explains the puzzling experimental observation that dissolving a nonpolar solute in hot water has positive entropy. PMID:16375338

  2. Hydrogen-Bond Cooperativity in Formamide2 -Water: A Model for Water-Mediated Interactions.

    PubMed

    Blanco, Susana; Pinacho, Pablo; López, Juan Carlos

    2016-08-01

    The rotational spectrum of formamide2 -H2 O formed in a supersonic jet has been characterized by Fourier-transform microwave spectroscopy. This adduct provides a simple model of water-mediated interaction involving the amide linkages, as occur in protein folding or amide-association processes, showing the interplay between self-association and solvation. Mono-substituted (13) C, (15) N, (18) O, and (2) H isotopologues have been observed and their data used to investigate the structure. The adduct forms an almost planar three-body sequential cycle. The two formamide molecules link on one side through an N-H⋅⋅⋅O hydrogen bond and on the other side through a water-mediated interaction with the formation of C=O⋅⋅⋅H-O and O⋅⋅⋅H-N hydrogen bonds. The analysis of the quadrupole coupling effects of two (14) N-nuclei reveals the subtle inductive forces associated to cooperative hydrogen bonding. These forces are involved in the changes in the C=O and C-N bond lengths with respect to pure formamide. PMID:27351296

  3. 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.

  4. Photocatalytic hydrogen production from a simple water-soluble [FeFe]-hydrogenase model system.

    PubMed

    Cao, Wei-Ning; Wang, Feng; Wang, Hong-Yan; Chen, Bin; Feng, Ke; Tung, Chen-Ho; Wu, Li-Zhu

    2012-08-21

    Combined with a simple water soluble [FeFe]-hydrogenase mimic 1, Ru(bpy)(3)(2+) and ascorbic acid enable hydrogen production photocatalytically. More than 88 equivalents of H(2) were achieved in water, which is much better than that obtained in an organic solvent or a mixture of organic solvent and water. PMID:22772838

  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. Process for exchanging hydrogen isotopes between gaseous hydrogen and water

    DOEpatents

    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.

  7. Water balance model for mean annual hydrogen and oxygen isotope distributions in surface waters of the contiguous United States

    NASA Astrophysics Data System (ADS)

    Bowen, Gabriel J.; Kennedy, Casey D.; Liu, Zhongfang; Stalker, Jeremy

    2011-12-01

    The stable H and O isotope composition of river and stream water records information on runoff sources and land-atmosphere water fluxes within the catchment and is a potentially powerful tool for network-based monitoring of ecohydrological systems. Process-based hydrological models, however, have thus far shown limited power to replicate observed large-scale variation in U.S. surface water isotope ratios. Here we develop a geographic information system-based model to predict long-term annual average surface water isotope ratios across the contiguous United States. We use elevation-explicit, gridded precipitation isotope maps as model input and data from a U.S. Geological Survey monitoring program for validation. We find that models incorporating monthly variation in precipitation-evapotranspiration (P-E) amounts account for the majority (>89%) of isotopic variation and have reduced regional bias relative to models that do not consider intra-annual P-E effects on catchment water balance. Residuals from the water balance model exhibit strong spatial patterning and correlations that suggest model residuals isolate additional hydrological signal. We use interpolated model residuals to generate optimized prediction maps for U.S. surface water δ2H and δ18O values. We show that the modeled surface water values represent a relatively accurate and unbiased proxy for drinking water isotope ratios across the United States, making these data products useful in ecological and criminal forensics applications that require estimates of the local environmental water isotope variation across large geographic regions.

  8. Water balance model for mean annual hydrogen and oxygen isotope distributions in surface waters of the contiguous US

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The stable H and O isotope composition of river and stream water records information on runoff sources and land/atmosphere water fluxes within the catchment, and is a potentially powerful tool for network-based monitoring of large ecohydrological systems. Process-based hydrological models, however,...

  9. Hydrogen by electrolysis of water

    NASA Technical Reports Server (NTRS)

    1975-01-01

    Hydrogen production by electrolytic decomposition of water is explained. Power efficiency, efficient energy utilization, and costs were emphasized. Four systems were considered: two were based on current electrolyzer technology using present efficiency values for electrical generation by fossil fired and nuclear thermal stations, and two using projected electrolyzer technology with advanced fossil and nuclear plants.

  10. 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.

  11. 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.

  12. Hydrogen-bond kinetics in liquid water

    NASA Astrophysics Data System (ADS)

    Luzar, Alenka; Chandler, David

    1996-01-01

    HYDROGEN bonds play a crucial role in the behaviour of water1-4 their spatial patterns and fluctuations characterize the structure and dynamics of the liquid5-7. The processes of breaking and making hydrogen bonds in the condensed phase can be probed indirectly by a variety of experimental techniques8, and more quantitative information can be obtained from computer simulations9. In particular, simulations have revealed that on long timescales the relaxation behaviour of hydrogen bonds in liquid water exhibit non-exponential kinetics7,10-13, suggesting that bond making and breaking are not simple processes characterized by well defined rate constants. Here we show that these kinetics can be understood in terms of an interplay between diffusion and hydrogen-bond dynamics. In our model, which can be extended to other hydrogen-bonded liquids, diffusion governs whether a specific pair of water molecules are near neighbours, and hydrogen bonds between such pairs form and persist at random with average lifetimes determined by rate constants for bond making and breaking.

  13. 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. PMID:27447299

  14. Water and hydrogen are immiscible in Earth's mantle.

    PubMed

    Bali, Enikő; Audétat, Andreas; Keppler, Hans

    2013-03-14

    In the deep, chemically reducing parts of Earth's mantle, hydrous fluids contain significant amounts of molecular hydrogen (H2). Thermodynamic models of fluids in Earth's mantle so far have always assumed that molecular hydrogen and water are completely miscible. Here we show experimental evidence that water and hydrogen can coexist as two separate, immiscible phases. Immiscibility between water and hydrogen may be the cause of the formation of enigmatic, ultra-reducing domains in the mantle that contain moissanite (SiC) and other phases indicative of extremely reducing conditions. Moreover, the immiscibility between water and hydrogen may provide a mechanism for the rapid oxidation of Earth's upper mantle immediately following core formation. PMID:23486061

  15. 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.

  16. Coverage-dependent thermodynamic analysis of the formation of water and hydrogen peroxide on a platinum model catalyst.

    PubMed

    de Morais, Rodrigo Ferreira; Franco, Alejandro A; Sautet, Philippe; Loffreda, David

    2015-05-01

    Understanding the selectivity of the oxygen reduction reaction, especially the formation of water versus hydrogen peroxide in fuel cells, is an ongoing challenge in electrochemistry, surface science and catalysis. In this study, we propose a comprehensive thermodynamic analysis of the reaction intermediates for the formation of water on Pt(111). Density functional theory calculations of all the elementary steps linking hydroxyl and hydroperoxyl surface species with water and hydrogen peroxide have been performed at low (1/12 ML, ML = monolayer) and high (1/4 ML) coverages. The reaction energy variation for the two competing elementary events (molecular oxygen dissociation and hydroperoxyl formation) is strongly coverage-dependent. For the direct dissociation, an increase is observed at low coverage with respect to the usual high coverage picture. The stability of the reaction intermediates is investigated from thermodynamic diagrams. At 353 K and a total pressure of 1 atm, water and hydroxyl surface species are expected to compete for adsorption on Pt(111). PMID:25848757

  17. 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

  18. 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.

  19. pH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases.

    PubMed

    Kure, Bunsho; Matsumoto, Takahiro; Ichikawa, Koji; Fukuzumi, Shunichi; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

    2008-09-21

    The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni(I)(mu-SR)(2)Ru(I) complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes acts as H(-), and the complexes catalyse the hydrogenation of carbonyl compounds. PMID:18728883

  20. 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.

  1. 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)

  2. Chemical Kinetic Modeling of Hydrogen Combustion Limits

    SciTech Connect

    Pitz, W J; Westbrook, C K

    2008-04-02

    A detailed chemical kinetic model is used to explore the flammability and detonability of hydrogen mixtures. In the case of flammability, a detailed chemical kinetic mechanism for hydrogen is coupled to the CHEMKIN Premix code to compute premixed, laminar flame speeds. The detailed chemical kinetic model reproduces flame speeds in the literature over a range of equivalence ratios, pressures and reactant temperatures. A series of calculation were performed to assess the key parameters determining the flammability of hydrogen mixtures. Increased reactant temperature was found to greatly increase the flame speed and the flammability of the mixture. The effect of added diluents was assessed. Addition of water and carbon dioxide were found to reduce the flame speed and thus the flammability of a hydrogen mixture approximately equally well and much more than the addition of nitrogen. The detailed chemical kinetic model was used to explore the detonability of hydrogen mixtures. A Zeldovich-von Neumann-Doring (ZND) detonation model coupled with detailed chemical kinetics was used to model the detonation. The effectiveness on different diluents was assessed in reducing the detonability of a hydrogen mixture. Carbon dioxide was found to be most effective in reducing the detonability followed by water and nitrogen. The chemical action of chemical inhibitors on reducing the flammability of hydrogen mixtures is discussed. Bromine and organophosphorus inhibitors act through catalytic cycles that recombine H and OH radicals in the flame. The reduction in H and OH radicals reduces chain branching in the flame through the H + O{sub 2} = OH + O chain branching reaction. The reduction in chain branching and radical production reduces the flame speed and thus the flammability of the hydrogen mixture.

  3. 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.

  4. Water-hydrogen isotope exchange process analysis

    SciTech Connect

    Fedorchenko, O.; Alekseev, I.; Uborsky, V.

    2008-07-15

    The use of a numerical method is needed to find a solution to the equation system describing a general case of heterogeneous isotope exchange between gaseous hydrogen and liquid water in a column. A computer model of the column merely outputting the isotope compositions in the flows leaving the column, like the experimental column itself, is a 'black box' to a certain extent: the solution is not transparent and occasionally not fully comprehended. The approximate analytical solution was derived from the ZXY-diagram (McCabe-Thiele diagram), which illustrates the solution of the renewed computer model called 'EVIO-4.2' Several 'unusual' results and dependences have been analyzed and explained. (authors)

  5. 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.

  6. 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%.

  7. 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

  8. 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)

  9. 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.

  10. 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.

  11. 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. PMID:27492605

  12. Hydrophobicity and hydrogen-bonded network in liquid water

    NASA Astrophysics Data System (ADS)

    Li, Je-Luen; Wingreen, Ned; Tang, Chao; Car, Roberto

    2004-03-01

    Hydrophobicity is the main driving force behind numerous important biological processes at molecular level, including protein folding and the formation of biological membranes. Yet few experimental probes can measure the local water structure around a hydrophobic solute, and our understanding of the detailed structure of hydrophobic hydration has to rely on molecular dynamics simulation. As a model system, several groups studied two methane molecules in liquid water and obtained the potential of mean force using Lennard-Jones potential and various water models. However, hydrophobic effect critically depends on the description of hydrogen-bonded network, and classical simulations may not be sufficient to descirbe the forming and breaking of hydrogen bonds. In this work, we apply ab initio molecular dynamics simulations to study this model system. Besides the potential of mean force between 2 methanes in water, the role of the local water structure will be highlighted.

  13. 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

  14. 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.

  15. 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.

  16. 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 Central

    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

    2009-01-01

    It has been shown that molecular hydrogen (H2) 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 H2-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 H2 showed that H2 as low as 0.08 ppm had almost the same effect as saturated H2 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 H2-containing water, whereas production of superoxide (O2•−) detected by intravascular injection of dihydroethidium (DHE) was not reduced significantly. Our results indicated that low concentration of H2 in drinking water can reduce oxidative stress in the brain. Thus, drinking H2-containing water may be useful in daily life to prevent or minimize the risk of life style-related oxidative stress and neurodegeneration. PMID:19789628

  17. 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

    2009-01-01

    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. PMID:19789628

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. Photosynthetic water splitting for hydrogen fuel synthesis

    NASA Astrophysics Data System (ADS)

    Greenbaum, E.

    Three key advances in photosynthesis research are reported. A significant advance in microalgal water splitting has been made. In the linear, low-intensity region of the light saturation curves, equivalent solar conversion efficiencies of 10% have been measured. A technological advance in the ability to genetically screen individual algal colonies has been made. Successive subcultures of anaerobiosis-stressed Chlamydomonas reinhardtii exhibited enhanced capacity for photoproduction of hydrogen and oxygen.

  4. Hydrogen Generation by Solar Photolysis of Water

    NASA Astrophysics Data System (ADS)

    Graetzel, Michael

    2004-03-01

    Prospects of near term fuel cell applications for transportation and communication have stimulated recently great interest in systems that can generate hydrogen through water cleavage by sunlight. A device that appears very promising to accomplish this goal is a tandem cell based on two superimposed photoactive layers [1]. The top layer consists of nanocrystalline oxide film absorbing the blue part of the solar spectrum and producing oxygen from water under light excitation. This is placed directly on top of a dye-sensitized nanocrystalline TiO2 film (DSC) capturing the green and red part of the solar spectrum. The voltage generated by this second photosystem enables hydrogen production to proceed without application of an external electric bias. The overall reaction corresponds to the splitting of water into hydrogen and oxygen by visible light. The maximum conversion efficiency achieved so far with these systems is about 6-7 electrode a nanocrystalline WO3 film. The use of nanoparticles for the top layer has several great advantages. They are translucent avoiding losses by light scattering and their small size is within the minority carrier diffusion length, allowing the valence band hole reaction with water at the particle surface to proceed with high efficiency. Recent work has focused on replacing the WO3 by semiconductor oxide absorbing a larger fraction of visible light than tungsten trioxide, e.g. Fe2O3.The principles and current state of this research will be briefly reviewed. Literature 1. M. Graetzel, "Photoelectrochemical Cells" Nature, 414, 332-344 (2001)

  5. The hydrogen bond network structure within the hydration shell around simple osmolytes: Urea, tetramethylurea, and trimethylamine-N-oxide, investigated using both a fixed charge and a polarizable water model

    NASA Astrophysics Data System (ADS)

    Kuffel, Anna; Zielkiewicz, Jan

    2010-07-01

    Despite numerous experimental and computer simulation studies, a controversy still exists regarding the effect of osmolytes on the structure of surrounding water. There is a question, to what extent some of the contradictory results may arise from differences in potential models used to simulate the system or parameters employed to describe physical properties of the mixture and interpretation of the results. Bearing this in mind, we determine two main aims of this work as follows: description of the water-water hydrogen bond network structure within the solvation layer around solute molecules (urea, trimethylamine-N-oxide, and tetramethylurea), and also comparison of rigid simple point charges (SPC) and polarizable (POL3) models of water. The following quantities have been examined: radial distribution functions of water molecules around the investigated solutes, both local and overall characteristics of the hydrogen bond network structure (using recently elaborated method), along with estimation of the mean energy of a single hydrogen bond, and also the probability distributions which describe the orientation of a single water particle plane relatively to the center of mass of the solute molecule. As an independent method for the evaluation of the degree of changes in local structural ordering, a harmonic approximation has been adopted to estimate the absolute entropy of water. It was found that within the solvation shell of the investigated solutes, the structure of hydrogen bond network changes only slightly comparing to bulk water. Therefore, we conclude that the investigated osmolyte molecules do not disturb significantly the structure of surrounding water. This conclusion was also confirmed by calculations of the absolute entropy of water using a harmonic approximation. In the immediate vicinity of the solutes, we observe that the water-water hydrogen bonds are slightly more stable; they are slightly less distorted and a little shorter than in bulk water

  6. The hydrogen bond network structure within the hydration shell around simple osmolytes: urea, tetramethylurea, and trimethylamine-N-oxide, investigated using both a fixed charge and a polarizable water model.

    PubMed

    Kuffel, Anna; Zielkiewicz, Jan

    2010-07-21

    Despite numerous experimental and computer simulation studies, a controversy still exists regarding the effect of osmolytes on the structure of surrounding water. There is a question, to what extent some of the contradictory results may arise from differences in potential models used to simulate the system or parameters employed to describe physical properties of the mixture and interpretation of the results. Bearing this in mind, we determine two main aims of this work as follows: description of the water-water hydrogen bond network structure within the solvation layer around solute molecules (urea, trimethylamine-N-oxide, and tetramethylurea), and also comparison of rigid simple point charges (SPC) and polarizable (POL3) models of water. The following quantities have been examined: radial distribution functions of water molecules around the investigated solutes, both local and overall characteristics of the hydrogen bond network structure (using recently elaborated method), along with estimation of the mean energy of a single hydrogen bond, and also the probability distributions which describe the orientation of a single water particle plane relatively to the center of mass of the solute molecule. As an independent method for the evaluation of the degree of changes in local structural ordering, a harmonic approximation has been adopted to estimate the absolute entropy of water. It was found that within the solvation shell of the investigated solutes, the structure of hydrogen bond network changes only slightly comparing to bulk water. Therefore, we conclude that the investigated osmolyte molecules do not disturb significantly the structure of surrounding water. This conclusion was also confirmed by calculations of the absolute entropy of water using a harmonic approximation. In the immediate vicinity of the solutes, we observe that the water-water hydrogen bonds are slightly more stable; they are slightly less distorted and a little shorter than in bulk water

  7. 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.

  8. 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.

  9. 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.

  10. 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. PMID:26514915

  11. Hydrogen isotope composition of magmatic water

    SciTech Connect

    Taylor, B.E. )

    1992-01-01

    Isotopic tracing of H[sub 2]O degassing in both small and very large rhyolitic magmas in continental tectonic settings (USA and New Zealand), and isotopic studies of high-temperature fumaroles (USA, Japan, and elsewhere) indicate that the hydrogen isotope compositions of magmatic waters vary primarily with the composition of source material and tectonic setting. Water from felsic magmas in volcanic arc settings has a mean [delta]D value off [minus]25 [+-] 5 permil, whereas water from volcanic and plutonic magmas in continental settings has a slightly lower mean [delta]D of [minus]40 [+-] 10 permil. These differences reflect the variation in composition of source materials: hydrated oceanic crust and marine sediments for the arc volcanoes, and largely metamorphic crust for magmas in continental settings. The isotopic record in certain ore deposits associated with felsic magmas (e.g., W skarns, Sn-W veins) and geothermal systems records the influx at critical times of magmatic water with a [delta]D value of [minus]35 to [minus]45 permil. This is best documented where isotopic contrast between magmatic and meteoric waters is large. The [delta]D of MORB H[sub 2]O presumably lies between the mean [delta]D for MORB glass ([minus]75 permil), the [delta]D of H[sub 2]O in equilibrium with this glass ([delta]D ca. [minus]35; assuming closed-system degassing).

  12. 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.

  13. 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.

  14. Hydrogen bonding, structure, and dynamics of benzonitrile-water

    NASA Astrophysics Data System (ADS)

    Melandri, Sonia; Consalvo, Daniela; Caminati, Walther; Favero, Paolo G.

    1999-09-01

    Rotational transitions with high quantum numbers J and K of the 1:1 complex of benzonitrile with H2O and D2O have been investigated in the frequency range 60-78 GHz with the free jet absorption microwave technique to get detailed information on the unusual hydrogen bond and on the dynamics of the large amplitude motions of the water moiety. With respect to previous microwave studies [V. Storm, D. Consalvo, and H. Dreizler, Z. Naturforsch. A 52, 293 (1997); R. M. Helm, H.-P. Vogel, H. J. Neusser, V. Storm, D. Consalvo, and H. Dreizler, 52, 655 (1997); V. Storm, H. Dreizler, and D. Consalvo, Chem. Phys. 239, 109 (1998)] the position of the water oxygen has been confirmed and the planar configuration of the complex has been determined. The distance of the oxygen atom to the ortho hydrogen is 2.48 Å, the angle to the ortho C-H bond is 144° and the angle between the free hydrogen atom of water with the same C-H bond is 164°. A coupled analysis of the 0+ and 0- states observed for the normal species was performed and the experimental data were reproduced by a flexible model which allowed the determination of the barrier to internal rotation of water [V2=287(20) cm-1] and the structural relaxation associated with the dynamic process.

  15. 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.

  16. Hydrogen Sticking on Amorphous Water-Ice: A Numerical Study

    NASA Astrophysics Data System (ADS)

    Dupuy, John; Lewis, Steven; Stancil, Phillip C.

    2016-01-01

    Gas-grain and gas-phase reactions dominate the formation of molecules in the interstellar medium (ISM). Gas-grain reactions require a substrate on which the reaction is able to occur. The formation of molecular hydrogen (H2) in the ISM is a prime example of a gas-grain reaction. In these reactions, an atom of hydrogen will strike a surface, adsorb to the surface, interact with the molecular structure of substrate (in this case water), form molecular hydrogen, and then be ejected from the surface. We perform classical molecular dynamics (MD) simulations of hydrogen atoms sticking to an amorphous water-ice surface. This study examines the first step in the process; the sticking of the atom to the substrate. This talk emphasizes the importance of accurately defining a sticking event in calculating sticking probabilities which are used to obtain a reasonable model for H2 formation in the ISM. With these sticking probabilities calculated, sticking coefficients are obtained for various ice substrate temperatures and incident H-atom kinetic energies.

  17. A multilateral mechanistic study into asymmetric transfer hydrogenation in water.

    PubMed

    Wu, Xiaofeng; Liu, Jianke; Di Tommaso, Devis; Iggo, Jonathan A; Catlow, C Richard A; Bacsa, John; Xiao, Jianliang

    2008-01-01

    The mechanism of aqueous-phase asymmetric transfer hydrogenation (ATH) of acetophenone (acp) with HCOONa catalyzed by Ru-TsDPEN has been investigated by stoichiometric reactions, NMR probing, kinetic and isotope effect measurements, DFT modeling, and X-ray structure analysis. The chloride [RuCl(TsDPEN)(p-cymene)] (1), hydride [RuH(TsDPEN)(p-cymene)] (3), and the 16-electorn species [Ru(TsDPEN-H)(p-cymene)] (4) were shown to be involved in the aqueous ATH, with 1 being the precatalyst, and 3 as the active catalyst detectable by NMR in both stoichiometric and catalytic reactions. The formato complex [Ru(OCOH)(TsDPEN)(p-cymene)] (2) was not observed; its existence, however, was demonstrated by its reversible decarboxylation to form 3. Both 1 and 3 were protonated under acidic conditions, leading to ring opening of the TsDPEN ligand. 4 reacted with water, affording a hydroxyl species. In a homogeneous DMF/H(2)O solvent, the ATH was found to be first order in the concentration of catalyst and acp, and inhibited by CO(2). In conjunction with the NMR results, this suggests that hydrogen transfer to ketone is the rate-determining step. The addition of water stabilized the ruthenium catalyst and accelerated the ATH reaction; it does so by participating in the catalytic cycle. DFT calculations revealed that water hydrogen bonds to the ketone oxygen at the transition state of hydrogen transfer, lowering the energy barrier by about 4 kcal mol(-1). The calculations also suggested that the hydrogen transfer is more step-wise in nature rather than concerted. This is supported to some degree by the kinetic isotope effects, which were obscured by extensive H/D scrambling. PMID:18604853

  18. 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.

  19. Molecular hydrogen solvated in water - A computational study

    NASA Astrophysics Data System (ADS)

    Śmiechowski, Maciej

    2015-12-01

    The aqueous hydrogen molecule is studied with molecular dynamics simulations at ambient temperature and pressure conditions, using a newly developed flexible and polarizable H2 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 H2 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 H2O. The calculated self-diffusion coefficient of H2(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 H2 experiences an extremely short-scale decay, making the H2-H2O 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 H2(aq) under differing pressure conditions, including accurate reproduction of the experimentally noted trends with solute pressure or concentration.

  20. 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)

  1. 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.

  2. Hydrogen bonding of water-ethanol in alcoholic beverages.

    PubMed

    Nose, Akira; Hojo, Masashi

    2006-10-01

    An alcoholic beverage is a type of water-ethanol solution with flavor and taste. The properties of the hydrogen bonding of water-ethanol in alcoholic beverages have not been clarified sufficiently. We investigated factors that could affect the hydrogen-bonding structure of water-ethanol on the basis of proton nuclear magnetic resonance (1H NMR) chemical shifts of the OH of water-ethanol and Raman OH stretching spectra. Not only acids (H+ and HA: undissociated acids) but also bases (OH- and A-: conjugate-base anions from weak acids) strengthened the hydrogen-bonding structure of water-ethanol. It was also demonstrated that the hydrogen bonding is strengthened by chemical components in alcoholic beverages (whiskey, Japanese sake, shochu). It can be suggested that hydrogen-bonding donors as well as acceptors in alcohol beverages, which exist as the initial components or are gained later on, should cause the tight association between water and ethanol molecules. PMID:17116572

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. Hadronic chemistry applied to hydrogen and water molecules

    NASA Astrophysics Data System (ADS)

    Tangde, Vijay M.

    2012-09-01

    The decades of research of R M Santilli resulted into the formulation of iso-, geno- and hyper- mathematics [1, 2] that helped in understanding numerous diversified problems and removing inadequacies in most of the established and celebrated theories of 20th century physics and chemistry, for example, the theories of relativity, quantum mechanics (chemistry), astrophysics, particle physics, and so on. This involves the isotopic, genotopic, etc. lifting of Lie algebra that generated Lie admissible mathematics to properly describe irreversible processes. The studies on Hadronic m Mechanics based on Santilli's mathematics for the first time has removed the very fundamental limitations of quantum chemistry [3, 4] [2, 3, 4]. Herein, we review a Santilli-Shillady model[3, 4, 5] of hydrogen and water molecules characterized by a bond at short distances of the two valance electrons into a singlet quasi-particle state called isoelectronium for hydrogen molecule and two isoelctronia (one per H-O dimer) in case of water molecule. We especially emphasis on: the numerically exact representation of binding energies from unadulterated first axiomatic principle, the reduction of the hydrogen molecule to a restricted three body problem that admits exact analytic solutions and the reduction of computer time by at least a factor of 1000 folds due to a much faster convergent series.

  8. 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

  9. Molecular orbital analysis of the hydrogen bonded water dimer

    NASA Astrophysics Data System (ADS)

    Wang, Bo; Jiang, Wanrun; Dai, Xin; Gao, Yang; Wang, Zhigang; Zhang, Rui-Qin

    2016-02-01

    As an essential interaction in nature, hydrogen bonding plays a crucial role in many material formations and biological processes, requiring deeper understanding. Here, using density functional theory and post-Hartree-Fock methods, we reveal two hydrogen bonding molecular orbitals crossing the hydrogen-bond’s O and H atoms in the water dimer. Energy decomposition analysis also shows a non-negligible contribution of the induction term. Our finding sheds light on the essential understanding of hydrogen bonding in ice, liquid water, functional materials and biological systems.

  10. Molecular orbital analysis of the hydrogen bonded water dimer

    PubMed Central

    Wang, Bo; Jiang, Wanrun; Dai, Xin; Gao, Yang; Wang, Zhigang; Zhang, Rui-Qin

    2016-01-01

    As an essential interaction in nature, hydrogen bonding plays a crucial role in many material formations and biological processes, requiring deeper understanding. Here, using density functional theory and post-Hartree-Fock methods, we reveal two hydrogen bonding molecular orbitals crossing the hydrogen-bond’s O and H atoms in the water dimer. Energy decomposition analysis also shows a non-negligible contribution of the induction term. Our finding sheds light on the essential understanding of hydrogen bonding in ice, liquid water, functional materials and biological systems. PMID:26905305

  11. 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.

  12. Hydrogen isotope separation by catalyzed exchange between hydrogen and liquid water

    SciTech Connect

    Butler, J.P.

    1980-04-01

    The discovery, at Chalk River Nuclear Laboratories, of a simple method of wetproofing platinum catalysts so that they retain their activity in liquid water stimulated a concentrated research program for the development of catalysts for the hydrogen-water isotopic exchange reaction. This paper reviews 10 years of study which have resulted in the development of highly active platinum catalysts which remain effective in water for periods greater than a year. The most efficient way to use these catalysts for the separation of hydrogen isotopes is in a trickle bed reactor which effects a continuous separation. The catalyst is packed in a column with hydrogen and water flowing countercurrently through the bed. The overall isotope transfer rate measured for the exchange reaction is influenced by various parameters, such as hydrogen and water flow rates, temperature, hydrogen pressure, and platinum metal loading. The effect of these parameters as well as the improved performance obtained by diluting the hydrophobic catalyst with inert hydrophilic packing are discussed. The hydrophobic catalysts can be effectively used in a variety of applications of particular interest in the nuclear industry. A Combined Electrolysis Catalytic Exchange - Heavy Water Process (CECE-HWP) is being developed at Chalk River with the ultimate aim of producing parasitic heavy water from electrolytic hydrogen streams. Other more immediate applications include the final enrichment of heavy water and the extraction of tritium from light and heavy water. Pilot plant studies on these latter processes are currently in progress.

  13. 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

  14. Spectroscopic and thermodynamic properties of molecular hydrogen dissolved in water at pressures up to 200 MPa

    SciTech Connect

    Borysow, Jacek Rosso, Leonardo del; Celli, Milva; Ulivi, Lorenzo; Moraldi, Massimo

    2014-04-28

    We have measured the Raman Q-branch of hydrogen in a solution with water at a temperature of about 280 K and at pressures from 20 to 200 MPa. From a least-mean-square fitting analysis of the broad Raman Q-branch, we isolated the contributions from the four lowest individual roto-vibrational lines. The vibrational lines were narrower than the pure rotational Raman lines of hydrogen dissolved in water measured previously, but significantly larger than in the gas. The separations between these lines were found to be significantly smaller than in gaseous hydrogen and their widths were slightly increasing with pressure. The lines were narrowing with increasing rotational quantum number. The Raman frequencies of all roto-vibrational lines were approaching the values of gas phase hydrogen with increasing pressure. Additionally, from the comparison of the integrated intensity signal of Q-branch of hydrogen to the integrated Raman signal of the water bending mode, we have obtained the concentration of hydrogen in a solution with water along the 280 K isotherm. Hydrogen solubility increases slowly with pressure, and no deviation from a smooth behaviour was observed, even reaching thermodynamic conditions very close to the transition to the stable hydrogen hydrate. The analysis of the relative hydrogen concentration in solution on the basis of a simple thermodynamic model has allowed us to obtain the molar volume for the hydrogen gas/water solution. Interestingly, the volume relative to one hydrogen molecule in solution does not decrease with pressure and, at high pressure, is larger than the volume pertinent to one molecule of water. This is in favour of the theory of hydrophobic solvation, for which a larger and more stable structure of the water molecules is expected around a solute molecule.

  15. Effect of Water Hydrogen Bonding on the Solvent-Mediated "Oscillatory" Repulsion of C60 Fullerenes in Water.

    PubMed

    Djikaev, Yuri S; Ruckenstein, Eli

    2015-05-01

    The solvent-mediated interaction of C60 fullerenes in liquid water is examined by using the combination of the probabilistic hydrogen bond model with the density functional theory. This combination allows one to take into account the effect of hydrogen bonding between water molecules on their interaction with fullerenes and to construct an approximation for the distribution of water molecules in the system, which provides an efficient foundation for studying hydrophobic phenomena. Our numerical evaluations predict the solvent-induced interaction of two C60 fullerenes in water at 293 K to have an oscillatory-repulsive character (previously observed in molecular dynamics simulations) only when the vicinal water-water hydrogen bonds are slightly weaker than bulk ones. Besides indicating the direction of the energetic alteration of water-water hydrogen bonds near C60 fullerenes, our model also suggests that the hydrogen bonding ability of water plays a defining role in the solvent-mediated C60-C60 repulsion. PMID:26263346

  16. 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.

  17. 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.

  18. Selective electrochemical generation of hydrogen peroxide from water oxidation

    DOE PAGESBeta

    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

  19. 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.

  20. Hydrogen bond cooperativity and the three-dimensional structures of water nonamers and decamers.

    PubMed

    Pérez, Cristóbal; Zaleski, Daniel P; Seifert, Nathan A; Temelso, Berhane; Shields, George C; Kisiel, Zbigniew; Pate, Brooks H

    2014-12-22

    Broadband rotational spectroscopy of water clusters produced in a pulsed molecular jet expansion has been used to determine the oxygen atom geometry in three isomers of the nonamer and two isomers of the decamer. The isomers for each cluster size have the same nominal geometry but differ in the arrangement of their hydrogen bond networks. The nearest neighbor OO distances show a characteristic pattern for each hydrogen bond network isomer that is caused by three-body effects that produce cooperative hydrogen bonding. The observed structures are the lowest energy cluster geometries identified by quantum chemistry and the experimental and theoretical OO distances are in good agreement. The cooperativity effects revealed by the hydrogen bond OO distance variations are shown to be consistent with a simple model for hydrogen bonding in water that takes into account the cooperative and anticooperative bonding effects of nearby water molecules. PMID:25348841

  1. Liquid Water vs. Hydrogen Cyanide on Enceladus

    NASA Astrophysics Data System (ADS)

    Glein, C. R.; Zolotov, M. Y.; Shock, E. L.

    2008-12-01

    The Ion and Neutral Mass Spectrometer onboard the Cassini spacecraft detected hydrogen cyanide (HCN) in plumes on Enceladus [1]. We explored computationally the thermodynamic stability and kinetic reactivity of HCN. Thermochemical equilibrium calculations show that HCN is unstable in liquid water, and should be overwhelmingly hydrolyzed to formic acid (HCOOH) and ammonia (NH3) under all conditions relevant to Enceladus. Even in an aqueous solution with an unreasonably high NH3 activity of 10, the HCOOH/HCN activity ratio is predicted to be greater than 107 at 0°C. This ratio decreases with increasing NH3 activity and with increasing temperature. Even at high temperatures (e.g., 200°C), it is at least 3-4 orders-of-magnitude above unity. It is notable that neither formic acid nor ammonia have been detected in any plumes [1]. We thus infer that the detected HCN is unlikely to have equilibrated with an aqueous solution below Enceladus' surface. Chemical kinetic considerations indicate that the hydrolysis lifetime of HCN has a complex dependence on pH, and decreases with increasing temperature. We find that, even at the pH value most conducive to the survival of HCN (~5), HCN can persist for only about 5 Ma in liquid water at 0°C. Thus, the HCN in the plumes could not have come from a long-lasting ocean or sea, and probably came from a recent aqueous melt or some icy phase. A liquid source for the HCN would be more restrictive than an ice source. For example, an aqueous solution must have a pH between 4-6 for HCN to be preserved in it for at least ~1 Ma at 0°C. However, this pH restriction would be lifted if the HCN source were a very young pool (i.e., centuries-millennia old). On the other hand, it is expected that HCN could survive indefinitely in an icy matrix. The proposed HCN sources may be less favorable abodes for life than a long-lived aqueous reservoir. Reference: [1] Waite J.H. et al. (2008) Eur. Planet. Sci. Congr. 3, EPSC2008-A-00593.

  2. 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.

  3. 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.

  4. On the interpretation of the Q-branch of hydrogen in water

    NASA Astrophysics Data System (ADS)

    Borysow, Jacek; Moraldi, Massimo

    2016-06-01

    The Raman Q branch of hydrogen dissolved in water is interpreted by means of a theory based on perturbative methods. Consistent with experimental results on pure rotational S(j) lines, in the theory we assume that the shifts of the lines composing the Q branch do not depend on the rotational states. It is found that an important mechanism determining the structure of the Q branch is the motional narrowing effect, particularly for the transitions involving ortho-hydrogen. A simple model of the Q branch allows the estimation of the rotational and vibrational relaxation properties of hydrogen in solution with water.

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

    PubMed

    Zou, Xiaoxin; Zhang, Yu

    2015-08-01

    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. PMID:25886650

  6. Loss of water from Venus. I - Hydrodynamic escape of hydrogen

    NASA Technical Reports Server (NTRS)

    Kasting, J. F.; Pollack, J. B.

    1983-01-01

    A one-dimensional photochemical-dynamic model is used to study hydrodynamic loss of hydrogen from a primitive, water-rich atmosphere on Venus. The escape flux is calculated as a function of the H2O mixing ratio at the atmospheric cold trap. The cold trap mixing ratio is then related in an approximate fashion to the H2O concentration in the lower atmosphere. Hydrodynamic escape should have been the dominant loss process for hydroogen when the H2O mass mixing ratio in the lower atmosphere exceeded approximately 0.1. The escape rate would have depended upon the magnitude of the solar ultraviolet flux and the atmospheric EUV heating efficiency and, to a lesser extent, on the O2 content of the atmosphere. The time required for Venus to have lost the bulk of a terrestrial ocean of water is on the order of a billion years. Deuterium would have been swept away along with hydrogen if the escape rate was high enough, but some D/H enrichment should have occurred as the escape rate slowed down.

  7. 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.

  8. 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.

  9. Modeling the oxidation of phenolic compounds by hydrogen peroxide photolysis.

    PubMed

    Zhang, Tianqi; Cheng, Long; Ma, Lin; Meng, Fanchao; Arnold, Robert G; Sáez, A Eduardo

    2016-10-01

    Hydrogen peroxide UV photolysis is among the most widely used advanced oxidation processes (AOPs) for the destruction of trace organics in waters destined for reuse. Previous kinetic models of hydrogen peroxide photolysis focus on the dynamics of hydroxyl radical production and consumption, as well as the reaction of the target organic with hydroxyl radicals. However, the rate of target destruction may also be affected by radical scavenging by reaction products. In this work, we build a predictive kinetic model for the destruction of p-cresol by hydrogen peroxide photolysis based on a complete reaction mechanism that includes reactions of intermediates with hydroxyl radicals. The results show that development of a predictive kinetic model to evaluate process performance requires consideration of the complete reaction mechanism, including reactions of intermediates with hydroxyl radicals. PMID:27448315

  10. Hydrogen-rich water ameliorates bronchopulmonary dysplasia (BPD) in newborn rats.

    PubMed

    Muramatsu, Yukako; Ito, Mikako; Oshima, Takahiro; Kojima, Seiji; Ohno, Kinji

    2016-09-01

    Bronchopulmonary dysplasia (BPD) is characterized by developmental arrest of the alveolar tissue. Oxidative stress is causally associated with development of BPD. The effects of hydrogen have been reported in a wide range of disease models and human diseases especially caused by oxidative stress. We made a rat model of BPD by injecting lipopolysaccharide (LPS) into the amniotic fluid at E16.5. The mother started drinking hydrogen-rich water from E9.5 and also while feeding milk. Hydrogen normalized LPS-induced abnormal enlargement of alveoli at P7 and P14. LPS increased staining for nitrotyrosine and 8-OHdG of the lungs, and hydrogen attenuated the staining. At P1, LPS treatment decreased expressions of genes for FGFR4, VEGFR2, and HO-1 in the lungs, and hydrogen increased expressions of these genes. In contrast, LPS treatment and hydrogen treatment had no essential effect on the expression of SOD1. Inflammatory marker proteins of TNFα and IL-6 were increased by LPS treatment, and hydrogen suppressed them. Treatment of A549 human lung adenocarcinoma epithelial cells with 10% hydrogen gas for 24 hr decreased production of reactive oxygen species in both LPS-treated and untreated cells. Lack of any known adverse effects of hydrogen makes hydrogen a promising therapeutic modality for BPD. Pediatr Pulmonol. 2016; 51:928-935. © 2016 Wiley Periodicals, Inc. PMID:26845501

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

    PubMed Central

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

    2016-01-01

    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. PMID:27026206

  12. 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

    2016-01-01

    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. PMID:27026206

  13. 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

  14. Miscibility Calculations for Water and Hydrogen in Giant Planets

    NASA Astrophysics Data System (ADS)

    Soubiran, François; Militzer, Burkhard

    2015-06-01

    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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Computer simulation of the water and hydrogen distillation and CECE process and its experimental verification

    SciTech Connect

    Fedorchenko, O.A.; Alekseev, I.A.; Trenin, V.D.; Uborski, V.V.

    1995-10-01

    Mathematical simulation procedures have been developed for three processes of hydrogen isotopes separation: (1) a non steady-state water distillation; (2) a cryogenic distillation; and (3) a combined electrolysis and multistage water/hydrogen catalytic exchange (CECE) process. The simulation procedures possess some special features. Thus, the comparatively large step of integration and as a result of this high fast-acting is the peculiarity of the model for the dynamic behaviour of water distillation column operating at total reflux. The simulation procedure for CECE process considers six components and three phases (liquid water, water vapour, and hydrogen gas) and allows one to carry out computations for any mole fraction stock. This procedure, as the one for cryogenic distillation process, is not based on the Newton-Raphson method, and, in spite of this, convergence is reached by a small number of iterations (4 - 11). 8 refs., 4 figs., 6 tabs.

  20. 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.

  1. 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.

  2. Understanding the role of hydrogen bonds in water dynamics and protein stability.

    PubMed

    Bianco, Valentino; Iskrov, Svilen; Franzese, Giancarlo

    2012-01-01

    The mechanisms of cold and pressure denaturation of proteins are a matter of debate, but it is commonly accepted that water plays a fundamental role in the process. It has been proposed that the denaturation process is related to an increase of hydrogen bonds among hydration water molecules. Other theories suggest that the causes of denaturation are the density fluctuations of surface water, or the destabilization of hydrophobic contacts as a consequence of water molecule inclusions inside the protein, especially at high pressures. We review some theories that have been proposed to give insight into this problem, and we describe a coarse-grained model of water that compares well with experiments for proteins' hydration water. We introduce its extension for a homopolymer in contact with the water monolayer and study it by Monte Carlo simulations in an attempt to understand how the interplay of water cooperativity and interfacial hydrogen bonds affects protein stability. PMID:23277668

  3. Dynamical models of hydrogenated amorphous silicon

    NASA Astrophysics Data System (ADS)

    Mousseau, Normand; Lewis, Laurent J.

    1991-04-01

    The results of our molecular-dynamics simulation of bulk hydrogenated amorphous silicon using empirical potentials are presented. More specifically, we discuss a dynamical procedure for incorporating hydrogen into a pure amorphous silicon matrix, which is derived from the concept of floating bonds put forward by Pantelides [Phys. Rev. Lett. 57, 2979 (1986)]. The structures resulting from this model are compared with those obtained with use of a static approach recently developed by us. This method exhibits considerable improvement over the previous one and, in particular, unambiguously reveals the strain-relieving role of hydrogen. While the former model leads to substantial overcoordination, the present one results in almost perfect tetrahedral bonding, with an average coordination number Z=4.03, the lowest value ever achieved using a Stillinger-Weber potential. The simulations are also used to calculate the vibrational densities of states, which are found to be in good accord with corresponding neutron-scattering measurements.

  4. 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. PMID:27479235

  5. Concerted hydrogen-atom abstraction in photosynthetic water oxidation.

    PubMed

    Westphal, K L; Tommos, C; Cukier, R I; Babcock, G T

    2000-06-01

    Photosystem II evolves oxygen by using water in the unlikely role of a reductant. The absorption of sunlight by chlorophyll produces highly oxidizing equivalents that are filled with electrons stripped from water. This proton-coupled redox chemistry occurs at the oxygen-evolving complex, which contains a tetramanganese cluster, a redox-active tyrosine amino acid hydrogen-bonded to a histidine amino acid, a calcium ion and chloride. Hydrogen-atom abstraction by the tyrosyl radical from water bound to the manganese cluster is now widely held to occur in this process, at least for some of the steps in the catalytic cycle. We discuss kinetic and energetic constraints on the hydrogen-atom abstraction process. PMID:10837268

  6. Theoretical investigation of the injection and evaporation of water in a hydrogen/oxygen steam generator

    NASA Astrophysics Data System (ADS)

    Beer, Stefan

    1991-07-01

    Water is injected into the gas stream for the purpose of cooling the reaction products resulting from the stochiometric combustion of hydrogen with oxygen. The penetration of the jet decisively influences the temperature profile across the flow cross section in the water vapor. The penetration of the water jet into the stream is calculated using the jet shedding model and compared with the garden hose model. Models for the evaporation of water droplets in superheated steam are developed for calculating the evaporation paths. The parameters which influence the injection and evaporation process are subjected to variation and their effects in the evaporation paths are analyzed.

  7. 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.

  8. 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

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

    PubMed

    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

  10. 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.

  11. 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.

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

    PubMed

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

    2016-08-01

    Hydrogen isotope (δ(2)H) analysis is widely used in animal ecology to study continental-scale movement because δ(2)H can trace precipitation and climate. To understand the biochemical underpinnings of how hydrogen is incorporated into biomolecules, we measured the δ(2)H of individual amino acids (AAs) in Escherichia coli cultured in glucose-based or complex tryptone-based media in waters with δ(2)H values ranging from -55‰ to +1,070‰. The δ(2)H values of AAs in tryptone spanned a range of ∼250‰. In E. coli grown on glucose, the range of δ(2)H among AAs was nearly 200‰. The relative distributions of δ(2)H of AAs were upheld in cultures grown in enriched waters. In E. coli grown on tryptone, the δ(2)H of nonessential AAs varied linearly with the δ(2)H of media water, whereas δ(2)H of essential AAs was nearly identical to δ(2)H 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 δ(2)H can route directly at the molecular level. We conclude that the patterns and distributions in δ(2)H of AAs are determined through biosynthetic reactions, suggesting that δ(2)H could become a new biosignature for studying novel microbial pathways. Our results also show that δ(2)H of AAs in an organism's tissues provides a dual tracer for food and environmental (e.g., drinking) water. PMID:27444017

  13. Experimental study of hydrogen production by direct decomposition of water

    NASA Astrophysics Data System (ADS)

    Bilgen, E.; Galindo, J.; Baykara, S. Z.

    The hydrogen production by direct decomposition of water in a solar furnace is studied. The set-up is a horizontal axis system consisting of two 1.0 kW parabolic concentrators, both powered by a single heliostat. A temperature of 3000 K is possible. The water is fed to the reactor installed at the focal space of the concentrator, and the steam is decomposed at about 2500 K. The reactor consisted of a cylindrical cavity type refractory receiver covered with a silica cupola. The steam was introduced at a known rate into the cavity and the product gases were quenched. After the condensation of steam, hydrogen and oxygen were collected in a reservoir. Results indicate that with an optimized system, it is possible to produce hydrogen at about 70 percent rate of the theoretical value at the temperature level studied.

  14. Process modeling of hydrogen production from municipal solid waste

    SciTech Connect

    Thorsness, C.B.

    1995-01-01

    The ASPEN PLUS commercial simulation software has been used to develop a process model for a conceptual process to convert municipal solid waste (MSW) to hydrogen. The process consists of hydrothermal treatment of the MSW in water to create a slurry suitable as feedstock for an oxygen blown Texaco gasifier. A method of reducing the complicated MSW feed material to a manageable set of components is outlined along with a framework for modeling the stoichiometric changes associated with the hydrothermal treatment process. Model results indicate that 0.672 kmol/s of hydrogen can be produced from the processing of 30 kg/s (2600 tonne/day) of raw MSW. A number of variations on the basic processing parameters are explored and indicate that there is a clear incentive to reduce the inert fraction in the processed slurry feed and that cofeeding a low value heavy oil may be economically attractive.

  15. Fluorescence Quenching of Benzaldehyde in Water by Hydrogen Atom Abstraction.

    PubMed

    Fletcher, Katharyn; Bunz, Uwe H F; Dreuw, Andreas

    2016-09-01

    We computed the mechanism of fluorescence quenching of benzaldehyde in water through relaxed potential energy surface scans. Time-dependent density functional theory calculations along the protonation coordinate from water to benzaldehyde reveal that photoexcitation to the bright ππ* (S3 ) state is immediately followed by ultrafast decay to the nπ* (S1 ) state. Evolving along this state, benzaldehyde (BA) abstracts a hydrogen atom, resulting in a BAH(.) and OH(.) radical pair. Benzaldehyde does not act as photobase in water, but abstracts a hydrogen atom from a nearby solvent molecule. The system finally decays back to the ground state by non-radiative decay and an electron transfers back to the OH(.) radical. Proton transfer from BAH(+) to OH(-) restores the initial situation, BA in water. PMID:27305520

  16. On Dipole Moments and Hydrogen Bond Identification in Water Clusters.

    PubMed

    Bakó, Imre; Mayer, István

    2016-06-30

    It is demonstrated that the localized orbitals calculated for a water cluster have small delocalization tails along the hydrogen bonds, that are crucial in determining the resulting dipole moments of the system. (By cutting them, one gets much smaller dipole moments for the individual monomers-close to the values one obtains by using a Bader-type analysis.) This means that the individual water monomers can be delimited only in a quite fuzzy manner, and the electronic charge density in a given point cannot be assigned completely to that or another molecule. Thus, one arrives to the brink of breaking the concept of a water cluster consisting of individual molecules. The analysis of the tails of the localized orbitals can also be used to identify the pairs of water molecules actually forming hydrogen bonds. PMID:27280888

  17. 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.

  18. 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.

  19. EPANET WATER QUALITY MODEL

    EPA Science Inventory

    EPA NET represents a third generation of water quality modeling software developed by the U.S. EPA's Drinking Water Research Division, offering significant advances in the state of the art for network water quality analysis. PANET performs extended period simulation of hydraulic ...

  20. Probing Defects and Correlations in the Hydrogen-Bond Network of ab Initio Water.

    PubMed

    Gasparotto, Piero; Hassanali, Ali A; Ceriotti, Michele

    2016-04-12

    The hydrogen-bond network of water is characterized by the presence of coordination defects relative to the ideal tetrahedral network of ice, whose fluctuations determine the static and time-dependent properties of the liquid. Because of topological constraints, such defects do not come alone but are highly correlated coming in a plethora of different pairs. Here we discuss in detail such correlations in the case of ab initio water models and show that they have interesting similarities to regular and defective solid phases of water. Although defect correlations involve deviations from idealized tetrahedrality, they can still be regarded as weaker hydrogen bonds that retain a high degree of directionality. We also investigate how the structure and population of coordination defects is affected by approximations to the interatomic potential, finding that, in most cases, the qualitative features of the hydrogen-bond network are remarkably robust. PMID:26881726

  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 sticking of atomic hydrogen on amorphous water ice

    SciTech Connect

    Veeraghattam, Vijay K.; Manrodt, Katie; Lewis, Steven P.; Stancil, P. C. E-mail: lewis@physast.uga.edu

    2014-07-20

    Using classical molecular dynamics, we have simulated the sticking and scattering process of a hydrogen atom on an amorphous ice film to predict the sticking probability of hydrogen on ice surfaces. A wide range of initial kinetic energies of the incident hydrogen atom (10 K-600 K) and two different ice temperatures (10 K and 70 K) were used to investigate this fundamental process in interstellar chemistry. We report here the sticking probability of atomic hydrogen as a function of incident kinetic energy, gas temperature, and substrate temperature, which can be used in astrophysical models. The current results are compared to previous theoretical and experimental studies that have reported a wide range in the sticking coefficient.

  3. 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.

  4. 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

  5. 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.

  6. Hydrogen evolution from water through metal sulfide reactions.

    PubMed

    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 M2S(X)(-) (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. PMID:24289348

  7. Modeling of the Process of Three-Isotope (H, D, T) Exchange Between Hydrogen Gas and Water Vapour on Pt-SDBC Catalyst over a Wide Range of Deuterium Concentration

    SciTech Connect

    Fedorchenko, O.A.; Alekseev, I.A.; Tchijov, A.S.; Uborsky, V.V.

    2005-07-15

    The large scale studies of Combined Electrolysis and Catalytic Exchange (CECE) process in Petersburg Nuclear Physics Institute showed a complicated influence of various factors on the process caused by the presence of two simultaneous isotope exchange sub processes: counter-current phase exchange (between liquid water and water vapour) and co-current catalytic exchange (between hydrogen gas and water vapour). A laboratory scale set-up of glass made apparatuses was established in such a way that it allows us to study phase and catalytic exchange apart. A computer model of the set-up has been developed.The catalytic isotope exchange model formulation is presented. A collection of reversible chemical reactions is accompanied by diffusion of the gaseous reactants and reaction products in the pores of catalyst carrier. This has some interesting features that are demonstrated. Thus it was noted that the flow rates ratio (gas to vapour - {lambda} = G/V) as well as the concentrations of reactants exert influence on the process efficiency.

  8. 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.

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

    PubMed

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

    2016-05-21

    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. PMID:27208929

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

    SciTech Connect

    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.

  11. 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.

  12. 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

  13. 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.

  14. 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

    2016-01-01

    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

  15. 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.

  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. 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.

  18. Electrocatalytic hydrogen evolution in acidic water with molecular cobalt tetraazamacrocycles.

    PubMed

    McCrory, Charles C L; Uyeda, Christopher; Peters, Jonas C

    2012-02-15

    A series of water-soluble molecular cobalt complexes of tetraazamacrocyclic ligands are reported for the electrocatalytic production of H(2) from pH 2.2 aqueous solutions. The comparative data reported for this family of complexes shed light on their relative efficiencies for hydrogen evolution in water. Rotating disk electrode voltammetry data are presented for each of the complexes discussed, as are data concerning their respective pH-dependent electrocatalytic activity. In particular, two diimine-dioxime complexes were identified as exhibiting catalytic onset at comparatively low overpotentials relative to other reported homogeneous cobalt and nickel electrocatalysts in aqueous solution. These complexes are stable at pH 2.2 and produce hydrogen with high Faradaic efficiency in bulk electrolysis experiments over time intervals ranging from 2 to 24 h. PMID:22280515

  19. 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.

  20. 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.

  1. Leaf water and plant wax hydrogen isotopes in a European sample network

    NASA Astrophysics Data System (ADS)

    Nelson, D. B.; Kahmen, A.

    2014-12-01

    The hydrogen isotopic composition of plant waxes in sediments is now routinely used as a hydroclimate proxy. This application is based largely on empirical calibrations that have demonstrated continental-scale correlations between source water and lipid hydrogen isotope values. But at smaller spatial scales and for individual locations it is increasingly recognized that factors that modify apparent fractionation between source water and leaf lipid hydrogen isotope values must also be considered. 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. Recent advances in theory have permitted mechanistic models to be developed that can be used to predict the mean leaf water hydrogen and oxygen 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. This will provide

  2. 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.

  3. 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.

  4. Electrons and Hydrogen-Bond Connectivity in Liquid Water

    SciTech Connect

    Fernandez-Serra, M.V.; Artacho, Emilio

    2006-01-13

    The network connectivity in liquid water is revised in terms of electronic signatures of hydrogen bonds (HBs) instead of geometric criteria, in view of recent x-ray absorption studies. The analysis is based on ab initio molecular-dynamics simulations at ambient conditions. Even if instantaneous threadlike structures are observed in the electronic network, they continuously reshape in oscillations reminiscent of the r and t modes in ice ({tau}{approx}170 fs). However, two water molecules initially joined by a HB remain effectively bound over many periods regardless of its electronic signature.

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. STREAM WATER QUALITY MODEL

    EPA Science Inventory

    QUAL2K (or Q2K) is a river and stream water quality model that is intended to represent a modernized version of the QUAL2E (or Q2E) model (Brown and Barnwell 1987). Q2K is similar to Q2E in the following respects:

    • One dimensional. The channel is well-mixed vertically a...

    • 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

    • 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.

    • Viscosity of Water under Electric Field: Anisotropy Induced by Redistribution of Hydrogen Bonds.

      PubMed

      Zong, Diyuan; Hu, Han; Duan, Yuanyuan; Sun, Ying

      2016-06-01

      The viscosity of water under an external electric field of 0.00-0.90 V/nm was studied using both molecular dynamics simulations and atomistic modeling accounting for intermolecular potentials. For all temperatures investigated, the water viscosity becomes anisotropic under an electric field: the viscosity component parallel to the field increases monotonically with the field strength, E, while the viscosity perpendicular to the field first decreases and then increases with E. This anisotropy is believed to be mainly caused by the redistribution of hydrogen bonds under the electric field. The preferred orientation of hydrogen bonds along the field direction leads to an increase of the energy barrier of a water molecule to its neighboring site, and hence increases the viscosity in that direction. However, the probability of hydrogen bonds perpendicular to the electric field decreases with E, together with the increase of the average number of hydrogen bonds per molecule, causing the perpendicular component of water viscosity to first decrease and then increase with the electric field. PMID:27163345

    • 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

    • A Transferable Coarse-Grained Model for Hydrogen Bonding Liquids

      PubMed Central

      Golubkov, Pavel A.; Wu, Johnny C.; Ren, Pengyu

      2008-01-01

      We present here a recent development of a generalized coarse-grained model for use in molecular simulations. In this model, interactions between coarse-grained particles consist of both van der Waals and explicit electrostatic components. As a result, the coarse-grained model offers the transferability that is lacked by most current effectivepotential based approaches. The previous center-of-mass framework1 is generalized here to include arbitrary off-center interaction sites for both Gay-Berne and multipoles. The new model has been applied to molecular dynamic simulations of neat methanol liquid. By placing a single point multipole at the oxygen atom rather than at the center of mass of methanol, there is a significant improvement in the ability to capture hydrogen-bonding. The critical issue of transferability of the coarse-grained model is verified on methanol-water mixtures, using parameters derived from neat liquids without any modification. The mixture density and internal energy from coarse-grained molecular dynamics simulations show good agreement with experimental measurements, on a par with what has been obtained from more detailed atomic models. By mapping the dynamics trajectory from the coarse-grained simulation into the all-atom counterpart, we are able to investigate atomic .level structure and interaction. Atomic radial distribution functions of neat methanol, neat water and mixtures compare favorably to experimental measurements. Furthermore, hydrogen-bonded 6- and 7-molecule chains of water and methanol observed in the mixture are in agreement with previous atomic simulations. PMID:18688358

    • 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

    • 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.

    • A method for the modulation of membrane fluidity: homogeneous catalytic hydrogenation of phospholipids and phospholipids and phospholipid-water model biomembranes.

      PubMed Central

      Chapman, D; Quinn, P J

      1976-01-01

      The fatty acids associated with phospholipids of cell membranes, and particularly their degree of unsaturation, contribute to the fluidity of their structure and hance determine many of their biological properties. We describe a technique for modulating membrane fluidity which consists of hydrogenating the unsaturated double bonds of membrane phospholipids. This has been accomplished using a homogeneous catalyst. The process has been applied to phospholipids in organic solvents, to phospholipids dispersed as multibilayers in aqueous systems, and also to sonicated preparations of phospholipids arranged as single bilayer vesicles. Preliminary experiments have also been performed with biological membranes. These results indicate that the process of homogeneous catalysis for the modulation of lipid fluidity of biological cell membranes may have considerable future biological and biochemical application. PMID:1069280

    • Stretching of hydrogen-bonded OH in the lowest singlet excited electronic state of water dimer.

      PubMed

      Chipman, Daniel M

      2006-01-28

      The lowest singlet excited electronic state of water monomer in the gas phase is strictly dissociative along a OH stretch coordinate but changes its nature when the stretched OH moiety is hydrogen bonded to a neighboring water molecule. This work extends previous exploration of the water dimer excited singlet potential-energy surface, using computational methods that are reliable even at geometries well removed from the ground-state equilibrium. First, the hydrogen-bonded OH moiety is stretched far enough to establish the existence of a barrier that is sufficient to support a quasibound vibrational state of the OH oscillator near the Franck-Condon region. Second, the constraint of an icelike structure is relaxed, and it is found that a substantial fraction of liquidlike structures also supports a quasibound vibrational state. These potential-energy explorations on stretching of the hydrogen-bonded OH moiety in a water dimer are discussed as a model for understanding the initial dynamics upon excitation into the lowest excited singlet state of condensed water. The possibility is raised that the excited-state lifetime may be long enough to allow for exciton migration, which would provide a mechanism for energy transport in condensed water phases. PMID:16460160

    • 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

    • 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.

  1. 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.

  2. The influence of environmental water on the hydrogen stable isotope ratio in aquatic consumers.

    PubMed

    Solomon, Christopher T; Cole, Jonathan J; Doucett, Richard R; Pace, Michael L; Preston, Nicholas D; Smith, Laura E; Weidel, Brian C

    2009-08-01

    Aquatic food webs are subsidized by allochthonous resources but the utilization of these resources by consumers can be difficult to quantify. Stable isotope ratios of hydrogen (deuterium:hydrogen; deltaD) potentially distinguish allochthonous inputs because deltaD differs between terrestrial and aquatic primary producers. However, application of this tracer is limited by uncertainties regarding the trophic fractionation of deltaD and the contributions of H from environmental water (often called "dietary water") to consumer tissue H. We addressed these uncertainties using laboratory experiments, field observations, modeling, and a literature synthesis. Laboratory experiments that manipulated the deltaD of water and food for insects, cladoceran zooplankton, and fishes provided strong evidence that trophic fractionation of deltaD was negligible. The proportion of tissue H derived from environmental water was substantial yet variable among studies; estimates of this proportion, inclusive of lab, field, and literature data, ranged from 0 to 0.39 (mean 0.17 +/- 0.12 SD). There is a clear need for additional studies of environmental water. Accounting for environmental water in mixing models changes estimates of resource use, although simulations suggest that uncertainty about the environmental water contribution does not substantially increase the uncertainty in estimates of resource use. As long as this uncertainty is accounted for, deltaD may be a powerful tool for estimating resource use in food webs. PMID:19471971

  3. Radiolytic hydrogen generation at silicon carbide-water interfaces

    NASA Astrophysics Data System (ADS)

    Schofield, Jennifer; Reiff, Sarah C.; Pimblott, Simon M.; LaVerne, Jay A.

    2016-02-01

    While many of the proposed uses of SiC in the nuclear industry involve systems that are assumed to be dry, almost all materials have dissociated chemisorbed water associated with their surface, which can undergo chemistry in radiation fields. Silicon carbide α-phase and β-phase nanoparticles with water were irradiated with γ-rays and 5 MeV 4He ions followed by the determination of the production of molecular hydrogen, H2, and characterization of changes in the particle surface. The yields of H2 from SiC-water slurries were always greater than expected from a simple mixture rule indicating that the presence of SiC was influencing the production of H2 from water, probably through an energy transfer from the solid to liquid phase. Although the increase in H2 yields was modest, a decrease in the water mass percentage led to an increase in H2 yields, especially for very low amounts of water. Surface analysis techniques included diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), nitrogen absorption with the Brunauer - Emmett - Teller (BET) methodology for surface area determination, X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). Little change in the SiC surface was observed following radiolysis except for some conversion of β-phase SiC to the α-phase and the formation of SiO2 with He ion radiolysis.

  4. 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

  5. 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 ...

  6. Hydrogen Production:. Ceramic Materials for High Temperature Water Electrolysis

    NASA Astrophysics Data System (ADS)

    Hammou, A.

    2006-06-01

    Hydogen, H2 is regarded as the main energy vector for the future. Today, the world production of hydrogen rises to 550 billion Nm3 (44 Mt) corresponding to 1,5% of the primary energy production. Contrary to fossil fuels, H2 does not exist in a native form and its use obviously requires its fabrication and storage. The future status of H2 as a fuel for electricity production (fuel cells) and for automobile transportation makes necessary a considerable increase of its production. Some H2 manufactoring processes are briefly described in the first part of this article : (i) steam methane reforming, (ii) water decomposition by thermochemical cycles, (iii) water decomposition by photoelectrochemistry, (iv) water or organic compounds decomposition in using bacteria or alguae. The second part concerns the H2 production by water electrolysis. This manufactoring process does not exceed 1% of the total production of hydrogen. It is expected that the electrolysers working at high temperature (700-900°C) using ceramic oxides based electrolytes are the more promising. Two groups are considered: electrolysers with proton conductors or oxide ion conductors as electrolytes. Proton conductors belong to the perovskite oxides family MCe1-xLnxO3 with M = Ba, Sr and Ln = Lanthanide. For these conductors, few results on water electrolysis at high temperature are available in the litterature and will be shown here. Electrolysers using oxide ion conductors are more promising. The selected materials are those developped for SOFCs : YSZ for the electrolyte, Ni based cermets for the cathode materials and La1-xSrxMO3±δ with M = Mn, Co, Ni, Fe ... The electrochemical characteristics of the anodic and cathodic interfaces as well as the perfomances of electrolysers working at high temperature are presented.

  7. 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.

  8. 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.

  9. 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

  10. 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

  11. Protein hydrogen exchange: testing current models.

    PubMed

    Skinner, John J; Lim, Woon K; Bédard, Sabrina; Black, Ben E; Englander, S Walter

    2012-07-01

    To investigate the determinants of protein hydrogen exchange (HX), HX rates of most of the backbone amide hydrogens of Staphylococcal nuclease were measured by NMR methods. A modified analysis was used to improve accuracy for the faster hydrogens. HX rates of both near surface and well buried hydrogens are spread over more than 7 orders of magnitude. These results were compared with previous hypotheses for HX rate determination. Contrary to a common assumption, proximity to the surface of the native protein does not usually produce fast exchange. The slow HX rates for unprotected surface hydrogens are not well explained by local electrostatic field. The ability of buried hydrogens to exchange is not explained by a solvent penetration mechanism. The exchange rates of structurally protected hydrogens are not well predicted by algorithms that depend only on local interactions or only on transient unfolding reactions. These observations identify some of the present difficulties of HX rate prediction and suggest the need for returning to a detailed hydrogen by hydrogen analysis to examine the bases of structure-rate relationships, as described in the companion paper (Skinner et al., Protein Sci 2012;21:996-1005). PMID:22544567

  12. 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

  13. Effect of the Hydrogen Bond in Photoinduced Water Dissociation: A Double-Edged Sword.

    PubMed

    Yang, Wenshao; Wei, Dong; Jin, Xianchi; Xu, Chenbiao; Geng, Zhenhua; Guo, Qing; Ma, Zhibo; Dai, Dongxu; Fan, Hongjun; Yang, Xueming

    2016-02-18

    Photoinduced water dissociation on rutile-TiO2 was investigated using various methods. Experimental results reveal that the water dissociation occurs via transferring an H atom to a bridge bonded oxygen site and ejecting an OH radical to the gas phase during irradiation. The reaction is strongly suppressed as the water coverage increases. Further scanning tunneling microscopy study demonstrates that hydrogen bonds between water molecules have a dramatic effect on the reaction. Interestingly, a single hydrogen bond in water dimer enhances the water dissociation reaction, while one-dimensional hydrogen bonds in water chains inhibit the reaction. Density functional theory calculations indicate that the effect of hydrogen bonds on the OH dissociation energy is likely the origin of this remarkable behavior. The results suggest that avoiding a strong hydrogen bond network between water molecules is crucial for water splitting. PMID:26810945

  14. Proton and hydrogen currents in photosynthetic water oxidation.

    PubMed

    Tommos, C; Babcock, G T

    2000-05-12

    The photosynthetic processes that lead to water oxidation involve an evolution in time from photon dynamics to photochemically-driven electron transfer to coupled electron/proton chemistry. The redox-active tyrosine, Y(Z), is the component at which the proton currents necessary for water oxidation are switched on. The thermodynamic and kinetic implications of this function for Y(Z) are discussed. These considerations also provide insight into the related roles of Y(Z) in preserving the high photochemical quantum efficiency in Photosystem II (PSII) and of conserving the highly oxidizing conditions generated by the photochemistry in the PSII reaction center. The oxidation of Y(Z) by P(680)(+) can be described well by a treatment that invokes proton coupling within the context of non-adiabatic electron transfer. The reduction of Y(.)(Z), however, appears to proceed by an adiabatic process that may have hydrogen-atom transfer character. PMID:10812034

  15. Hydrogen bonding in the ethanol-water dimer.

    PubMed

    Finneran, Ian A; Carroll, P Brandon; Allodi, Marco A; Blake, Geoffrey A

    2015-10-01

    We report the first rotational spectrum of the ground state of the isolated ethanol-water dimer using chirped-pulse Fourier transform microwave spectroscopy between 8-18 GHz. With the aid of isotopic substitutions, and ab initio calculations, we identify the measured conformer as a water-donor/ethanol-acceptor structure. Ethanol is found to be in the gauche conformation, while the monomer distances and orientations likely reflect a cooperation between the strong (O-HO) and weak (C-HO) hydrogen bonds that stabilizes the measured conformer. No other conformers were assigned in an argon expansion, confirming that this is the ground-state structure. This result is consistent with previous vibrationally-resolved Raman and infrared work, but sheds additional light on the structure, due to the specificity of rotational spectroscopy. PMID:26325657

  16. WATER-GAS SHIFT WITH INTEGRATED HYDROGEN SEPARATION

    SciTech Connect

    Maria Flytzani-Stephanopoulos; Jerry Meldon; Xiaomei Qi

    2001-12-01

    Optimization of the water-gas shift (WGS) reaction system for hydrogen production for fuel cells is of particular interest to the energy industry. To this end, it is desirable to couple the WGS reaction to hydrogen separation using a semi-permeable membrane, with both processes carried out at high temperature to improve reaction kinetics. Reduced equilibrium conversion of the WGS reaction at high temperatures is overcome by product H{sub 2} removal via the membrane. This project involves 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 will be examined in the project. In the first year of the project, we prepared a series of nanostructured Cu- and Fe-containing ceria catalysts by a special gelation/precipitation technique followed by air calcination at 650 C. Each sample was characterized by ICP for elemental composition analysis, BET-N2 desorption for surface area measurement, and by temperature-programmed reduction in H{sub 2} to evaluate catalyst reducibility. Screening WGS tests with catalyst powders were conducted in a flow microreactor at temperatures in the range of 200-550 C. On the basis of both activity and stability of catalysts in simulated coal gas, and in CO{sub 2}-rich gases, a Cu-CeO{sub 2} catalyst formulation was selected for further study in this project. Details from the catalyst development and testing work are given in this report. Also in this report, we present H{sub 2} permeation data collected with unsupported flat membranes of pure Pd and Pd-alloys over a wide temperature window.

  17. Hydrogen bond cooperativity and anticooperativity within the water hexamer.

    PubMed

    Guevara-Vela, José Manuel; Romero-Montalvo, Eduardo; Mora Gómez, Víctor Arturo; Chávez-Calvillo, Rodrigo; García-Revilla, Marco; Francisco, Evelio; Pendás, Ángel Martín; Rocha-Rinza, Tomás

    2016-07-20

    The hydrogen bond (HB), arguably the most important non-covalent interaction in chemistry, is getting renewed attention particularly in materials engineering. We address herein HB non-additive features by examining different structures of the water hexamer (cage, prism, book, bag and ring). To that end, we rely on the interacting quantum atoms (IQA) topological energy partition, an approach that has been successfully used to study similar effects in smaller water clusters (see Chem. - Eur. J., 19, 14304). Our IQA interaction energies, , are used to classify the strength of HBs in terms of the single/double character of the donor and acceptor H2O molecules involved in the interaction. The strongest hydrogen bonds on this new scale entail double donors and acceptors that show larger values of than those observed in homodromic cycles, paradigms of cooperative effects. Importantly, this means that besides the traditional HB anticooperativity ascribed to double acceptors and donors, the occurrence of these species is also related to HB strengthening. Overall, we hope that the results of this research will lead to a further understanding of the HB non-additivity in intramolecular and intermolecular interactions. PMID:27149337

  18. A Newtonian Model of the Hydrogen Atom

    NASA Astrophysics Data System (ADS)

    Espinosa, James; Woodyard, James

    2010-03-01

    Classical physics was deemed useless in atomic physics in the early 1900's by the vast majority of the physics community. There were multiple problems that were believed to be insoluble, such as blackbody radiation and the photoelectric and Compton effects. Another outstanding problem had been the explanation of atomic spectra. By the 1920's, a very powerful theory called quantum mechanics was created which explained all atomic experiments. Nevertheless, a few physicists, most notably Albert Einstein, rejected this theory on the grounds that it did not give a complete description of the microscopic world. Another more radical view held by Walter Ritz is that Newtonian physics is applicable to all of atomic physics. Over the last couple of years, we have presented classical explanations of many of the ``insoluble'' problems given by textbooks. We will present a model of the hydrogen atom that stays within the framework of Newton. Using only the assumption that the stable building blocks of matter are the electron, positron, and neutrino, we will deduce the following results from our model: orbital stability, line spectra, and scattering cross sections for electrons and protons. We will also qualitatively demonstrate how to explain the lifetime of excited states.

  19. Oxygen and hydrogen isotope signatures of Northeast Atlantic water masses

    NASA Astrophysics Data System (ADS)

    Voelker, Antje H. L.; Colman, Albert; Olack, Gerard; Waniek, Joanna J.; Hodell, David

    2015-06-01

    Only a few studies have examined the variation of oxygen and hydrogen isotopes of seawater in NE Atlantic water masses, and data are especially sparse for intermediate and deep-water masses. The current study greatly expands this record with 527 δ18O values from 47 stations located throughout the mid- to low-latitude NE Atlantic. In addition, δD was analyzed in the 192 samples collected along the GEOTRACES North Atlantic Transect GA03 (GA03_e=KN199-4) and the 115 Iberia-Forams cruise samples from the western and southern Iberian margin. An intercomparison study between the two stable isotope measurement techniques (cavity ring-down laser spectroscopy and magnetic-sector isotope ratio mass spectrometry) used to analyze GA03_e samples reveals relatively good agreement for both hydrogen and oxygen isotope ratios. The surface (0-100 m) and central (100-500 m) water isotope data show the typical, evaporation related trend of increasing values equatorward with the exception for the zonal transect off Cape Blanc, NW Africa. Off Cape Blanc, surface water isotope signatures are modified by the upwelling of fresher Antarctic Intermediate Water (AAIW) that generally has isotopic values of 0.0 to 0.5‰ for δ18O and 0 to 2‰ for δD. Along the Iberian margin the Mediterranean Outflow Water (MOW) is clearly distinguished by its high δ18O (0.5-1.1‰) and δD (3-6‰) values that can be traced into the open Atlantic. Isotopic values in the NE Atlantic Deep Water (NEADW) are relatively low (δ18O: -0.1 to 0.5‰; δD: -1 to 4‰) and show a broader range than observed previously in the northern and southern convection areas. The NEADW is best observed at GA03_e Stations 5 and 7 in the central NE Atlantic basin. Antarctic Bottom Water isotope values are relatively high indicating modification of the original Antarctic source water along the flow path. The reconstructed δ18O-salinity relationship for the complete data set has a slope of 0.51, i.e., slightly steeper than the 0

  20. 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.

  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 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.

  3. Supercomputer modeling of hydrogen combustion in rocket engines

    NASA Astrophysics Data System (ADS)

    Betelin, V. B.; Nikitin, V. F.; Altukhov, D. I.; Dushin, V. R.; Koo, Jaye

    2013-08-01

    Hydrogen being an ecological fuel is very attractive now for rocket engines designers. However, peculiarities of hydrogen combustion kinetics, the presence of zones of inverse dependence of reaction rate on pressure, etc. prevents from using hydrogen engines in all stages not being supported by other types of engines, which often brings the ecological gains back to zero from using hydrogen. Computer aided design of new effective and clean hydrogen engines needs mathematical tools for supercomputer modeling of hydrogen-oxygen components mixing and combustion in rocket engines. The paper presents the results of developing verification and validation of mathematical model making it possible to simulate unsteady processes of ignition and combustion in rocket engines.

  4. 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).

  5. Modeling of Hydrogen Retention in Metallic Plasma Facing Components

    NASA Astrophysics Data System (ADS)

    Guterl, Jerome; Smirnov, R.

    2012-10-01

    The retention of hydrogen isotopes in the vacuum vessel of the ITER device is a critical plasma wall interaction issue for safety (tritium inventory) and operational reasons (hydrogen recycling). In particular, long-term retention of hydrogen have been observed both in the near-surface region and in the bulk of material in experiments reproducing ITER first wall conditions [1]. In this work, we present a modeling of the long-term hydrogen retention in a plasma exposed metallic walltaking into account processes both at the wall surface (material erosion, hydrogen adsorption, etc.) and in the bulk (hydrogen implantation, creation of trap sites, etc.). Using numerical simulations, the model is applied to analyze retention as a function of various parameters of the wall irradiated by hydrogen plasma for beryllium wall. Depth profiles of retained hydrogen for several ion energies as well as dependencies of retained hydrogen amount on wall temperature are obtained, showing good agreement with experimental data. The role of radiation-induced point-defects in the hydrogen retention as well as other aspects of retention are discussed in application to ITER conditions. [4pt] [1] R.A. Anderl, et al., J. Nucl. Mater. 273 (1999) 1

  6. 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.

  7. Relation between cooperative effects in cyclic water, methanol/water, and methanol trimers and hydrogen bonds in methanol/water, ethanol/water, and dimethylether/water heterodimers

    NASA Astrophysics Data System (ADS)

    Masella, Michel; Flament, Jean Pierre

    1998-05-01

    Ab initio calculations at the MP2 level have been performed on water, methanol/water, ethanol/water, and dimethylether/water dimers and on water, methanol/water, and methanol cyclic trimers. Several properties of their hydrogen bonds have been investigated, such as interoxygen distances, O-H bond lengths, binding energies, electronic densities at hydrogen bond (HB) critical points and OH stretch vibrational frequencies. Results exhibit HB enhancements for dimers where the acceptor molecule corresponds to water (HDA dimers) as compared to dimers where the donor is water (HDD dimers). In particular, HB reinforcement depends on the number of alkyl groups bonded to the donor oxygen. For trimers, a comparison among their HB properties and those of dimers shows that HB reinforcements (as compared to isolated dimers) occurring in trimers correlate with HB reinforcements observed in (HDA dimers (as compared to (HDDs). In particular, HB properties of the cyclic water trimer are close to those of alcohol/water HDA dimers, and for the methanol cyclic trimer to that of the dimethylether/water HDA dimer. All of these results agree with an orbital interpretation of hydrogen bonding in terms of charge transfer from donor lone pairs to acceptor antibond σOH*, even if all of the HB properties in cyclic trimers may not be explained from this approach.

  8. 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.

  9. 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.

  10. Spectroscopic modeling of water molecule

    NASA Astrophysics Data System (ADS)

    Danylo, R. I.; Okhrimenko, B. A.

    2013-12-01

    This research is devoted to the vibrational spectroscopy inverse problem solution that gives a possibility to design a molecule and make conclusions about its geometry. The valence angle finding based on the usage of inverse spectral vibrational spectroscopy problem is a well-known task. 3N-matrix method was chosen to solve the proposed task. The usage of this method permits to make no assumptions about the molecule force field, besides it can be applied to molecules of matter in liquid state. Anharmonicity constants assessment is an important part of the valence angle finding. The reduction to zero vibrations is necessary because used matrix analytical expression were found in the harmonic approach. In order to find the single-valued inverse spectral problem of vibrational spectroscopy solution a shape parameter characterizing "mixing" of ω1 and ω2 vibrations forms must be found. The minimum of such a function Υ called a divergence parameter was found. This function characterizes method's accuracy. The valence angle assessment was reduced to the divergence parameter minimization. The β value concerning divergence parameter minimum was interpreted as the desired valence angle. The proposed method was applied for water molecule in liquid state: β = (88,8 ±1,7)° . The found angle fits the water molecule nearest surrounding tetrahedral model including hydrogen bond curvature in the first approximation.

  11. 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

  12. Reverse hydrogen spillover on and hydrogenation of supported metal clusters: insights from computational model studies.

    PubMed

    Vayssilov, Georgi N; Petrova, Galina P; Shor, Elena A Ivanova; Nasluzov, Vladimir A; Shor, Alexei M; St Petkov, Petko; Rösch, Notker

    2012-05-01

    "Reverse" spillover of hydrogen from hydroxyl groups of the support onto supported transition metal clusters, forming multiply hydrogenated metal species, is an essential aspect of various catalytic systems which comprise small, highly active transition metal particles on a support with a high surface area. We review and analyze the results of our computational model studies related to reverse hydrogen spillover, interpreting available structural and spectral data for the supported species and examining the relationship between metal-support and metal-hydrogen interactions. On the examples of small clusters of late transition metals, adsorbed in zeolite cavities, we showed with computational model studies that reverse spillover of hydrogen is energetically favorable for late transition metals, except for Au. This preference is crucial for the chemical reactivity of such bifunctional catalytic systems because both functions, of metal species and of acidic sites, are strongly modified, in some cases even suppressed - due to partial oxidation of the metal cluster and the conversion of protons from acidic hydroxyl groups to hydride ligands of the metal moiety. Modeling multiple hydrogen adsorption on metal clusters allowed us to quantify how (i) the support affects the adsorption capacity of the clusters and (ii) structure and oxidation state of the metal moiety changes upon adsorption. In all models of neutral systems we found that the metal atoms are partially positively charged, compensated by a negative charge of the adsorbed hydrogen ligands and of the support. In a case study we demonstrated with calculated thermodynamic parameters how to predict the average hydrogen coverage of the transition metal cluster at a given temperature and hydrogen pressure. PMID:22353996

  13. 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...

  14. 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.

  15. A first-principles investigation of III-V semiconductor-water interfaces for solar hydrogen production

    NASA Astrophysics Data System (ADS)

    Wood, Brandon; Ogitsu, Tadashi; Schwegler, Eric

    2011-03-01

    Photoelectrochemical devices promise sustainable hydrogen production using sunlight and water. Currently, the highest efficiency devices use III-V semiconductor photoelectrodes; however, stability of these materials under operating conditions remains an issue. In an effort to understand the chemical properties of the electrode-water interface, we have performed first-principles molecular dynamics simulations on model III-V surfaces in realistic aqueous environments. The structure, stability, and chemical activity of these surfaces are investigated, with the aim of understanding the reactive states precursory to photoexcitation and hydrogen evolution. Our results show that surface oxide nucleation is key to facilitating surface reactivity, and that the surface oxygen bonding arrangement is important for determining of the available pathways for water dissociation and corrosion. This points to the importance of III-V surface oxides as intermediates in the water-dissociation component of hydrogen evolution. Prepared by LLNL under Contract DE-AC52-07NA27344.

  16. 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.

  17. 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.

  18. Photoelectrochemical water splitting: silicon photocathodes for hydrogen evolution

    NASA Astrophysics Data System (ADS)

    Warren, Emily L.; Boettcher, Shannon W.; McKone, James R.; Lewis, Nathan S.

    2010-08-01

    The development of low cost, scalable, renewable energy technologies is one of today's most pressing scientific challenges. We report on progress towards the development of a photoelectrochemical water-splitting system that will use sunlight and water as the inputs to produce renewable hydrogen with oxygen as a by-product. This system is based on the design principle of incorporating two separate, photosensitive inorganic semiconductor/liquid junctions to collectively generate the 1.7-1.9 V at open circuit needed to support both the oxidation of H2O (or OH-) and the reduction of H+ (or H2O). Si microwire arrays are a promising photocathode material because the high aspect-ratio electrode architecture allows for the use of low cost, earth-abundant materials without sacrificing energy-conversion efficiency, due to the orthogonalization of light absorption and charge-carrier collection. Additionally, the high surfacearea design of the rod-based semiconductor array inherently lowers the flux of charge carriers over the rod array surface relative to the projected geometric surface of the photoelectrode, thus lowering the photocurrent density at the solid/liquid junction and thereby relaxing the demands on the activity (and cost) of any electrocatalysts. Arrays of Si microwires grown using the Vapor Liquid Solid (VLS) mechanism have been shown to have desirable electronic light absorption properties. We have demonstrated that these arrays can be coated with earth-abundant metallic catalysts and used for photoelectrochemical production of hydrogen. This development is a step towards the demonstration of a complete artificial photosynthetic system, composed of only inexpensive, earth-abundant materials, that is simultaneously efficient, durable, and scalable.

  19. 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

  20. 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.

  1. 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.

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

    PubMed

    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(')-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. PMID:24832276

  3. Modelling of discrete TDS-spectrum of hydrogen desorption

    NASA Astrophysics Data System (ADS)

    Rodchenkova, Natalia I.; Zaika, Yury V.

    2015-12-01

    High concentration of hydrogen in metal leads to hydrogen embrittlement. One of the methods to evaluate the hydrogen content is the method of thermal desorption spectroscopy (TDS). As the sample is heated under vacuumization, atomic hydrogen diffuses inside the bulk and is desorbed from the surface in the molecular form. The extraction curve (measured by a mass-spectrometric analyzer) is recorded. In experiments with monotonous external heating it is observed that background hydrogen fluxes from the extractor walls and fluxes from the sample cannot be reliably distinguished. Thus, the extraction curve is doubtful. Therefore, in this case experimenters use discrete TDS-spectrum: the sample is removed from the analytical part of the device for the specified time interval, and external temperature is then increased stepwise. The paper is devoted to the mathematical modelling and simulation of experimental studies. In the corresponding boundary-value problem with nonlinear dynamic boundary conditions physical- chemical processes in the bulk and on the surface are taken into account: heating of the sample, diffusion in the bulk, hydrogen capture by defects, penetration from the bulk to the surface and desorption. The model aimed to analyze the dynamics of hydrogen concentrations without preliminary artificial sample saturation. Numerical modelling allows to choose the point on the extraction curve that corresponds to the initial quantity of the surface hydrogen, to estimate the values of the activation energies of diffusion, desorption, parameters of reversible capture and hydride phase decomposition.

  4. 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.

  5. On the nature of hydrogen bonding between the phosphatidylcholine head group and water and dimethylsulfoxide

    NASA Astrophysics Data System (ADS)

    Dabkowska, Aleksandra P.; Lawrence, M. Jayne; McLain, Sylvia E.; Lorenz, Christian D.

    2013-01-01

    Molecular dynamics simulations are used to provide a detailed investigation of the hydrogen bond networks around the phosphatidylcholine (PC) head group in 1,2-dipropionyl-sn-glycero-3-phosphocholine in pure water, 10 mol.% and 30 mol.% dimethylsulfoxide (DMSO)-water solutions. Specifically, it is observed that DMSO replaces those water molecules that are within the first solvation shell of the choline, phosphate and ester groups of the PC head group, but are not hydrogen-bonded to the group. The effect of the presence of DMSO on the hydrogen bond network around the PC head groups of the lipid changes with the concentration of DMSO. In comparison to the hydrogen bond network observed in the pure water system, the number of hydrogen-bonded chains of solvent molecules increases slightly for the 10 mol.% DMSO system, while, in the 30 mol.% DMSO system, the number of hydrogen-bonded chains of solvent molecules decreases.

  6. Hydrogen Tunneling in Enzymes and Biomimetic Models

    SciTech Connect

    Layfield, Joshua P.; Hammes-Schiffer, Sharon

    2013-12-20

    Hydrogen transfer reactions play an important role throughout chemistry and biology. In general, hydrogen transfer reactions encompass proton and hydride transfer, which are associated with the transfer of a positively or negatively charged species, respectively, and proton-coupled electron transfer (PCET), which corresponds to the net transfer of one electron and one proton in the simplest case. Such PCET reactions can occur by either a sequential mechanism, in which the proton or electron transfers first, or a concerted mechanism, in which the electron and proton transfer in a single kinetic step with no stable intermediate. Furthermore, concerted PCET reactions can be subdivided into hydrogen atom transfer (HAT), which corresponds to the transfer of an electron and proton between the same donor and acceptor (i.e., the transfer of a predominantly neutral species), and electron-proton transfer (EPT), which corresponds to the transfer of an electron and proton between different donors and acceptors, possibly even in different directions. In all of these types of hydrogen transfer reactions, hydrogen tunneling could potentially play a signficant role. The theoretical development portion of this Review was supported by the National Science Foundation under CHE-10-57875. The biological portion of this Review was funded by NIH Grant No. GM056207. The biomimetic portion was supported as part of the Center for Molecular Electro-catalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  7. Hydrogen Tunneling in Enzymes and Biomimetic Models

    SciTech Connect

    Layfield, Joshua P.; Hammes-Schiffer, Sharon

    2014-04-09

    Hydrogen transfer reactions play an important role throughout chemistry and biology. In general, hydrogen transfer reactions encompass proton and hydride transfer, which are associated with the transfer of a positively or negatively charged species, respectively, and proton-coupled electron transfer (PCET), which corresponds to the net transfer of one electron and one proton in the simplest case. Such PCET reactions can occur by either a sequential mechanism, in which the proton or electron transfers first, or a concerted mechanism, in which the electron and proton transfer in a single kinetic step with no stable intermediate. Furthermore, concerted PCET reactions can be subdivided into hydrogen atom transfer (HAT), which corresponds to the transfer of an electron and proton between the same donor and acceptor (i.e., the transfer of a predominantly neutral species), and electron-proton transfer (EPT), which corresponds to the transfer of an electron and proton between different donors and acceptors, possibly even in different directions. In all of these types of hydrogen transfer reactions, hydrogen tunneling could potentially play a significant role. The biomimetic portion was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  8. 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.

  9. 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.

  10. 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

  11. Model calculations for diffuse molecular clouds. [interstellar hydrogen cloud model

    NASA Technical Reports Server (NTRS)

    Glassgold, A. E.; Langer, W. D.

    1974-01-01

    A steady state isobaric cloud model is developed. The pressure, thermal, electrical, and chemical balance equations are solved simultaneously with a simple one dimensional approximation to the equation of radiative transfer appropriate to diffuse clouds. Cooling is mainly by CII fine structure transitions, and a variety of heating mechanisms are considered. Particular attention is given to the abundance variation of H2. Inhomogeneous density distributions are obtained because of the attenuation of the interstellar UV field and the conversion from atomic to molecular hyrodgen. The effects of changing the model parameters are described and the applicability of the model to OAO-3 observations is discussed. Good qualitative agreement with the fractional H2 abundance determinations has been obtained. The observed kinetic temperatures near 80 K can also be achieved by grain photoelectron heating. The problem of the electron density is solved taking special account of the various hydrogen ions as well as heavier ones.

  12. Cellular Metabolic Activity and the Oxygen and Hydrogen Stable Isotope Composition of Intracellular Water and Metabolites

    NASA Astrophysics Data System (ADS)

    Kreuzer-Martin, H. W.; Hegg, E. L.

    2008-12-01

    biomass of Bacillus subtilis, a Gram-positive bacterium, showed the same pattern. Rapidly-dividing cells derived fewer of their O and H atoms from environmental water than did more slowly-growing cells and spores. To test whether a eukaryotic cell, surrounded by only a membrane, would also maintain an isotopic gradient and a detectable percentage of metabolic water, we applied our approach to cultured rat fibroblasts. Preliminary results showed that approximately 50% of the O and H atoms in exponentially growing cells were derived from metabolic activity. In quiescent cells, metabolic activity generated approximately 25% of the O and H atoms in intracellular water. Thus far, the data we have obtained is consistent with the following model: (1) Intracellular water is composed of water that diffuses in from the extracellular environment and water that is created as a result of metabolic activity. (2) The relative amounts of environmental and metabolic water inside a cell are a function of the cell's metabolic activity. (3) The oxygen and hydrogen isotope ratios of cellular metabolites are a function of those of intracellular water, and therefore reflect the metabolic activity of the cell at the time of biosynthesis.

  13. A model of hydrogen passive autocatalytic recombiner and its validation via CFD simulations

    NASA Astrophysics Data System (ADS)

    Orszulik, Magdalena; Fic, Adam; Bury, Tomasz; Składzień, Jan

    2013-12-01

    Passive autocatalytic recombiners (PAR) is the only used method for hydrogen removal from the containment buildings in modern nuclear reactors. Numerical models of such devices, based on the CFD approach, are the subject of this paper. The models may be coupled with two types of computer codes: the lumped parameter codes, and the computational fluid dynamics codes. This work deals with 2D numerical model of PAR and its validation. Gaseous hydrogen may be generated in water nuclear reactor systems in a course of a severe accident with core overheating. Therefore, a risk of its uncontrolled combustion appears which may be destructive to the containment structure.

  14. 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.

  15. Water templated hydrogen-bonded network of pyridine amide appended carbamate in solid state

    NASA Astrophysics Data System (ADS)

    Ghosh, Kumaresh; Adhikari, Suman; Fröhlich, Roland

    2006-03-01

    The pyridine amide appended carbamates 1 and 2 have been synthesized and their hydrogen-bonded self-assemblies in solid state have been described. The self-association pattern is dependent on the nature the anchored group of the carbamate moiety and influenced by water inclusion. Inclusion of water molecule gives a ladder type hydrogen bonded assemblies with cavities.

  16. 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

  17. Tight-binding model for hydrogen-silicon interactions

    SciTech Connect

    Min, B.J.; Lee, Y.H.; Wang, C.Z.; Chan, C.T.; Ho, K.M. Department of Physics and Astronomy, Ames Laboratory, Iowa State University, Ames, Iowa 50011 )

    1992-03-15

    We have developed an empirical tight-binding model for use in molecular-dynamics simulations to study hydrogen-silicon systems. The hydrogen-silicon interaction is constructed to reproduce the electronic energy levels and vibration frequencies of silane (SiH{sub 4}). Further use of the model in the studies of disilane (Si{sub 2}H{sub 6}) and of hydrogen on the Si(111) surface also yields results in good agreement with first-principles calculations and experiments.

  18. 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.

  19. 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

  20. General model of electrochemical hydrogen absorption into metals

    SciTech Connect

    Lasia, A.; Gregoire, D.

    1995-10-01

    A general model for the hydrogen adsorption and hydrogen absorption into metals has been proposed. It includes reactions of hydrogen evolution M+H{sub 2}O+e=MH{sub ads}+OH{sup {minus}}; MH{sub ads}+H{sub 2}O+e=M+H{sub 2}+OH{sup {minus}}; and 2MH{sub ads}+2M+H{sub 2}; hydrogen absorption MH{sub ads}+MH{sub abs}; and hydrogen diffusion into metal. This problem leads to a system of differential equations which was solved using the differential algebraic equations method. Solutions were obtained for constant potential and constant current charging/discharging in the case of semi-infinite and finite length diffusion for planar, spherical, and cylindrical diffusion. Numerical solutions give new information about the reaction mechanism and may be useful in the determination of the kinetics of these processes.

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

    PubMed

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

    2016-03-01

    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. PMID:26623663

  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. Incorporation of parametric uncertainty into complex kinetic mechanisms: Application to hydrogen oxidation in supercritical water

    SciTech Connect

    Phenix, B.D.; Dinaro, J.L.; Tatang, M.A.; Tester, J.W.; Howard, J.B.; McRae, G.J.

    1998-01-01

    In this study, uncertainty analysis is applied to a supercritical water hydrogen oxidation mechanism to determine the effect of uncertainties in reaction rate constants and species thermochemistry on predicted species concentrations. Forward rate constants and species thermochemistry are assumed to be the sole contributors to uncertainty in the reaction model with all other model parameters and inputs treated as deterministic quantities. Uncertainty propagation is performed using traditional Monte Carlo (MC) simulation and a new, more computationally efficient, probabilistic collocation method called the Deterministic Equivalent Modeling Method (DEMM). The results of both analyses show that there is considerable uncertainty in all predicted species concentrations. The predicted H{sub 2} and O{sub 2} concentrations vary {+-}70% from their median values. Similarly, the HO{sub 2} concentration ranges from +90 to {minus}70% of its median, while the H{sub 2}O{sub 2} concentration varies by +180 to {minus}80%. In addition, the DEMM methodology identified two key model parameters, the standard-state heat of formation of HO{sub 2} radical and the forward rate constant for H{sub 2}O{sub 2} dissociation, as the largest contributors to the uncertainty in the predicted hydrogen and oxygen species concentrations. The analyses further show that the change in model predictions due to the inclusion of real-gas effects, which are potentially important for SCWO process modeling, is small relative to the uncertainty introduced by the model parameters themselves.

  4. Hydrogenation of Carbon Dioxide by Water: Alkali-Promoted Synthesis of Formate

    SciTech Connect

    Hrbek, J.; Hoffmann, F.M.; Yang, Y.; Paul, J.; White, M.G.

    2010-07-15

    Conversion of carbon dioxide utilizing protons from water decomposition is likely to provide a sustainable source of fuels and chemicals in the future. We present here a time-evolved infrared reflection absorption spectroscopy (IRAS) and temperature-programmed desorption (TPD) study of the reaction of CO{sub 2} + H{sub 2}O in thin potassium layers. Reaction at temperatures below 200 K results in the hydrogenation of carbon dioxide to potassium formate. Thermal stability of the formate, together with its sequential transformation to oxalate and to carbonate, is monitored and discussed. The data of this model study suggest a dual promoter mechanism of the potassium: the activation of CO{sub 2} and the dissociation of water. Reaction at temperatures above 200 K, in contrast, is characterized by the absence of formate and the direct reaction of CO{sub 2} to oxalate, due to a drastic reduction of the sticking coefficient of water at higher temperatures.

  5. Kinetic modeling of α-hydrogen abstractions from unsaturated and saturated oxygenate compounds by hydrogen atoms.

    PubMed

    Paraskevas, Paschalis D; Sabbe, Maarten K; Reyniers, Marie-Françoise; Papayannakos, Nikos G; Marin, Guy B

    2014-10-01

    Hydrogen-abstraction reactions play a significant role in thermal biomass conversion processes, as well as regular gasification, pyrolysis, or combustion. In this work, a group additivity model is constructed that allows prediction of reaction rates and Arrhenius parameters of hydrogen abstractions by hydrogen atoms from alcohols, ethers, esters, peroxides, ketones, aldehydes, acids, and diketones in a broad temperature range (300-2000 K). A training set of 60 reactions was developed with rate coefficients and Arrhenius parameters calculated by the CBS-QB3 method in the high-pressure limit with tunneling corrections using Eckart tunneling coefficients. From this set of reactions, 15 group additive values were derived for the forward and the reverse reaction, 4 referring to primary and 11 to secondary contributions. The accuracy of the model is validated upon an ab initio and an experimental validation set of 19 and 21 reaction rates, respectively, showing that reaction rates can be predicted with a mean factor of deviation of 2 for the ab initio and 3 for the experimental values. Hence, this work illustrates that the developed group additive model can be reliably applied for the accurate prediction of kinetics of α-hydrogen abstractions by hydrogen atoms from a broad range of oxygenates. PMID:25209711

  6. Determination of intramolecular hydrogen bonds in amikacin in water solution by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Gaggelli, Elena; Gaggelli, Nicola; Maccotta, Antonella; Valensin, Gianni; Marini, Domenico; Di Cocco, Maria Enrica; Delfini, Maurizio

    1995-10-01

    An NMR investigation has been carried out on amikacin in water solution in the physiological pH range. Two-dimenstional heterocorrelated maps provide 1H NMR chemical shifts from the unambiguous assignment of the 13C NMR spectrum. Reorientational dynamics at the molecular level are interpreted in terms of a pseudoisotropic motion with a correlation time of 0.17 ns at 300 K. The pH and temperature dependences of 13C NMR chemical shifts are interpreted to delineate protonation equilibria (all p Ks are determined) and to assess the occurrence of two intermolecular hydrogen bonds, which are confirmed by molecular modelling.

  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. 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.

  9. 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.

  10. Disequilibrium of hydrogen sulfide in ground water by aeration. Final report

    SciTech Connect

    Ritchey, J.D.

    1981-04-24

    This study examines removal of hydrogen sulfide gas by aeration as a result of bubbling air through water in the well before it is pumped out of the ground. The field study demonstrated that a substantial amount of hydrogen sulfide gas could be successfully removed by the method tested. Evaluation of water analyses indicated three processes that caused reduction in the concentration of hydrogen sulfide gas: (1) hydrogen sulfide gas was released from water to air by gas transfer--indicated by a strong 'rotten egg odor,' characteristic of hydrogen sulfide gas that was emitted from the wellhead; (2) hydrogen sulfide gas was oxidized to elemental sulfur--evidenced by an increase in dissolved oxygen measured in water samples and by clouding of pumped water; and (3) hydrogen sulfide gas was partially ionized--indicated by an increase in the pH and the redox potential of water samples. This field study demonstrates that in-well aeration is an effective method of hydrogen sulfide gas removal in domestic wells with potential application in larger installations.

  11. 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.

  12. 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.

  13. Hydrogen Bonding in Liquid Water and in the Hydration Shell of Salts.

    PubMed

    Dagade, Dilip H; Barge, Seema S

    2016-03-16

    A near-IR spectral study on pure water and aqueous salt solutions is used to investigate stoichiometric concentrations of different types of hydrogen-bonded water species in liquid water and in water comprising the hydration shell of salts. Analysis of the thermodynamics of hydrogen-bond formation signifies that hydrogen-bond making and breaking processes are dominated by enthalpy with non-negligible heat capacity effects, as revealed by the temperature dependence of standard molar enthalpies of hydrogen-bond formation and from analysis of the linear enthalpy-entropy compensation effects. A generalized method is proposed for the simultaneous calculation of the spectrum of water in the hydration shell and hydration number of solutes. Resolved spectra of water in the hydration shell of different salts clearly differentiate hydrogen bonding of water in the hydration shell around cations and anions. A comparison of resolved liquid water spectra and resolved hydration-shell spectra of ions highlights that the ordering of absorption frequencies of different kinds of hydrogen-bonded water species is also preserved in the bound state with significant changes in band position, band width, and band intensity because of the polarization of water molecules in the vicinity of ions. PMID:26749515

  14. Hydrogen Bonding between Metal-Ion Complexes and Noncoordinated Water: Electrostatic Potentials and Interaction Energies.

    PubMed

    Andrić, Jelena M; Misini-Ignjatović, Majda Z; Murray, Jane S; Politzer, Peter; Zarić, Snežana D

    2016-07-01

    The hydrogen bonding of noncoordinated water molecules to each other and to water molecules that are coordinated to metal-ion complexes has been investigated by means of a search of the Cambridge Structural Database (CSD) and through quantum chemical calculations. Tetrahedral and octahedral complexes that were both charged and neutral were studied. A general conclusion is that hydrogen bonds between noncoordinated water and coordinated water are much stronger than those between noncoordinated waters, whereas hydrogen bonds of water molecule in tetrahedral complexes are stronger than in octahedral complexes. We examined the possibility of correlating the computed interaction energies with the most positive electrostatic potentials on the interacting hydrogen atoms prior to interaction and obtained very good correlation. This study illustrates the fact that electrostatic potentials computed for ground-state molecules, prior to interaction, can provide considerable insight into the interactions. PMID:26989883

  15. 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.

  16. 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

  17. On Modeling Hydrogen-Induced Crack Propagation Under Sustained Load

    NASA Astrophysics Data System (ADS)

    Dadfarnia, Mohsen; Somerday, Brian p.; Schembri, Philip E.; Sofronis, Petros; Foulk, James W.; Nibur, Kevin A.; Balch, Dorian K.

    2014-08-01

    The failure of hydrogen containment components is generally associated with subcritical cracking. Understanding subcritical crack growth behavior and its dependence on material and environmental variables can lead to methods for designing structural components in a hydrogen environment and will be beneficial in developing materials resistant to hydrogen embrittlement. In order to identify the issues underlying crack propagation and arrest, we present a model for hydrogen-induced stress-controlled crack propagation under sustained loading. The model is based on the assumptions that (I) hydrogen reduces the material fracture strength and (II) crack propagation takes place when the opening stress over the characteristic distance ahead of a crack tip is greater than the local fracture strength. The model is used in a finite-element simulation of crack propagation coupled with simultaneous hydrogen diffusion in a model material through nodal release. The numerical simulations show that the same physics, i.e., diffusion-controlled crack propagation, can explain the existence of both stages I and II in the velocity versus stress intensity factor ( V- K) curve.

  18. Modeling atomic hydrogen diffusion in GaAs

    NASA Astrophysics Data System (ADS)

    Kagadei, Valerii A.; Nefyodtsev, E.

    2004-05-01

    The hydrogen diffusion model in GaAs in conditions of an intense flow of penetrating atoms has been developed. It is shown that the formation undersurface diffusion barrier layer from immobile interstitial molecules of hydrogen reduce probability of atoms penetration into crystal and rate of their diffusion in GaAs, and influence on the process of shallow- and/or deep-centers passivation. It is exhibited that the influence of diffusion barrier should be taken into account at optimum mode selection of GaAs structure hydrogenation.

  19. 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.

  20. High-Yield Hydrogen Production from Starch and Water by a Synthetic Enzymatic Pathway

    PubMed Central

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

    2007-01-01

    Background The future hydrogen economy offers a compelling energy vision, but there are four main obstacles: hydrogen production, storage, and distribution, as well as fuel cells. Hydrogen production from inexpensive abundant renewable biomass can produce cheaper hydrogen, decrease reliance on fossil fuels, and achieve zero net greenhouse gas emissions, but current chemical and biological means suffer from low hydrogen yields and/or severe reaction conditions. Methodology/Principal Findings Here we demonstrate a synthetic enzymatic pathway consisting of 13 enzymes for producing hydrogen from starch and water. The stoichiometric reaction is C6H10O5 (l)+7 H2O (l)→12 H2 (g)+6 CO2 (g). The overall process is spontaneous and unidirectional because of a negative Gibbs free energy and separation of the gaseous products with the aqueous reactants. Conclusions Enzymatic hydrogen production from starch and water mediated by 13 enzymes occurred at 30°C as expected, and the hydrogen yields were much higher than the theoretical limit (4 H2/glucose) of anaerobic fermentations. Significance The unique features, such as mild reaction conditions (30°C and atmospheric pressure), high hydrogen yields, likely low production costs ($∼2/kg H2), and a high energy-density carrier starch (14.8 H2-based mass%), provide great potential for mobile applications. With technology improvements and integration with fuel cells, this technology also solves the challenges associated with hydrogen storage, distribution, and infrastructure in the hydrogen economy. PMID:17520015

  1. 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. PMID:12198544

  2. 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.

  3. A mechanistic model for interpretation of hydrogen and oxygen isotope ratios in tree-ring cellulose

    NASA Astrophysics Data System (ADS)

    Roden, John S.; Lin, Guanghui; Ehleringer, James R.

    2000-01-01

    A mechanistic model is presented to quantify both the physical and biochemical fractionation events associated with hydrogen and oxygen isotope ratios in tree-ring cellulose. The model predicts the isotope ratios of tree-rings, incorporating both humidity and source water environmental information. Components of the model include (1) hydrogen and oxygen isotope effects associated with leaf water enrichment; (2) incorporation of leaf water isotope ratio values into photosynthetic carbohydrates along with the biochemical fractionation associated with autotrophic synthesis; (3) transport of exported carbohydrates (such as sucrose) from leaves to developing xylem in shoots and stems where cellulose is formed; (4) a partial exchange of oxygen and hydrogen isotopes in carbohydrates with xylem sap water during conversion into cellulose; and (5) a biochemical fractionation associated with cellulose synthesis. A modified version of the Craig-Gordon model for evaporative enrichment adequately described leaf water δD and δ 18O values. The leaf water model was robust over a wide range of leaf waters for both controlled experiments and field studies, far exceeding the range of values to be expected under natural conditions. The isotopic composition of cellulose was modeled using heterotrophic and autotrophic fractionation factors from the literature as well as the experimentally derived proportions of H and O that undergo exchange with xylem water during cellulose synthesis in xylem cells of tree-rings. The fraction of H and O from carbohydrates that exchange with xylem sap water was estimated to be 0.36 and 0.42, respectively. The proportions were based on controlled, long-term greenhouse experiments and field studies where the variations in the δD and δ 18O of tree-ring cellulose were measured under different source water isotopic compositions. The model prediction that tree-ring cellulose contains information on environmental water source and atmospheric vapor pressure

  4. Two fluid model using kinetic theory for modeling of one-step hydrogen production gasifier

    SciTech Connect

    Yu, L.; Lu, J.; Zhang, X.P.; Zhang, S.J.; Wang, X.L.

    2008-11-15

    A Two Fluid Model (TFM) using kinetic theory of granular flow has been developed to describe an innovative process of hydrogen production in a single step. An extended Multi-species of Solid Phase (MSP) method is proposed to simulate the gas-solid heterogeneous reactions in an entrained flow gasifier, as opposed to Single-species of Solid Phase (SSP) in previous studies. The intrinsic equations of methane steam reforming and water-gas shift reactions are used for a good understanding of the reaction mechanism for high concentration of hydrogen production under higher pressure. On the basis of the results of computing, the main feature of core-annular reaction zone is predicted in the fully developed flow region. And the similar flame-like structure for velocity and temperature is observed to emerge from the feed injection zone at the bottom of gasifier. The model well illustrates the effects of CaO on enhancing the concentration of hydrogen and sequestering CO{sub 2} in the process of coal gasification. The advantages of pressure gasification are also shown that coal conversion increases with increasing pressure while H{sub 2}S concentration and tar content decreases. Moreover, there is a steep increase in H{sub 2}S and tar species initiated from the entrance of gasifier and then a decrease at the next section. The model shows good agreement with the measurements of flow field and gas products concentration in laboratory-scale plants.

  5. 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.

  6. 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.

  7. 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.

  8. Competitive adsorption-driven separation of water/methanol mixtures using hydrogen as a third competitor.

    PubMed

    Lee, Dong-Wook; Yu, Chang-Yeol; Lee, Kew-Ho

    2009-12-01

    In this study, we report competitive adsorption-driven separation of a water/methanol mixture in Pd-deposited silica membranes, which is induced by introducing hydrogen carrier gas as a third competitor. After replacing helium carrier gas by hydrogen carrier gas, water vapor permeance showed a slight decrease, whereas methanol vapor permeance significantly decreased. The water/methanol separation factor remarkably increased from 1.7-16.5 to 6.8-58.2 in the feed water content of 5.8-83.0 wt.%. From single vapor permeation tests in the presence of carrier gas (hydrogen or helium), it was confirmed that those permeation behavior was derived from stronger effect of the competitive adsorption between hydrogen and methanol vapor than that between hydrogen and water vapor. That is, hydrogen carrier gas dominantly inhibits adsorption of methanol vapor on the membrane surface, and the partial pressure of methanol on the membrane surface decreases, which leads to a decrease in methanol permeance with reduced driving force. In addition, temperature programmed desorption (TPD) results of water and methanol from Pd/silica particles also demonstrated that hydrogen carrier gas suppresses methanol adsorption on Pd/silica surface more dominantly than water adsorption. PMID:19772967

  9. 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. PMID:26989250

  10. 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.