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Sample records for hydrogen desorption kinetics

  1. Hydrogen desorption kinetics for aqueous hydrogen fluoride and remote hydrogen plasma processed silicon (001) surfaces

    SciTech Connect

    King, Sean W. Davis, Robert F.; Carter, Richard J.; Schneider, Thomas P.; Nemanich, Robert J.

    2015-09-15

    The desorption kinetics of molecular hydrogen (H{sub 2}) from silicon (001) surfaces exposed to aqueous hydrogen fluoride and remote hydrogen plasmas were examined using temperature programmed desorption. Multiple H{sub 2} desorption states were observed and attributed to surface monohydride (SiH), di/trihydride (SiH{sub 2/3}), and hydroxide (SiOH) species, subsurface hydrogen trapped at defects, and hydrogen evolved during the desorption of surface oxides. The observed surface hydride species were dependent on the surface temperature during hydrogen plasma exposure with mono, di, and trihydride species being observed after low temperature exposure (150 °C), while predominantly monohydride species were observed after higher temperature exposure (450 °C). The ratio of surface versus subsurface H{sub 2} desorption was also found to be dependent on the substrate temperature with 150 °C remote hydrogen plasma exposure generally leading to more H{sub 2} evolved from subsurface states and 450 °C exposure leading to more H{sub 2} desorption from surface SiH{sub x} species. Additional surface desorption states were observed, which were attributed to H{sub 2} desorption from Si (111) facets formed as a result of surface etching by the remote hydrogen plasma or aqueous hydrogen fluoride treatment. The kinetics of surface H{sub 2} desorption were found to be in excellent agreement with prior investigations of silicon surfaces exposed to thermally generated atomic hydrogen.

  2. Isotope effects on desorption kinetics of hydrogen isotopes implanted into stainless steel by glow discharge

    SciTech Connect

    Matsuyama, M.; Kondo, M.; Noda, N.; Tanaka, M.; Nishimura, K.

    2015-03-15

    In a fusion device the control of fuel particles implies to know the desorption rate of hydrogen isotopes by the plasma-facing materials. In this paper desorption kinetics of hydrogen isotopes implanted into type 316L stainless steel by glow discharge have been studied by experiment and numerical calculation. The temperature of a maximum desorption rate depends on glow discharge time and heating rate. Desorption spectra observed under various experimental conditions have been successfully reproduced by numerical simulations that are based on a diffusion-limited process. It is suggested, therefore, that desorption rate of a hydrogen isotope implanted into the stainless steel is limited by a diffusion process of hydrogen isotope atoms in bulk. Furthermore, small isotope effects were observed for the diffusion process of hydrogen isotope atoms. (authors)

  3. Kinetic Modification on Hydrogen Desorption of Lithium Hydride and Magnesium Amide System.

    PubMed

    Miyaoka, Hiroki; Wang, Yongming; Hino, Satoshi; Isobe, Shigehito; Tokoyoda, Kazuhiko; Ichikawa, Takayuki; Kojima, Yoshitsugu

    2015-06-29

    Various synthesis and rehydrogenation processes of lithium hydride (LiH) and magnesium amide (Mg(NH₂)₂) system with 8:3 molar ratio are investigated to understand the kinetic factors and effectively utilize the essential hydrogen desorption properties. For the hydrogen desorption with a solid-solid reaction, it is expected that the kinetic properties become worse by the sintering and phase separation. In fact, it is experimentally found that the low crystalline size and the close contact of LiH and Mg(NH₂)₂ lead to the fast hydrogen desorption. To preserve the potential hydrogen desorption properties, thermochemical and mechanochemical rehydrogenation processes are investigated. Although the only thermochemical process results in slowing the reaction rate due to the crystallization, the ball-milling can recover the original hydrogen desorption properties. Furthermore, the mechanochemical process at 150 °C is useful as the rehydrogenation technique to preserve the suitable crystalline size and mixing state of the reactants. As a result, it is demonstrated that the 8LiH and 3Mg(NH₂)₂ system is recognized as the potential hydrogen storage material to desorb more than 5.5 mass% of H₂ at 150 °C.

  4. Kinetic Modification on Hydrogen Desorption of Lithium Hydride and Magnesium Amide System

    PubMed Central

    Miyaoka, Hiroki; Wang, Yongming; Hino, Satoshi; Isobe, Shigehito; Tokoyoda, Kazuhiko; Ichikawa, Takayuki; Kojima, Yoshitsugu

    2015-01-01

    Various synthesis and rehydrogenation processes of lithium hydride (LiH) and magnesium amide (Mg(NH2)2) system with 8:3 molar ratio are investigated to understand the kinetic factors and effectively utilize the essential hydrogen desorption properties. For the hydrogen desorption with a solid-solid reaction, it is expected that the kinetic properties become worse by the sintering and phase separation. In fact, it is experimentally found that the low crystalline size and the close contact of LiH and Mg(NH2)2 lead to the fast hydrogen desorption. To preserve the potential hydrogen desorption properties, thermochemical and mechanochemical rehydrogenation processes are investigated. Although the only thermochemical process results in slowing the reaction rate due to the crystallization, the ball-milling can recover the original hydrogen desorption properties. Furthermore, the mechanochemical process at 150 °C is useful as the rehydrogenation technique to preserve the suitable crystalline size and mixing state of the reactants. As a result, it is demonstrated that the 8LiH and 3Mg(NH2)2 system is recognized as the potential hydrogen storage material to desorb more than 5.5 mass% of H2 at 150 °C. PMID:28793414

  5. Kinetics of hydrogen desorption from MgH2 and AlH3 hydrides

    NASA Astrophysics Data System (ADS)

    Terent'ev, P. B.; Gerasimov, E. G.; Mushnikov, N. V.; Uimin, M. A.; Maikov, V. V.; Gaviko, V. S.; Golovatenko, V. D.

    2015-12-01

    Kinetic parameters of the process of thermal decomposition of the MgH2 hydride (obtained by the method of the mechanoactivation of magnesium in a hydrogen atmosphere) and of the commercial AlH3 hydride have been studied upon the rapid heating in the range of temperatures of 150-510°C at hydrogen pressures of 0-2 atm. The time dependences of the amount of hydrogen released by the metal hydrides at different temperatures and pressures have been determined. It has been shown that the activation energies of the hydrogen desorption are 135 kJ/mol for MgH2 and 107 kJ/mol for AlH3. The maximum rates of hydrogen desorption from the investigated metal hydrides have been established, and the temperatures and initial pressures that ensure the maximum rate and maximum volume of the hydrogen release have been determined.

  6. The Influence of Desorption Kinetics on Hydrogen Permeation in Iron.

    DTIC Science & Technology

    1987-07-30

    grains. Because of the allotropic transition of iron at 9144C and the presence of trace impurities in the bulk, the preparation of an atomically clean and...their presence results in the retardation or enhancement of the desorption process. For example, pre-adsorbed subnionolayers of sulfur , oxygen and...electrochemical permeation study (23]. In that investigation it was noticed that sulfur deposition on the membrane surface resulted in reduced permeation flux

  7. Size-dependent kinetic enhancement in hydrogen absorption and desorption of the Li-Mg-N-H system.

    PubMed

    Liu, Yongfeng; Zhong, Kai; Luo, Kun; Gao, Mingxia; Pan, Hongge; Wang, Qidong

    2009-02-11

    High operating temperature and slow kinetics retard the practical applications of the Li-Mg-N-H system for hydrogen storage. To alleviate these problems, a first attempt was carried out by synthesizing Li(2)MgN(2)H(2) through sintering a mixture of Mg(NH(2))(2)-2LiNH(2) and investigating its size-dependent hydrogen storage performance. A dramatically enhanced kinetics for hydrogen absorption/desorption was achieved with a reduction in the particle size. For the dehydrogenation reaction, a three-dimensional diffusion-controlled kinetic mechanism was identified for the first time by analyzing isothermal hydrogen desorption curves with a linear plot method. The experimental improvement and mechanistic understanding on the dehydrogenation kinetics of the Li-Mg-N-H system shed light on how to further decrease the operating temperature and enhance the hydrogen absorption/desorption rate of the amide/hydride combined materials.

  8. Effect of transition-metal additives on hydrogen desorption kinetics of MgH2

    NASA Astrophysics Data System (ADS)

    Roy, Anindya; Janotti, Anderson; Van de Walle, Chris G.

    2013-01-01

    Using first-principles calculations, we study the effect of transition-metal additives (Ti, Fe, Co, and Ni) on the rate of hydrogen desorption in MgH2. The presence of large concentrations of transition-metal impurities causes the Fermi level to shift according to the position of the transition-metal acceptor/donor levels in the band gap. This shift can lower the formation energy of native defects and increase their concentration. The resulting higher rates of hydrogen desorption enhance the prospect of MgH2 as a solid-state hydrogen-storage material.

  9. Thermodynamic and kinetic size effects for hydrogen-desorption in catalytically-doped magnesium hydride: Nanoparticle versus bulk surface effects

    NASA Astrophysics Data System (ADS)

    Reich, Jason; Wang, L.-L.; Johnson, D. D.

    2010-03-01

    Using density-functional methods with simulated annealing, we show that there are no size effects for hydrogen desorption energies in nanoparticles (NPs) of MgH2. Recently reported exothermic desorption energies in MgH2-doped NP (Mg30XH62) are shown to be spurious, resulting from metastable NP configurations before dehyrogenation. We confirm that the 93-atom NPs are amorphous, with structures that are sensitive to the presence of dopants, found via simulated annealing techniques. We find that dehydrogenation energies are similar between bulk surfaces and nanoparticles, showing that the thermodynamics is unchanged by particle size as desorption is determined only by the local hydrogen-metal bond. We then discuss the effects of nanoparticle size and presence of dopants on the kinetic barriers between NPs and bulk surfaces. The takehome message is: In modeling desorption events, especially within amorphous NPs, metastable, local minimum must be carefully avoided, and, in doing so, an accurate and physically reasonable picture emerges for the thermodynamic and kinetic behavior.

  10. Gas Diffusion in Metals: Fundamental Study of Helium-Point Defect Interactions in Iron and Kinetics of Hydrogen Desorption from Zirconium Hydride

    NASA Astrophysics Data System (ADS)

    Hu, Xunxiang

    The behavior of gaseous foreign species (e.g., helium and hydrogen), which are either generated, adsorbed or implanted within the structural materials (e.g., iron and zirconium) exposed to irradiation environments, is an important and largely unsolved topic, as they intensively interact with the irradiation-induced defects, or bond with the lattice atoms to form new compounds, and impose significant effects on their microstructural and mechanical properties in fission and fusion reactors. This research investigates two cases of gas diffusion in metals (i.e., the helium-point defect interactions in iron and kinetics of hydrogen desorption from zirconium hydride) through extensive experimental and modeling studies, with the objective of improving the understanding of helium effects on the microstructures of iron under irradiation and demonstrating the kinetics of hydrogen diffusion and precipitation behavior in zirconium that are crucial to predict cladding failures and hydride fuel performance. The study of helium effects in structural materials aims to develop a self-consistent, experimentally validated model of helium---point defect, defect cluster and intrinsic defects through detailed inter-comparisons between experimental measurements on helium ion implanted iron single crystals and computational models. The combination of thermal helium desorption spectrometry (THDS) experiment with the cluster dynamic model helps to reveal the influence of impurities on the energetics and kinetics of the He-defect interactions and to realize the identification of possible mechanisms governing helium desorption peaks. Positron annihilation spectroscopy is employed to acquire additional information on He-vacancy cluster evolution, which provides an opportunity to validate the model qualitatively. The inclusion of He---self-interstitial clusters extends the cluster dynamic model while MD simulations explore the effects of dislocation loops on helium clustering. In addition, the

  11. Erbium hydride thermal desorption : controlling kinetics.

    SciTech Connect

    Ferrizz, Robert Matthew

    2007-08-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report show that hydride film processing parameters directly impact thermal stability. Issues to be addressed include desorption kinetics for dihydrides and trihydrides, and the effect of film growth parameters, loading parameters, and substrate selection on desorption kinetics.

  12. Quantitative analysis of desorption and decomposition kinetics of formic acid on Cu(111): The importance of hydrogen bonding between adsorbed species

    SciTech Connect

    Shiozawa, Yuichiro; Koitaya, Takanori; Mukai, Kozo; Yoshimoto, Shinya; Yoshinobu, Jun

    2015-12-21

    Quantitative analysis of desorption and decomposition kinetics of formic acid (HCOOH) on Cu(111) was performed by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy, and time-resolved infrared reflection absorption spectroscopy. The activation energy for desorption is estimated to be 53–75 kJ/mol by the threshold TPD method as a function of coverage. Vibrational spectra of the first layer HCOOH at 155.3 K show that adsorbed molecules form a polymeric structure via the hydrogen bonding network. Adsorbed HCOOH molecules are dissociated gradually into monodentate formate species. The activation energy for the dissociation into monodentate formate species is estimated to be 65.0 kJ/mol at a submonolayer coverage (0.26 molecules/surface Cu atom). The hydrogen bonding between adsorbed HCOOH species plays an important role in the stabilization of HCOOH on Cu(111). The monodentate formate species are stabilized at higher coverages, because of the lack of vacant sites for the bidentate formation.

  13. Hydrogen absorption and desorption kinetics in fullerite C60 single crystals. Low-temperature micromechanical and structural characteristics of the interstitial solid solution C60(H2)x

    NASA Astrophysics Data System (ADS)

    Fomenko, L. S.; Lubenets, S. V.; Natsik, V. D.; Stetsenko, Yu. E.; Yagotintsev, K. A.; Strzhemechny, M. A.; Prokhvatilov, A. I.; Osipyan, Yu. A.; Izotov, A. N.; Sidorov, N. S.

    2008-01-01

    The microhardness HV and lattice parameter a of C60 single crystals are measured at room temperature as functions of the hydrogen saturation time t for several values of the saturation temperature (250, 300, and 350°C) at a fixed hydrogen pressure p =30atm. According to the measurements of HV and a, the kinetics of hydrogen absorption is described by a simple exponential law with a single, temperature-dependent characteristic time. In highly saturated samples the microhardness is 4 times greater than for the initial C60 crystal, while the lattice parameter is 0.2% larger. The temperature dependence of the microhardness HV and lattice parameter a of C60(H2)x crystals is investigated in the temperature interval 77-300K. The introduction of hydrogen lowers the temperature of the fcc-sc phase transition, and the transition becomes strongly broadened in temperature. The dependence of the microhardness of the saturated sample on the hold time in air at room temperature is described by the sum of two exponentials with different characteristic times. Kinetics of this kind is presumably due to two processes: desorption of hydrogen from the sample, which causes a decrease of the microhardness, and a simultaneous penetration of gaseous impurities into the sample from the surrounding air, which is accompanied by hardening. The influence of the H2 molecules on the characteristic of the intermolecular interaction in fullerite C60 is discussed and the intercalation-induced processes of dislocation slip and microfracture.

  14. Molecular beam-thermal hydrogen desorption from palladium

    SciTech Connect

    Lobo, R. F. M.; Berardo, F. M. V.; Ribeiro, J. H. F.

    2010-04-15

    Among the most efficient techniques for hydrogen desorption monitoring, thermal desorption mass spectrometry is a very sensitive one, but in certain cases can give rise to uptake misleading results due to residual hydrogen partial pressure background variations. In this work one develops a novel thermal desorption variant based on the effusive molecular beam technique that represents a significant improvement in the accurate determination of hydrogen mass absorbed on a solid sample. The enhancement in the signal-to-noise ratio for trace hydrogen is on the order of 20%, and no previous calibration with a chemical standard is required. The kinetic information obtained from the hydrogen desorption mass spectra (at a constant heating rate of 1 deg. C/min) accounts for the consistency of the technique.

  15. Superior hydrogen desorption kinetics of Mg(NH{sub 2}){sub 2} hollow nanospheres mixed with MgH{sub 2} nanoparticles

    SciTech Connect

    Xie Lei; Li Yaoqi; Yang Rong; Liu Yang; Li Xingguo

    2008-06-09

    Mg{sub 3}N{sub 2} nanocubes were prepared by vaporized bulk magnesium in ammonia atmosphere associated with plasma metal reaction. Then the product transformed to Mg(NH{sub 2}){sub 2} hollow nanospheres after it was reacted with NH{sub 3} based on the Kirkendall effect. The electron microscopy results suggested that the obtained hollow nanospheres were around 100 nm and the shell thickness was about 10 nm. Because of its short distance for Mg{sup 2+} diffusion and large specific surface area for interaction between Mg(NH{sub 2}){sub 2} and MgH{sub 2}, the structure dramatically enhanced the hydrogen desorption kinetics of Mg(NH{sub 2}){sub 2}-2MgH{sub 2}.

  16. Diffusion Analysis Of Hydrogen-Desorption Measurements

    NASA Technical Reports Server (NTRS)

    Danford, Merlin D.

    1988-01-01

    Distribution of hydrogen in metal explains observed desorption rate. Report describes application of diffusion theory to anaylsis of experimental data on uptake and elimination of hydrogen in high-strength alloys of 25 degree C. Study part of program aimed at understanding embrittlement of metals by hydrogen. Two nickel-base alloys, Rene 41 and Waspaloy, and one ferrous alloy, 4340 steel, studied. Desorption of hydrogen explained by distribution of hydrogen in metal. "Fast" hydrogen apparently not due to formation of hydrides on and below surface as proposed.

  17. Enhanced selective hydrogen desorption from metals

    SciTech Connect

    Knize, R.J.; Cecchi, J.L.

    1982-12-01

    The thermal desorption of hydrogen isotopes from a metal is usually a second order process, the rate for which becomes asymptotically slow. We present a method for enhancing the desorption rate of one particular isotope by maintaining a constant pressure of another molecular species. This results in an effective first order desorption and concomitant exponential decay of the concentration of the selected isotope. Data are presented for the enhanced desorption of deuterium from a Zr-Al getter. The results agree well with a theoretical model, which is discussed. This enhanced desorption method should be particularly useful for tritium operation in the Tokamak Fusion Test Reactor.

  18. Enhanced selective hydrogen desorption from metals

    SciTech Connect

    Knize, R.J.; Cecchi, J.L.

    1983-04-01

    The thermal desorption of hydrogen isotopes from a metal is usually a second order process the rate for which becomes asymptotically slow. We present a method for enhancing the desorption rate of one particular isotope by maintaining a constant pressure of another molecular species. This results in an effective first order desorption and concommitant exponential decay of the concentration of the selected isotope. Data is presented for the enhanced desorption of deuterium from a Zr--Al getter. The results agree well with a theoretical model, which is discussed. This enhanced desorption method should be particularly useful for tritium operation in the tokamak fusion test reactor.

  19. Surface changes on AlH3 during the hydrogen desorption

    NASA Astrophysics Data System (ADS)

    Kato, Shunsuke; Bielmann, Michael; Ikeda, Kazutaka; Orimo, Shin-ichi; Borgschulte, Andreas; Züttel, Andreas

    2010-02-01

    Surface change of α-AlH3 during the hydrogen desorption was investigated by means of in situ x-ray photoelectron spectroscopy combined with thermal desorption spectroscopy. The surface of AlH3 covered by an oxide layer significantly changes upon hydrogen desorption and the hydrogen desorption rate increases remarkably. In this study, the role of the surface oxide layer on AlH3 in view of the hydrogen desorption kinetics was investigated. AlH3 only decomposes into Al and H2 at the free surface and not in the bulk. Therefore, a closed surface oxide layer prevents the thermodynamically unstable AlH3 from decomposition.

  20. HYDROGEN AND ITS DESORPTION IN RHIC.

    SciTech Connect

    HSEUH,H.C.

    2002-11-11

    Hydrogen is the dominating gas specie in room temperature, ultrahigh vacuum systems of particle accelerators and storage rings, such as the Relativistic Heavy Ion Collider (RHIC) at Brookhaven. Rapid pressure increase of a few decades in hydrogen and other residual gases was observed during RHIC's recent high intensity gold and proton runs. The type and magnitude of the pressure increase were analyzed and compared with vacuum conditioning, beam intensity, number of bunches and bunch spacing. Most of these pressure increases were found to be consistent with those induced by beam loss and/or electron stimulated desorption from electron multipacting.

  1. Desorption and sublimation kinetics for fluorinated aluminum nitride surfaces

    SciTech Connect

    King, Sean W. Davis, Robert F.; Nemanich, Robert J.

    2014-09-01

    The adsorption and desorption of halogen and other gaseous species from surfaces is a key fundamental process for both wet chemical and dry plasma etch and clean processes utilized in nanoelectronic fabrication processes. Therefore, to increase the fundamental understanding of these processes with regard to aluminum nitride (AlN) surfaces, temperature programmed desorption (TPD) and x-ray photoelectron spectroscopy (XPS) have been utilized to investigate the desorption kinetics of water (H{sub 2}O), fluorine (F{sub 2}), hydrogen (H{sub 2}), hydrogen fluoride (HF), and other related species from aluminum nitride thin film surfaces treated with an aqueous solution of buffered hydrogen fluoride (BHF) diluted in methanol (CH{sub 3}OH). Pre-TPD XPS measurements of the CH{sub 3}OH:BHF treated AlN surfaces showed the presence of a variety of Al-F, N-F, Al-O, Al-OH, C-H, and C-O surfaces species in addition to Al-N bonding from the AlN thin film. The primary species observed desorbing from these same surfaces during TPD measurements included H{sub 2}, H{sub 2}O, HF, F{sub 2}, and CH{sub 3}OH with some evidence for nitrogen (N{sub 2}) and ammonia (NH{sub 3}) desorption as well. For H{sub 2}O, two desorption peaks with second order kinetics were observed at 195 and 460 °C with activation energies (E{sub d}) of 51 ± 3 and 87 ± 5 kJ/mol, respectively. Desorption of HF similarly exhibited second order kinetics with a peak temperature of 475 °C and E{sub d} of 110 ± 5 kJ/mol. The TPD spectra for F{sub 2} exhibited two peaks at 485 and 585 °C with second order kinetics and E{sub d} of 62 ± 3 and 270 ± 10 kJ/mol, respectively. These values are in excellent agreement with previous E{sub d} measurements for desorption of H{sub 2}O from SiO{sub 2} and AlF{sub x} from AlN surfaces, respectively. The F{sub 2} desorption is therefore attributed to fragmentation of AlF{sub x} species in the mass spectrometer ionizer. H{sub 2} desorption exhibited

  2. Adsorption and desorption of hydrogen at nonpolar GaN (1 1 ¯ 00 ) surfaces: Kinetics and impact on surface vibrational and electronic properties

    NASA Astrophysics Data System (ADS)

    Lymperakis, L.; Neugebauer, J.; Himmerlich, M.; Krischok, S.; Rink, M.; Kröger, J.; Polyakov, V. M.

    2017-05-01

    The adsorption of hydrogen at nonpolar GaN (1 1 ¯00 ) surfaces and its impact on the electronic and vibrational properties is investigated using surface electron spectroscopy in combination with density functional theory (DFT) calculations. For the surface mediated dissociation of H2 and the subsequent adsorption of H, an energy barrier of 0.55 eV has to be overcome. The calculated kinetic surface phase diagram indicates that the reaction is kinetically hindered at low pressures and low temperatures. At higher temperatures ab initio thermodynamics show, that the H-free surface is energetically favored. To validate these theoretical predictions experiments at room temperature and under ultrahigh vacuum conditions were performed. They reveal that molecular hydrogen does not dissociatively adsorb at the GaN (1 1 ¯00 ) surface. Only activated atomic hydrogen atoms attach to the surface. At temperatures above 820 K, the attached hydrogen gets desorbed. The adsorbed hydrogen atoms saturate the dangling bonds of the gallium and nitrogen surface atoms and result in an inversion of the Ga-N surface dimer buckling. The signatures of the Ga-H and N-H vibrational modes on the H-covered surface have experimentally been identified and are in good agreement with the DFT calculations of the surface phonon modes. Both theory and experiment show that H adsorption results in a removal of occupied and unoccupied intragap electron states of the clean GaN (1 1 ¯00 ) surface and a reduction of the surface upward band bending by 0.4 eV. The latter mechanism largely reduces surface electron depletion.

  3. Hydrogen absorption and desorption in rapidly solidified Mg- Al alloys

    NASA Astrophysics Data System (ADS)

    Urgnani, J.; Di Chio, M.; Palumbo, M.; Feuerbacher, M.; Fernandez, J. F.; Leardini, F.; Baricco, M.

    2009-01-01

    The addition of Al to Mg has been indicated as a suitable way to destabilise the hydride phase, in order to bring the absorption and desorption reactions close to reasonable temperatures and pressure values for hydrogen storage. Rapid solidification is known to refine the microstructure of Mg-Al alloys and it might improve the H2 absorption/desorption kinetics. In this paper, the interaction of H2 with rapidly solidified Mg-Al alloys have been studied for three different composition: Mg38.5Al61.5, Mg69Al31 and Mg72Al28. For Mg72Al28, no significant changes in the microstructure have been obtained by rapid solidification. In Mg69Al31, a significant grain refinement has been observed, whereas, for Mg38.5Al61.5, the formation of a metastable hexagonal phase has been found. In all cases, a disproportionation reaction has been observed after H2 absorption, leading to MgH2. After heating up to 430 °C the hydrogenated samples, a main desorption reaction from MgH2 has been observed, which brings again to the starting phases. Experimental results have been discussed on the basis of a thermodynamic assessment of the Mg-Al-H system.

  4. Desorption Kinetics of Methanol, Ethanol, and Water from Graphene

    SciTech Connect

    Smith, R. Scott; Matthiesen, Jesper; Kay, Bruce D.

    2014-09-18

    The desorption kinetics of methanol, ethanol, and water from graphene covered Pt(111) are investigated. The temperature programmed desorption (TPD) spectra for both methanol and ethanol have well-resolved first, second, third, and multilayer layer desorption peaks. The alignment of the leading edges is consistent with zero-order desorption kinetics from all layers. In contrast, for water the first and second layers are not resolved. At low water coverages (< 1 ML) the initial desorption leading edges are aligned but then fall out of alignment at higher temperatures. For thicker water layers (10 to 100 ML), the desorption leading edges are in alignment throughout the desorption of the film. The coverage dependence of the desorption behavoir suggests that at low water coverages the non-alignment of the desorption leading edges is due to water dewetting from the graphene substrate. Kinetic simulations reveal that the experimental results are consistent with zero-order desorption. The simulations also show that fractional order desorption kinetics would be readily apparent in the experimental TPD spectra.

  5. Kinetics of alkanethiol monolayer desorption from gold in air.

    PubMed

    Shadnam, Mohammad Reza; Amirfazli, A

    2005-10-14

    Thermal desorption of an alkanethiol monolayer from a gold substrate into a gaseous medium under ambient pressure was investigated using XPS and it was found that there exist 2 consecutive 1st order kinetics mechanisms with activation energies of 29.9 and 32.7 kcal mol(-1), respectively, i.e. on average approximately 15% higher than reports for liquid media desorption.

  6. Sequential desorption energy of hydrogen from nickel clusters

    SciTech Connect

    Deepika,; Kumar, Rakesh; R, Kamal Raj.; Kumar, T. J. Dhilip

    2015-06-24

    We report reversible Hydrogen adsorption on Nickel clusters, which act as a catalyst for solid state storage of Hydrogen on a substrate. First-principles technique is employed to investigate the maximum number of chemically adsorbed Hydrogen molecules on Nickel cluster. We observe a maximum of four Hydrogen molecules adsorbed per Nickel atom, but the average Hydrogen molecules adsorbed per Nickel atom decrease with cluster size. The dissociative chemisorption energy per Hydrogen molecule and sequential desorption energy per Hydrogen atom on Nickel cluster is found to decrease with number of adsorbed Hydrogen molecules, which on optimization may help in economical storage and regeneration of Hydrogen as a clean energy carrier.

  7. Current-Driven Hydrogen Desorption from Graphene: Experiment and Theory

    SciTech Connect

    Gao, L.; Pal, Partha P.; Seideman, Tamar; Guisinger, Nathan P.; Guest, Jeffrey R.

    2016-02-04

    Electron-stimulated desorption of hydrogen from the graphene/SiC(0001) surface at room temperature was investigated with ultrahigh vacuum scanning tunneling microscopy and ab initio calculations in order to elucidate the desorption mechanisms and pathways. Two different desorption processes were observed. In the high electron energy regime (4-8 eV), the desorption yield is independent of both voltage and current, which is attributed to the direct electronic excitation of the C-H bond. In the low electron energy regime (2-4 eV), however, the desorption yield exhibits a threshold dependence on voltage, which is explained by the vibrational excitation of the C-H bond via transient ionization induced by inelastic tunneling electrons. The observed current-independence of the desorption yield suggests that the vibrational excitation is a singleelectron process. We also observed that the curvature of graphene dramatically affects hydrogen desorption. Desorption from concave regions was measured to be much more probable than desorption from convex regions in the low electron energy regime (~ 2 eV), as would be expected from the identified desorption mechanism

  8. Hydrogen Desorption and Adsorption Measurements on Graphite Nanofibers

    NASA Technical Reports Server (NTRS)

    Ahn, C. C.; Ye, Y.; Ratnakumar, B. V.; Witham, C. K.; Bowman, R. C., Jr.; Fultz, B.

    1998-01-01

    Graphite nanofibers were synthesized and their hydrogen desorption and adsorption properties are reported for 77 and 300 K. Catalysts were made by several different methods including chemical routes, mechanical alloying and gas condensation.

  9. Hydrogen Desorption and Adsorption Measurements on Graphite Nanofibers

    NASA Technical Reports Server (NTRS)

    Ahn, C. C.; Ye, Y.; Ratnakumar, B. V.; Witham, C. K.; Bowman, R. C., Jr.; Fultz, B.

    1998-01-01

    Graphite nanofibers were synthesized and their hydrogen desorption and adsorption properties are reported for 77 and 300 K. Catalysts were made by several different methods including chemical routes, mechanical alloying and gas condensation.

  10. Synthesis and Hydrogen Desorption Properties of Aluminum Hydrides.

    PubMed

    Jeong, Wanseop; Lee, Sang-Hwa; Kim, Jaeyong

    2016-03-01

    Aluminum hydride (AlH3 or alane) is known to store maximum 10.1 wt.% of hydrogen at relatively low temperature (< 100 degrees C), which partially fulfills the U.S. department of energy requirements for gravimetric loading capacity. However, its detailed mechanisms of appearing of different phases, structural stability, and dynamics of hydrogen desorption are still not clear. To understand the desorption properties of hydrogen in alane, thermodynamically stable α-AlH3 was synthesized by employing an ethereal reaction method. The dependence of pathways on phase formation and the properties of hydrogen evolution were investigated, and the results were compared with the ones for γ-AlH3. It was found that γ-AlH3 requires 10 degrees C higher than that of γ-AlH3 to form, and its decomposition rate demonstrated enhanced endothermic stabilities. For desorption, all hydrogen atoms of alane evolved under an isothermal condition at 138 degrees C in less than 1 hour, and the sample completely transformed to pure aluminum. Our results show that the total amount of desorbed hydrogen from α-AlH3 exceeded 9.05 wt.%, with a possibility of further increase. Easy synthesis, thermal stability, and a large amount of hydrogen desorption of alane fulfill the requirements for light-weight hydrogen storage materials once the pathway of hydrogen cycling is provided.

  11. Hydrogen desorption from hydrogen fluoride and remote hydrogen plasma cleaned silicon carbide (0001) surfaces

    SciTech Connect

    King, Sean W. Tanaka, Satoru; Davis, Robert F.; Nemanich, Robert J.

    2015-09-15

    Due to the extreme chemical inertness of silicon carbide (SiC), in-situ thermal desorption is commonly utilized as a means to remove surface contamination prior to initiating critical semiconductor processing steps such as epitaxy, gate dielectric formation, and contact metallization. In-situ thermal desorption and silicon sublimation has also recently become a popular method for epitaxial growth of mono and few layer graphene. Accordingly, numerous thermal desorption experiments of various processed silicon carbide surfaces have been performed, but have ignored the presence of hydrogen, which is ubiquitous throughout semiconductor processing. In this regard, the authors have performed a combined temperature programmed desorption (TPD) and x-ray photoelectron spectroscopy (XPS) investigation of the desorption of molecular hydrogen (H{sub 2}) and various other oxygen, carbon, and fluorine related species from ex-situ aqueous hydrogen fluoride (HF) and in-situ remote hydrogen plasma cleaned 6H-SiC (0001) surfaces. Using XPS, the authors observed that temperatures on the order of 700–1000 °C are needed to fully desorb C-H, C-O and Si-O species from these surfaces. However, using TPD, the authors observed H{sub 2} desorption at both lower temperatures (200–550 °C) as well as higher temperatures (>700 °C). The low temperature H{sub 2} desorption was deconvoluted into multiple desorption states that, based on similarities to H{sub 2} desorption from Si (111), were attributed to silicon mono, di, and trihydride surface species as well as hydrogen trapped by subsurface defects, steps, or dopants. The higher temperature H{sub 2} desorption was similarly attributed to H{sub 2} evolved from surface O-H groups at ∼750 °C as well as the liberation of H{sub 2} during Si-O desorption at temperatures >800 °C. These results indicate that while ex-situ aqueous HF processed 6H-SiC (0001) surfaces annealed at <700 °C remain terminated by some surface C–O and

  12. Moisture desorption rates from TATB formulations: experiments and kinetic models.

    PubMed

    Glascoe, Elizabeth A; Dinh, Long N; Small, Ward; Overturf, George E

    2012-06-07

    The rate of water desorption from PBX-9502, a formulation containing 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), is measured using temperature-programmed desorption and modeled using conventional kinetic modeling methods. The results of these studies show two stages of moisture release. At lower temperatures, the release is likely assisted by thermal expansion of the TATB and melting of the Kel-F binder. At higher temperatures, a considerable amount of water is released and is attributed to sublimation of the TATB, which exposes new surfaces for water desorption.

  13. Hydrogen absorption-desorption properties of U 2Ti

    NASA Astrophysics Data System (ADS)

    Takuya, Yamamoto; Satoru, Tanaka; Michio, Yamawaki

    1990-02-01

    Hydrogen absorption-desorption properties of U 2Ti intermetallic compound was examined over the temperature range of 298 to 973 K and at hydrogen pressures below 10 5 Pa. It absorbs hydrogen up to 7.6 atoms per F.U. (formula unit) by two step reactions and hence each desorption isotherm is separated into two plateau regions. In the first plateau, a newly-found ternary hydride is formed, where the hydrogen concentration, cH, reaches 2.4 H atoms/F.U. In the second plateau, UH 3 is formed and cH reaches 7.6 H atoms/F.U. The specimen is disintegrated into fine powder in the second plateau, while in the first plateau the ternary hydride which was identified to be UTi 2H x, ( x = 4.8 to 6.2) showed high durability against powdering. It is predicted that UTi 2 can be suitable material for tritium storage.

  14. Kinetic effect of Pd additions on the hydrogen uptake of chemically activated, ultramicroporous carbon

    SciTech Connect

    Bhat, Vinay V; Contescu, Cristian I; Gallego, Nidia C

    2010-01-01

    The effect of mixing chemically-activated ultramicroporous carbon (UMC) with Pd nanopowder is investigated. Results show that Pd addition doubles the rate of hydrogen uptake, but does not enhance the hydrogen capacity or improve desorption kinetics. The effect of Pd on the rate of hydrogen adsorption supports the occurrence of the hydrogen spillover mechanism in the Pd - UMC system.

  15. A thermal desorption spectroscopy study of hydrogen trapping in polycrystalline α-uranium

    SciTech Connect

    Lillard, R. S.; Forsyth, R. T.

    2015-03-14

    The kinetics of hydrogen desorption from polycrystalline α-uranium (α-U) was examined using thermal desorption spectroscopy (TDS). The goal was to identify the major trap sites for hydrogen and their associated trap energies. In polycrystalline α-U six TDS adsorption peaks were observed at temperatures of 521 K, 556 K, 607 K, 681 K, 793 K and 905 K. In addition, the desorption was determined to be second order based on peak shape. The position of the first three peaks was consistent with desorption from UH3. To identify the trap site corresponding to the high temperature peaks the data were compared to a plastically deformed sample and a high purity single crystal sample. The plastically deformed sample allowed the identification of trapping at dislocations while the single crystal sample allow for the identification of high angle boundaries and impurities. Thus, with respect to the desorption energy associated with each peak, values between 12.9 and 26.5 kJ/mole were measured.

  16. A thermal desorption spectroscopy study of hydrogen trapping in polycrystalline α-uranium

    DOE PAGES

    Lillard, R. S.; Forsyth, R. T.

    2015-03-14

    The kinetics of hydrogen desorption from polycrystalline α-uranium (α-U) was examined using thermal desorption spectroscopy (TDS). The goal was to identify the major trap sites for hydrogen and their associated trap energies. In polycrystalline α-U six TDS adsorption peaks were observed at temperatures of 521 K, 556 K, 607 K, 681 K, 793 K and 905 K. In addition, the desorption was determined to be second order based on peak shape. The position of the first three peaks was consistent with desorption from UH3. To identify the trap site corresponding to the high temperature peaks the data were compared tomore » a plastically deformed sample and a high purity single crystal sample. The plastically deformed sample allowed the identification of trapping at dislocations while the single crystal sample allow for the identification of high angle boundaries and impurities. Thus, with respect to the desorption energy associated with each peak, values between 12.9 and 26.5 kJ/mole were measured.« less

  17. A thermal desorption spectroscopy study of hydrogen trapping in polycrystalline α-uranium

    NASA Astrophysics Data System (ADS)

    Lillard, R. S.; Forsyth, R. T.

    2015-06-01

    The kinetics of hydrogen desorption from polycrystalline α-uranium (α-U) was examined using thermal desorption spectroscopy (TDS). The goal was to identify the major trap sites for hydrogen and their associated trap energies. In polycrystalline α-U six TDS adsorption peaks were observed at temperatures of 521 K, 556 K, 607 K, 681 K, 793 K and 905 K. In addition, the desorption was determined to be second order based on peak shape. The position of the first three peaks was consistent with desorption from UH3. To identify the trap site corresponding to the high temperature peaks the data were compared to a plastically deformed sample and a high purity single crystal sample. The plastically deformed sample allowed the identification of trapping at dislocations while the single crystal sample allow for the identification of high angle boundaries and impurities. With respect to the desorption energy associated with each peak, values between 12.9 and 26.5 kJ/mole were measured.

  18. Hydrogen retention in tungsten materials studied by Laser Induced Desorption

    NASA Astrophysics Data System (ADS)

    Zlobinski, M.; Philipps, V.; Schweer, B.; Huber, A.; Reinhart, M.; Möller, S.; Sergienko, G.; Samm, U.; 't Hoen, M. H. J.; Manhard, A.; Schmid, K.; Textor Team

    2013-07-01

    Development of methods to characterise the first wall in ITER and future fusion devices without removal of wall tiles is important to support safety assessments for tritium retention and dust production and to understand plasma wall processes in general. Laser based techniques are presently under investigation to provide these requirements, among which Laser Induced Desorption Spectroscopy (LIDS) is proposed to measure the deuterium and tritium load of the plasma facing surfaces by thermal desorption and spectroscopic detection of the desorbed fuel in the edge of the fusion plasma. The method relies on its capability to desorb the hydrogen isotopes in a laser heated spot. The application of LID on bulk tungsten targets exposed to a wide range of deuterium fluxes, fluences and impact energies under different surface temperatures is investigated in this paper. The results are compared with Thermal Desorption Spectrometry (TDS), Nuclear Reaction Analysis (NRA) and a diffusion model.

  19. Role of deuterium desorption kinetics on the thermionic emission properties of polycrystalline diamond films with respect to kinetic isotope effects

    SciTech Connect

    Paxton, W. F. Howell, M.; Kang, W. P.; Davidson, J. L.; Brooks, M. M.; Tolk, N.

    2014-06-21

    The desorption kinetics of deuterium from polycrystalline chemical vapor deposited diamond films were characterized by monitoring the isothermal thermionic emission current behavior. The reaction was observed to follow a first-order trend as evidenced by the decay rate of the thermionic emission current over time which is in agreement with previously reported studies. However, an Arrhenius plot of the reaction rates at each tested temperature did not exhibit the typical linear behavior which appears to contradict past observations of the hydrogen (or deuterium) desorption reaction from diamond. This observed deviation from linearity, specifically at lower temperatures, has been attributed to non-classical processes. Though no known previous studies reported similar deviations, a reanalysis of the data obtained in the present study was performed to account for tunneling which appeared to add merit to this hypothesis. Additional investigations were performed by reevaluating previously reported data involving the desorption of hydrogen (as opposed to deuterium) from diamond which further indicated this reaction to be dominated by tunneling at the temperatures tested in this study (<775 °C). An activation energy of 3.19 eV and a pre-exponential constant of 2.3 × 10{sup 12} s{sup −1} were determined for the desorption reaction of deuterium from diamond which is in agreement with previously reported studies.

  20. Concentration-dependent kinetics of pollutant desorption from soils.

    PubMed

    Braida, Washington J; White, Jason C; Zhao, Dongye; Ferrandino, Francis J; Pignatello, Joseph J

    2002-12-01

    Sorption-desorption kinetics play a major role in transport and bioavailability of pollutants in soils. Contaminant concentration is a potentially important factor controlling kinetics. A previous paper dealt with the effect of solute concentration on fractional uptake rates of phenanthrene and pyrene from a finite aqueous source. In this study we determined the effect of initial phenanthrene sorbed concentration (q(0)) on the fractional mass desorption rates from each of six soils to a zero-concentration solution, approximated by including a polymer adsorbent (Tenax) as a third-phase sink. The soils were preequilibrated with phenanthrene for 180 d. Consistent with theory, the fractional desorption rates determined by empirical curve fitting increased with q(0) provided the isotherm was nonlinear. After 500 to 600 d of desorption at the steepest possible concentration gradient, all soils retained a highly resistant fraction, which ranged from 4 to 31% of q(0), except for one soil at a high q(0). The highly resistant fraction decreased with increasing q(0), for nonlinear isotherm cases, but increased with q(0) for linear or nearly linear isotherm cases. Application of a nonlinear diffusion model, the dual-mode diffusion model (DMDM), to the nonresistant fraction gave reasonably good fits. The DMDM attributes the increase with concentration of the apparent diffusivity to a decrease in the proportion of sorbate occupying immobile sites (holes) in soil organic matter. The concentration-dependent term in the expression for the apparent diffusivity correlated with either of two indices that reflect the linearity of the sorption isotherm. Bunker C oil present in one soil acted as a partition domain. The findings of this study are consistent with heterogeneous models of soil organic matter, and indicate that concentration effects should be taken into account whenever desorption rate is important.

  1. Adsorption-desorption kinetics of soft particles onto surfaces

    NASA Astrophysics Data System (ADS)

    Osberg, Brendan; Gerland, Ulrich

    A broad range of physical, chemical, and biological systems feature processes in which particles randomly adsorb on a substrate. Theoretical models usually assume ``hard'' (mutually impenetrable) particles, but in soft matter physics the adsorbing particles can be effectively compressible, implying ``soft'' interaction potentials. We recently studied the kinetics of such soft particles adsorbing onto one-dimensional substrates, identifying three novel phenomena: (i) a gradual density increase, or ''cramming'', replaces the usual jamming behavior of hard particles, (ii) a density overshoot, can occur (only for soft particles) on a time scale set by the desorption rate, and (iii) relaxation rates of soft particles increase with particle size (on a lattice), while hard particles show the opposite trend. The latter occurs since unjamming requires desorption and many-bodied reorganization to equilibrate -a process that is generally very slow. Here we extend this analysis to a two-dimensional substrate, focusing on the question of whether the adsorption-desorption kinetics of particles in two dimensions is similarly enriched by the introduction of soft interactions. Application to experiments, for example the adsorption of fibrinogen on two-dimensional surfaces, will be discussed.

  2. A kinetic Monte Carlo approach to diffusion-controlled thermal desorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Schablitzki, T.; Rogal, J.; Drautz, R.

    2017-06-01

    Atomistic simulations of thermal desorption spectra for effusion from bulk materials to characterize binding or trapping sites are a challenging task as large system sizes as well as extended time scales are required. Here, we introduce an approach where we combine kinetic Monte Carlo with an analytic approximation of the superbasins within the framework of absorbing Markov chains. We apply our approach to the effusion of hydrogen from BCC iron, where the diffusion within bulk grains is coarse grained using absorbing Markov chains, which provide an exact solution of the dynamics within a superbasin. Our analytic approximation to the superbasin is transferable with respect to grain size and elliptical shapes and can be applied in simulations with constant temperature as well as constant heating rate. The resulting thermal desorption spectra are in close agreement with direct kinetic Monte Carlo simulations, but the calculations are computationally much more efficient. Our approach is thus applicable to much larger system sizes and provides a first step towards an atomistic understanding of the influence of structural features on the position and shape of peaks in thermal desorption spectra. This article is part of the themed issue 'The challenges of hydrogen and metals'.

  3. Measurement of hydrogen solubility and desorption rate in V-4Cr-4Ti and liquid lithium-calcium alloys

    SciTech Connect

    Park, J.H.; Erck, R.; Park, E.T.

    1997-04-01

    Hydrogen solubility in V-4Cr-4Ti and liquid lithium-calcium was measured at a hydrogen pressure of 9.09 x 10{sup {minus}4} torr at temperatures between 250 and 700{degrees}C. Hydrogen solubility in V-4Cr-4Ti and liquid lithium decreased with temperature. The measured desorption rate of hydrogen in V-4Cr-4Ti is a thermally activated process; the activation energy is 0.067 eV. Oxygen-charged V-4Cr-4Ti specimens were also investigated to determine the effect of oxygen impurity on hydrogen solubility and desorption in the alloy. Oxygen in V-4Cr-4Ti increases hydrogen solubility and desorption kinetics. To determine the effect of a calcium oxide insulator coating on V-4Cr-4Ti, hydrogen solubility in lithium-calcium alloys that contained 0-8.0 percent calcium was also measured. The distribution ratio R of hydrogen between liquid lithium or lithium-calcium and V-4Cr-4Ti increased as temperature decreased (R {approx} 10 and 100 at 700 and 250{degrees}C, respectively). However at <267{degrees}C, solubility data could not be obtained by this method because of the slow kinetics of hydrogen permeation through the vanadium alloy.

  4. Thermal Desorption Analysis of Hydrogen in High Strength Martensitic Steels

    NASA Astrophysics Data System (ADS)

    Enomoto, M.; Hirakami, D.; Tarui, T.

    2012-02-01

    Thermal desorption analyses (TDA) were conducted in high strength martensitic steels containing carbon from 0.33 to 1.0 mass pct, which were charged with hydrogen at 1223 K (950 °C) under hydrogen of one atmospheric pressure and quenched to room temperature. In 0.33C steel, which had the highest M s temperature, only one desorption peak was observed around 373 K (100 °C), whereas two peaks, one at a similar temperature and the other around and above 573 K (300 °C), were observed in the other steels, the height of the second peak increasing with carbon content. In 0.82C steel, both peaks disappeared during exposure at room temperature in 1 week, whereas the peak heights decreased gradually over 2 weeks in specimens electrolytically charged with hydrogen and aged for varying times at room temperature. From computer simulation, by means of the McNabb-Foster theory coupled with theories of carbon segregation, these peaks are likely to be due to trapping of hydrogen in the strain fields and cores of dislocations, and presumably to a lesser extent in prior austenite grain boundaries. The results also indicate that carbon atoms prevent and even expel hydrogen from trapping sites during quenching and aging in these steels.

  5. Kinetics of ethylene oxide desorption from sterilized materials.

    PubMed

    Mendes, Gisela C; Brandão, Teresa R S; Silva, Cristina L M

    2013-01-01

    Ethylene oxide gas is commonly used to sterilize medical devices, and concerns about using this agent on biological systems are well-established. Medical devices sterilized by ethylene oxide must be properly aerated to remove residual gas and by-products. In this work, kinetics of ethylene oxide desorption from different sterilized materials were studied in a range of aeration temperatures. The experimental data were well-described by a Fickian diffusion mass transfer behavior, and diffusivities were estimated for two textile and two polymeric materials within the temperature range of 1.5 to 59.0 degrees C. The results will allow predictions of ethylene oxide desorption, which is a key step for the design of sterilization/aeration processes, contributing to an efficient removal of residual ethylene oxide content.

  6. Desorption kinetics of benzene in a sandy soil in the presence of powdered activated carbon.

    PubMed

    Choi, J-W; Kim, S-B; Kim, D-J

    2007-02-01

    Desorption kinetics of benzene was investigated with a modified biphasic desorption model in a sandy soil with five different powdered activated carbon (PAC) contents (0, 1, 2, 5, 10% w/w) as sorbents. Sorption experiments followed by series dilution desorption were conducted for each sorbent. Desorption of benzene was successively performed at two stages using deionized water and hexane. Modeling was performed on both desorption isotherm and desorption rate for water-induced desorption to elucidate the presence of sorption-desorption hysteresis and biphasic desorption and if present to quantify the desorption-resistant fraction (q (irr)) and labile fraction (F) of desorption site responsible for rapid process. Desorption isotherms revealed that sorption-desorption exhibited a severe hysteresis with a significant fraction of benzene being irreversibly adsorbed onto both pure sand and PAC, and that desorption-resistant fraction (q (irr)) increased with PAC content. Desorption kinetic modeling showed that desorption of benzene was biphasic with much higher (4-40 times) rate constant for rapid process (k (1)) than that for slow process (k (2)), and that the difference in the rate constant increased with PAC content. The labile fraction (F) of desorption site showed a decreasing tendency with PAC. The experimental results would provide valuable information on remediation methods for soils and groundwater contaminated with BTEX.

  7. Revisited reaction-diffusion model of thermal desorption spectroscopy experiments on hydrogen retention in material

    SciTech Connect

    Guterl, Jerome Smirnov, R. D.; Krasheninnikov, S. I.

    2015-07-28

    Desorption phase of thermal desorption spectroscopy (TDS) experiments performed on tungsten samples exposed to flux of hydrogen isotopes in fusion relevant conditions is analyzed using a reaction-diffusion model describing hydrogen retention in material bulk. Two regimes of hydrogen desorption are identified depending on whether hydrogen trapping rate is faster than hydrogen diffusion rate in material during TDS experiments. In both regimes, a majority of hydrogen released from material defects is immediately outgassed instead of diffusing deeply in material bulk when the evolution of hydrogen concentration in material is quasi-static, which is the case during TDS experiments performed with tungsten samples exposed to flux of hydrogen isotopes in fusion related conditions. In this context, analytical expressions of the hydrogen outgassing flux as a function of the material temperature are obtained with sufficient accuracy to describe main features of thermal desorption spectra (TDSP). These expressions are then used to highlight how characteristic temperatures of TDSP depend on hydrogen retention parameters, such as trap concentration or activation energy of detrapping processes. The use of Arrhenius plots to characterize retention processes is then revisited when hydrogen trapping takes place during TDS experiments. Retention processes are also characterized using the shape of desorption peaks in TDSP, and it is shown that diffusion of hydrogen in material during TDS experiment can induce long desorption tails visible aside desorption peaks at high temperature in TDSP. These desorption tails can be used to estimate activation energy of diffusion of hydrogen in material.

  8. Methylthiolate on Au(111): adsorption and desorption kinetics.

    PubMed

    Roper, Mark G; Jones, Robert G

    2008-03-07

    Low energy electron diffraction, Auger electron spectroscopy, X-ray photoelectron spectroscopy and line of sight mass spectrometry have been used to study the adsorption and desorption of dimethyldisulfide (DMDS) on Au(111). At 300 K adsorption is dissociative, forming a chemisorbed adlayer of methylthiolate with a 1/3 ML, (sq rt 3 x sq rt 3)R30 degrees, structure. At 100 K adsorption is molecular, with dissociation to form the 1/3 ML (sq rt 3 x sq rt 3)R30 degrees methylthiolate structure occurring at 138-160 K. A physisorbed DMDS layer, with a coverage of 1/6 ML of DMDS, forms on top of the (sq rt 3 x sq rt 3)R30 degrees chemisorbed MT surface for T < or = 180 K, with multilayers forming for T < or = 150 K. In temperature programmed desorption, multilayers of DMDS desorbed with zero order kinetics and an activation energy of 41 kJ mol(-1); the physisorbed layer desorbed with first order kinetics, exhibiting repulsive lateral interactions with an activation energy which varied from 63 kJ mol(-1) (theta = 0) to 51 kJ mol(-1) (theta = 1); the chemisorbed methylthiolate layer desorbed associatively as DMDS via the physisorbed layer, the activation energy for the reaction, 2 methylthiolate --> physisorbed DMDS, exhibiting repulsive lateral interactions with an activation energy which varied from 65 kJ mol(-1) (theta = 0) to 61 kJ mol(-1) (theta = 1). The physisorbed disulfide layer explains the pre-cursor state adsorption kinetics observed in sticking probability measurement, while its relatively facile formation provides a mechanism by which thiolate self-assembled monolayers can become mobile at room temperature.

  9. The influence of the potassium promoter on the kinetics and thermodynamics of CO adsorption on a bulk iron catalyst applied in Fischer-Tropsch synthesis: a quantitative adsorption calorimetry, temperature-programmed desorption, and surface hydrogenation study.

    PubMed

    Graf, Barbara; Muhler, Martin

    2011-03-07

    The adsorption of carbon monoxide on an either unpromoted or potassium-promoted bulk iron catalyst was investigated at 303 K and 613 K by means of pulse chemisorption, adsorption calorimetry, temperature-programmed desorption and temperature-programmed surface reaction in hydrogen. CO was found to adsorb mainly molecularly in the absence of H(2) at 303 K, whereas the presence of H(2) induced CO dissociation at higher temperatures leading to the formation of CH(4) and H(2)O. The hydrogenation of atomic oxygen chemisorbed on metallic iron was found to occur faster than the hydrogenation of atomically adsorbed carbon. At 613 K CO adsorption occurred only dissociatively followed by recombinative CO(2) formation according to C(ads) + 2O(ads)→ CO(2(g)). The presence of the potassium promoter on the catalyst surface led to an increasing strength of the Fe-C bond both at 303 K and 613 K: the initial differential heat of molecular CO adsorption on the pure iron catalyst at 303 K amounted to 102 kJ mol(-1), whereas it increased to 110 kJ mol(-1) on the potassium-promoted sample, and the initial differential heat of dissociative CO adsorption on the unpromoted iron catalyst at 613 K amounted to 165 kJ mol(-1), which increased to 225 kJ mol(-1) in the presence of potassium. The calorimetric CO adsorption experiments also reveal a change of the energetic distribution of the CO adsorption sites present on the catalyst surface induced by the potassium promoter, which was found to block a fraction of the CO adsorption sites.

  10. Temporal and spatial imaging of hydrogen storage materials: watching solvent and hydrogen desorption from aluminium hydride by transmission electron microscopy.

    PubMed

    Beattie, Shane D; Humphries, Terry; Weaver, Louise; McGrady, G Sean

    2008-10-07

    An in situ thermal desorption study of solvated aluminum hydride (alane) by transmission electron microscopy and selected area diffraction has permitted characterisation of the structural and morphological changes during desorption of solvent and hydrogen in real-time; this powerful technique for studying hydrogen storage materials complements several others already employed.

  11. A study of the kinetics of isothermal nicotine desorption from silicon dioxide

    NASA Astrophysics Data System (ADS)

    Adnadjevic, Borivoj; Lazarevic, Natasa; Jovanovic, Jelena

    2010-12-01

    The isothermal kinetics of nicotine desorption from silicon dioxide (SiO 2) was investigated. The isothermal thermogravimetric curves of nicotine at temperatures of 115 °C, 130 °C and 152 °C were recorded. The kinetic parameters ( Ea, ln A) of desorption of nicotine were calculated using various methods (stationary point, model constants and differential isoconversion method). By applying the "model-fitting" method, it was found that the kinetic model of nicotine desorption from silicon dioxide was a phase boundary controlled reaction (contracting volume). The values of the kinetic parameters, Ea,α and ln Aα, complexly change with changing degree of desorption and a compensation effect exists. A new mechanism of activation for the desorption of the absorbed molecules of nicotine was suggested in agreement with model of selective energy transfer.

  12. Hydride formation and thermal desorption spectra of hydrogen of cathodically charged single-phase gamma titanium aluminide

    SciTech Connect

    Takasaki, Akito; Furuya, Yoshio

    1999-02-05

    The authors have previously reported thermal desorption spectra of hydrogen obtained from cathodically charged two-phase (Ti{sub 3}Al ({alpha}{sub 2}) + TiAl ({gamma})) titanium aluminides by means of thermal desorption spectroscopy (TDS), in which hydrogen ion current (H{sub 2}{sup +}) corresponding to hydrogen evolution rate during heating was measured by a quadrupole mass spectrometer in an ultra-high vacuum condition. Several accelerated hydrogen evolutions (TDS peak temperatures) have been observed in a series of TDS measurement, and then the authors have suggested that these peaks were dependent on the microstructures ({alpha}{sub 2} and {gamma} phases) as well as dissociation of the hydride phase which formed during cathodic charging. A comparison with the TDS spectra from other series of titanium aluminides, such as a single-phase {gamma} alloy, might give clearer views of the microstructural dependence on hydrogen evolution kinetics. In this paper, hydride formation, hydrogen uptake and hydrogen evolution kinetic of a cathodically charged single-phase {gamma} titanium aluminide are investigated, and these results are compared with the previous ones obtained in two-phase ({alpha}{sub 2} + {gamma}) titanium aluminides.

  13. Synergy on catalytic effect of Fe-Zr additives mixed in different proportions on the hydrogen desorption from MgH{sub 2}

    SciTech Connect

    Kale, A.; Bazzanella, N.; Checchetto, R.; Miotello, A.

    2009-05-18

    Mg films with mixed Fe and Zr metallic additives were prepared by rf magnetron sputtering keeping the total metal content constant, about 7 at. %, and changing the [Fe]/[Zr] ratio. Isothermal hydrogen desorption curves showed that the kinetics depends on [Fe]/[Zr] ratio and is fastest when the [Fe]/[Zr] ratio is {approx}1.8. X-ray diffraction analysis revealed formation of Fe nanoclusters and Mg grain refinement. The improvement of the hydrogen desorption kinetics can be explained by the presence of atomically dispersed Zr and Fe nanoclusters acting as nucleation centers, as well as Mg grain refinement.

  14. The effects of added hydrogen on a helium atmospheric-pressure plasma jet ambient desorption/ionization source.

    PubMed

    Wright, Jonathan P; Heywood, Matthew S; Thurston, Glen K; Farnsworth, Paul B

    2013-03-01

    We present mass spectrometric data demonstrating the effect that hydrogen has on a helium-based dielectric-barrier discharge (DBD) atmospheric-pressure plasma jet used as an ambient desorption/ionization (ADI) source. The addition of 0.9 % hydrogen to the helium support gas in a 35-W plasma jet increased signals for a range of test analytes, with enhancement factors of up to 68, without proportional increases in background levels. The changes in signal levels result from a combination of changes in the desorption kinetics from the surface and increased ion production in the gas phase. The enhancement in ADI-MS performance despite the quenching of key plasma species reported in earlier studies suggests that ionization with a H2/He plasma jet is the result of an alternate mechanism involving the direct generation of ionized hydrogen.

  15. Effects of SWNT and metallic catalyst on hydrogen absorption/desorption performance of MgH2.

    PubMed

    Wu, Chengzhang; Wang, Ping; Yao, Xiangdong; Liu, Chang; Chen, Demin; Lu, Gao Qing; Cheng, Huiming

    2005-12-01

    The microstructure and absorption/desorption characteristics of composite MgH2 and 5 wt % as-prepared single-walled carbon nanotubes (MgH2-5ap) obtained by the mechanical grinding method were investigated. Experimental results show that the MgH2-5ap sample exhibits faster absorption kinetics and relatively lower desorption temperature than pure MgH2 or MgH2-purified single-walled carbon nanotube composite. Storage capacities of 6.0 and 4.2 wt % hydrogen for the MgH2-5ap composite were achieved in 60 min at 423 and 373 K, respectively. Furthermore, its desorption temperature was reduced by 70 K due to the introduction of as-prepared single-walled carbon nanotubes (SWNTs). In addition, the different effects of SWNTs and metallic catalysts contained in the as-prepared SWNTs were also investigated and a hydrogenation mechanism was proposed. It is suggested that metallic particles may be mainly responsible for the improvement of the hydrogen absorption kinetics, and SWNTs for the enhancement of hydrogen absorption capacity of MgH2.

  16. A kinetics study on promising hydrogen storage properties of Mg-based thin films at room temperature.

    PubMed

    Qu, Jianglan; Liu, Yang; Xin, Gongbiao; Zheng, Jie; Li, Xingguo

    2014-04-21

    Pd-Mg-Pd thin films with variable thickness of Mg layers were prepared. Their optical and electrical changes in both gasochromic and chemochromic processes were compared to investigate the kinetics of Mg-based thin films at room temperature. Hydrogen absorption and desorption kinetics of Pd-Mg-Pd thin films were strongly dependent on the thickness of the Mg layer. Especially, when the thickness was lowered to 60 nm, a MgH2 layer formed immediately after exposure to H2 at room temperature, while a Mg layer was rapidly generated during hydrogen desorption in ambient air. By means of optical and electrical resistance measurements, we found that the diffusion process contributed significantly to hydrogen absorption and desorption. The remarkable absorption and desorption kinetics at room temperature reported here suggested promising applications in Mg-based energy-efficient devices and hydrogen sensors.

  17. Factors influencing adsorption and desorption of trimethoprim on marine sediments: mechanisms and kinetics.

    PubMed

    Li, Jia; Zhang, Hua

    2017-08-05

    Adsorption-desorption behavior of ionic antibiotics in natural aquatic environment is complex, especially in coastal or estuary area where influencing factors such as pH and salinity usually varied in a wide range. In this study, batch-type and stirred flow chamber (SFC) experiments were carried out to simulate the sorption-desorption behavior of trimethoprim (TMP) in seawater-sediment system. Equilibrium and kinetic modeling were carried out to determine the rate and extent of TMP sorption on two marine sediments with different properties. Sediment BHB (K d , 6.40 L kg(-1)) has a greater sorption capacity compared with sediment LZB (K d , 3.40 L kg(-1)), which is related to the higher content of organic carbon and clay of sediment BHB. Adsorption of TMP varied in the pH range of 6.9 to 8.1 with maximum adsorption at pH 7.4. Increasing salinity and presence of phosphate and nitrate led to decreased TMP sorption. Attenuated total reflection Fourier transform infrared (ATR-FTIR) analysis demonstrated the formation of hydrogen bond between TMP and marine sediments. Adsorption of TMP on marine sediments was a non-equilibrium process that can be described with second-order kinetic model. Our analysis suggested that chemical non-equilibrium was the rate controlling process and intraparticle diffusion was also involved in TMP adsorption. A moderate desorption percentage (16.4-22.8% for LZB and 32.5-42.0%for BHB) was observed. Overall, the results showed that environmental factors and time-dependent processes need to be considered in modeling the fate and transport of TMP in coastal/estuarine waters.

  18. Hydrogen desorption from MgH2(110) surface with transition-metal catalyst: a DFT study of energetics and barriers

    NASA Astrophysics Data System (ADS)

    Wang, Lin-Lin; Johnson, Duane D.

    2011-03-01

    Transition-metal (TM) catalysts are widely used in hydrogen-storage materials to increase hydrogen absorption and desorption kinetics. Using density functional theory calculations, we elucidate the catalytic effect of Ti on H-desorption from Mg H2 (110) surface. Kinetic energy barriers of different reaction pathways of hydrogen desorption are calculated via nudged-elastic-band method. We find that Ti dopant is effective in reducing kinetic barriers, in agreement with experimental observations. We also find that magnetic degrees of freedom must be carefully included to describe the change of magnetic states during catalytic-enhanced desorption. As vacancy migration barriers are lower than desorption barrier, bulk diffusion of H inherently feeds into the favorable surface desorption mechanism. Supported by the DOE/BES under DE-FG02-03ER15476 (Catalysis), DEFC36-05GO15064 (Sandia Metal-Hydride Center of Excellence), DE-FG02-03ER46026 (Materials), and DE-AC02-07CH11358 at the Ames Laboratory operated by Iowa State University.

  19. Equilibrium, hysteresis and kinetics of cadmium desorption from sodium-feldspar using rhamnolipid biosurfactant.

    PubMed

    Aşçi, Yeliz; Açikel, Unsal; Açikel, Yeşim Sağ

    2012-09-01

    In this study, the sorption/desorption equilibruim and the desorption kinetics of Cd by rhamnolipid biosurfactant from Na-feldspar as a soil component were investigated. The linear, Langmuir and Freundlich isotherms adequately fitted the equilibrium sorption data with regression coefficients ranging from 0.9836 - 0.9879. However, both the sorption/desorption equilibria were well characterized by the Freundlich model. The extent of hysteresis was quantified based on the differences obtained from sorption and desorption isotherms regarding the quantity of Cd(II) sorbed, the Freundlich exponent, concentration-dependent metal distribution coefficients, and the irreversibility index based on the metal distribution coefficient. The kinetics of desorption of Cd from Na-feldspar was investigated using 77 mM rhamnolipid and at pH 6.8. The first-order, an empirical first-order desorption model (two-coefficient), Lagergren-pseudo-first-order, pseudo-second-order, Elovich and modified Freundlich models were used to describe the kinetic data to estimate the rate constants. To determine the rate-controlling step, the intra-particle diffusion model was also applied to the desorption process. The desorption kinetics of Cd(II) on Na-feldspar was represented better by the pseudo-second-order, Elovich and modified Freundlich equations with correlation coefficients ranging from 0.9941- 0.9982 than by first-order equations. The rate-controlling stage was suggested to be mainly the surface reaction mechanism.

  20. Liquefaction chemistry and kinetics: Hydrogen utilization studies

    SciTech Connect

    Rothenberger, K.S.; Warzinski, R.P.; Cugini, A.V.

    1995-12-31

    The objectives of this project are to investigate the chemistry and kinetics that occur in the initial stages of coal liquefaction and to determine the effects of hydrogen pressure, catalyst activity, and solvent type on the quantity and quality of the products produced. The project comprises three tasks: (1) preconversion chemistry and kinetics, (2) hydrogen utilization studies, and (3) assessment of kinetic models for liquefaction. The hydrogen utilization studies work will be the main topic of this report. However, the other tasks are briefly described.

  1. Trapping of hydrogen atoms in X-irradiated salts at room temperature and the decay kinetics

    NASA Technical Reports Server (NTRS)

    May, C. E.; Philipp, W. H.; Marsik, S. J.

    1974-01-01

    The salts (hypophosphites, formates, a phosphite, a phosphate, and an oxalate) were X-irradiated, whereby hydrogen formed chemically by a radiolytic process becomes trapped in the solid. By room temperature vacuum extraction, the kinetics for the evolution of this trapped hydrogen was studied mass spectrometrically. All salts except two exhibited second-order kinetics. The two exceptions (NaH2PO2(H2O) and K2HPO4) showed first-order kinetics. Based on experimental results, the escape of hydrogen involves three steps: the diffusion of hydrogen atoms from the bulk to the surface, association of these atoms on the surface (rate controlling step for second-order hydrogen evolution), and the desorption of molecular hydrogen from the surface. The hydrogen does not escape if the irradiated salt is stored in air, apparently because adsorbed air molecules occupy surface sites required in the escape mechanism.

  2. Protective coatings preventing hydrogen desorption from titanium during ion irradiation

    NASA Astrophysics Data System (ADS)

    Evsin, A. E.; Begrambekov, L. B.; Dovganyuk, S. S.; Kaplevsky, A. S.; Shutikova, M. I.

    2017-05-01

    Effect of yttria and titanium nitride coatings on features of deuterium desorption from titanium layer is investigated. It is shown that both coatings significantly raise the temperature of maximum of deuterium thermal desorption from titanium under linear heating and prevent desorption under prolonged keeping at the operating temperature of a neutron tube target. However, under irradiation with ions of H2 + O2 plasma the barrier properties of titanium nitride appear to degrade.

  3. Kinetics of Uranium(VI) Desorption from Contaminated Sediments: Effect of Geochemical Conditions and Model Evaluation

    SciTech Connect

    Liu, Chongxuan; Shi, Zhenqing; Zachara, John M.

    2009-09-01

    Stirred-flow cell experiments were performed to investigate the kinetics of uranyl [U(VI)] desorption from a contaminated sediment collected from the Hanford 300 Area at the US Department of Energy (DOE) Hanford Site, Washington. Three influent solutions of variable pH, Ca and carbonate concentrations that affected U(VI) aqueous and surface speciation were used under dynamic flow conditions to evaluate the effect of geochemical conditions on the rate of U(VI) desorption. The measured rate of U(VI) desorption varied with solution chemical composition that evolved as a result of thermodynamic and kinetic interactions between the influent solutions and sediment. The solution chemical composition that led to a lower equilibrium U(VI) sorption to the solid phase yielded a faster desorption rate. The experimental results were used to evaluate a multi-rate, surface complexation model (SCM) that has been proposed to describe U(VI) desorption kinetics in the Hanford sediment that contained complex sorbed U(VI) species in mass transfer limited domains. The model was modified and supplemented by including multi-rate, ion exchange reactions to describe the geochemical interactions between the solutions and sediment. With the same set of model parameters, the modified model reasonably well described the evolution of major ions and the rates of U(VI) desorption under variable geochemical and flow conditions, implying that the multi-rate SCM is an effective way to describe U(VI) desorption kinetics in subsurface sediments.

  4. Modelling of hydrogen thermal desorption spectrum in nonlinear dynamical boundary-value problem

    NASA Astrophysics Data System (ADS)

    Kostikova, E. K.; Zaika, Yu V.

    2016-11-01

    One of the technological challenges for hydrogen materials science (including the ITER project) is the currently active search for structural materials with various potential applications that will have predetermined limits of hydrogen permeability. One of the experimental methods is thermal desorption spectrometry (TDS). A hydrogen-saturated sample is degassed under vacuum and monotone heating. The desorption flux is measured by mass spectrometer to determine the character of interactions of hydrogen isotopes with the solid. We are interested in such transfer parameters as the coefficients of diffusion, dissolution, desorption. The paper presents a distributed boundary-value problem of thermal desorption and a numerical method for TDS spectrum simulation, where only integration of a nonlinear system of low order (compared with, e.g., the method of lines) ordinary differential equations (ODE) is required. This work is supported by the Russian Foundation for Basic Research (project 15-01-00744).

  5. Change in soft magnetic properties of Fe-based metallic glasses during hydrogen absorption and desorption

    SciTech Connect

    Novak, L.; Lovas, A.; Kiss, L.F.

    2005-08-15

    The stress level can be altered in soft magnetic amorphous alloys by hydrogen absorption. The resulting changes in the soft magnetic parameters are reversible or irreversible, depending on the chemical composition. Some of these effects are demonstrated in Fe-B, Fe-W-B, and Fe-V-B glassy ribbons, in which various magnetic parameters are measured mainly during hydrogen desorption. The rate of hydrogen desorption is also monitored by measuring the pressure change in a hermetically closed bomb. The observed phenomena are interpreted on the basis of induced stresses and chemical interactions between the solute metal and hydrogen.

  6. Long-term kinetics of uranyl desorption from sediments under advective conditions

    NASA Astrophysics Data System (ADS)

    Shang, Jianying; Liu, Chongxuan; Wang, Zheming; Zachara, John

    2014-02-01

    Long-term (>4 months) column experiments were performed to investigate the kinetics of uranyl (U(VI)) desorption in sediments collected from the Integrated Field Research Challenge site at the U.S. Department of Energy Hanford 300 Area. The experimental results were used to evaluate alternative multirate surface complexation reaction (MRSCR) approaches to describe the short and long-term kinetics of U(VI) desorption under flow conditions. The surface complexation reaction (SCR) stoichiometry and equilibrium constants and multirate parameters in the MRSCR models were independently characterized in batch and stirred flow-cell reactors. MRSCR models that were either additively constructed using the MRSCRs for individual size fractions, or composite in nature, could effectively describe short-term U(VI) desorption under flow conditions. The long-term desorption results, however, revealed that using the labile U concentration measured by carbonate extraction underestimated desorbable U(VI) and the long-term rate of U(VI) desorption. This study also found that the gravel size fraction (2-8 mm), which is typically treated as nonreactive in modeling U(VI) reactive transport because of low external surface area, can have an important effect on the U(VI) desorption in the sediment. This study demonstrates an approach to effectively extrapolate U(VI) desorption kinetics for field-scale application and identifies important parameters and uncertainties affecting model predictions.

  7. Numerical simulation of hydrogen desorption from high-density metal hydride hydrogen storage vessels

    NASA Astrophysics Data System (ADS)

    Sang-Kun, O.; Yi, Kyung-Woo; Cho, Sung-Wook

    2017-07-01

    Metal hydride (MH) alloys are a promising type of material in hydrogen storage applications, allowing for low-pressure, high-density storage. However, while many studies are being performed on enhancing the hydrogen storage properties of such alloys, there has been little research on large-scale storage vessels which make use of the alloys. In particular, large-scale, high-density storage devices must make allowances for the temperature variations caused by the heat of reaction between hydrogen and MH alloys, which may impact the storage characteristics. In this study, we propose a numerical model for the design and evaluation of hydrogen storage devices using MH alloys. Hydrogen desorption reaction behavior for an alloy is observed in terms of temperature and reaction rate. This behavioral correlation is used as the basis for a comprehensive simulation model of the alloy system. Calculated results are found to be in good agreement with experimentally measured data, indicating that the model may be applied to multiple system geometries, scales, and alloy compositions.

  8. Progress in improving thermodynamics and kinetics of new hydrogen storage materials

    NASA Astrophysics Data System (ADS)

    Song, Li-fang; Jiang, Chun-hong; Liu, Shu-sheng; Jiao, Cheng-li; Si, Xiao-liang; Wang, Shuang; Li, Fen; Zhang, Jian; Sun, Li-xian; Xu, Fen; Huang, Feng-lei

    2011-06-01

    Hydrogen storage material has been much developed recently because of its potential for proton exchange membrane (PEM) fuel cell applications. A successful solid-state reversible storage material should meet the requirements of high storage capacity, suitable thermodynamic properties, and fast adsorption and desorption kinetics. Complex hydrides, including boron hydride and alanate, ammonia borane, metal organic frameworks (MOFs), covalent organic frameworks (COFs) and zeolitic imidazolate frameworks (ZIFs), are remarkable hydrogen storage materials because of their advantages of high energy density and safety. This feature article focuses mainly on the thermodynamics and kinetics of these hydrogen storage materials in the past few years.

  9. Influence of aluminum location on hydrogen sorption kinetics of magnesium-based materials

    NASA Astrophysics Data System (ADS)

    Zhou, Shixue; Zhang, Tonghuan; Wang, Naifei; Li, Tao; Niu, Haili; Yu, Hao; Liu, Di

    2014-03-01

    Hydrogen storage materials from Mg-Al alloy and Mg+Al mixture were prepared by reactive milling under H2 atmosphere with carbonized anthracite as milling aid. The crystal structure of the materials and influence of Al location on hydrogen absorption/desorption kinetics were investigated. Results show that Mg partly got hydrided into β-MgH2 and γ-MgH2 during reactive milling. The average crystallite sizes of β-MgH2 in the as-milled Mg-Al alloy and Mg+Al mixture were calculated by Scherrer equation to be 10 nm and 17 nm, respectively. In the process of hydrogen desorption, the catalytic ability of Al in Mg crystal lattice was not as effective as that on particle surface. The apparent activation energies for hydrogen desorption of the two materials were estimated by Kissinger equation to be 112.2 kJ/mol and 63.7 kJ/mol, respectively. Mg17Al12 reacted with H2 to convert into MgH2 and elemental Al during static hydrogenation at 300°C. For the hydrogenated Mg+Al mixture, the obvious increase of crystallite size resulted in a low rate of hydrogen absorption and a high temperature for hydrogen desorption.

  10. Mg-based nanocomposites with high capacity and fast kinetics for hydrogen storage.

    PubMed

    Yao, Xiangdong; Wu, Chengzhang; Du, Aijun; Lu, Gao Qing; Cheng, Huiming; Smith, Sean C; Zou, Jin; He, Yinghe

    2006-06-22

    Magnesium and its alloys have shown a great potential in effective hydrogen storage due to their advantages of high volumetric/gravimetric hydrogen storage capacity and low cost. However, the use of these materials in fuel cells for automotive applications at the present time is limited by high hydrogenation temperature and sluggish sorption kinetics. This paper presents the recent results of design and development of magnesium-based nanocomposites demonstrating the catalytic effects of carbon nanotubes and transition metals on hydrogen adsorption in these materials. The results are promising for the application of magnesium materials for hydrogen storage, with significantly reduced absorption temperatures and enhanced ab/desorption kinetics. High level Density Functional Theory calculations support the analysis of the hydrogenation mechanisms by revealing the detailed atomic and molecular interactions that underpin the catalytic roles of incorporated carbon and titanium, providing clear guidance for further design and development of such materials with better hydrogen storage properties.

  11. Kinetics of neptunium(V) sorption and desorption on goethite: An experimental and modeling study

    NASA Astrophysics Data System (ADS)

    Tinnacher, Ruth M.; Zavarin, Mavrik; Powell, Brian A.; Kersting, Annie B.

    2011-11-01

    Various sorption phenomena, such as aging, hysteresis and irreversible sorption, can cause differences between contaminant (ad)sorption and desorption behavior and lead to apparent sorption 'asymmetry'. We evaluate the relevance of these characteristics for neptunium(V) (Np(V)) sorption/desorption on goethite using a 34-day flow-cell experiment and kinetic modeling. Based on experimental results, the Np(V) desorption rate is much slower than the (ad)sorption rate, and appears to decrease over the course of the experiment. The best model fit with a minimum number of fitting parameters was achieved with a multi-reaction model including (1) an equilibrium Freundlich site (site 1), (2) a kinetically-controlled, consecutive, first-order site (site 2), and (3) a parameter ψ, which characterizes the desorption rate on site 2 based on a concept related to transition state theory (TST). This approach allows us to link differences in adsorption and desorption kinetics to changes in overall reaction pathways, without assuming different adsorption and desorption affinities (hysteresis) or irreversible sorption behavior a priori. Using modeling as a heuristic tool, we determined that aging processes are relevant. However, hysteresis and irreversible sorption behavior can be neglected within the time-frame (desorption over 32 days) and chemical solution conditions evaluated in the flow-cell experiment. In this system, desorption reactions are very slow, but they are not irreversible. Hence, our data do not justify an assumption of irreversible Np(V) sorption to goethite in transport models, which effectively limits the relevance of colloid-facilitated Np(V) transport to near-field environments. However, slow Np(V) desorption behavior may also lead to a continuous contaminant source term when metals are sorbed to bulk mineral phases. Additional long-term experiments are recommended to definitely rule out irreversible Np(V) sorption behavior at very low surface loadings and

  12. GaN CVD Reactions: Hydrogen and Ammonia Decomposition and the Desorption of Gallium

    SciTech Connect

    Bartram, Michael E.; Creighton, J. Randall

    1999-05-26

    Isotopic labeling experiments have revealed correlations between hydrogen reactions, Ga desorption, and ammonia decomposition in GaN CVD. Low energy electron diffraction (LEED) and temperature programmed desorption (TPD) were used to demonstrate that hydrogen atoms are available on the surface for reaction after exposing GaN(0001) to deuterium at elevated temperatures. Hydrogen reactions also lowered the temperature for Ga desorption significantly. Ammonia did not decompose on the surface before hydrogen exposure. However, after hydrogen reactions altered the surface, N15H3 did undergo both reversible and irreversible decomposition. This also resulted in the desorption of N2 of mixed isotopes below the onset of GaN sublimation, This suggests that the driving force of the high nitrogen-nitrogen bond strength (226 kcal/mol) can lead to the removal of nitrogen from the substrate when the surface is nitrogen rich. Overall, these findings indicate that hydrogen can influence G-aN CVD significantly, being a common factor in the reactivity of the surface, the desorption of Ga, and the decomposition of ammonia.

  13. Determination of the thermal desorption kinetic parameters for samples with a temperature gradient

    NASA Astrophysics Data System (ADS)

    Kurenyova, T. Y.; Ryskin, M. E.; Shub, B. R.

    1981-08-01

    An application of the thermal desorption technique to the study of desorption from the samples with a temperature gradient is discussed. The kinetics of first- and second-order desorption from linearly and exponentially heated samples with a parabolic temperature profile is considered. It is shown that the low-temperature part of the thermal desorption curve is described by the same equations as those for the desorption from the nongradient surface with the less effective area and with the temperature equal to that at the center of the nonuniformly heated sample. The approximate analytical expressions for the amount of adsorbed surface species as a function of time are derived. These expressions enable to find the kinetics order, the activation energy E and the preexponential factor k0 for the desorption process from thermal desorption spectra. In a first approximation the corrections for the nonuniformity of the sample temperature do not substantially change the value of E but slightly increase the value of k0. The correction procedure for k0 is described in detail. The possible application of the proposed method to various experimental conditions is discussed.

  14. [Investigation of intermetalloid hydrogen sorption-desorption in physical-chemical life support system].

    PubMed

    Klimarev, S I

    2007-01-01

    A hydrogen accumulating alloy was tested for safe sorption and storage of electrolyzed hydrogen within life support system. The alloy of choice was intermetalloid LaNi5 absorbing and desorbing hydrogen at approximately room temperature and pressure A of 20 atm. Sorption was evaluated at hydrogen pressure A of 0.1; 0.2 and 0.3 atm. The rate of desorption was controlled at 2.0 l/min to maintain the standard carbon dioxide and hydrogen feed into the processor. Results of the investigation lead to the main conclusion that the hydrogen accumulating alloy can be an integral component of a new generation of life support systems.

  15. Theoretical and experimental studies of hydrogen adsorption and desorption on Ir surfaces.

    PubMed

    Kaghazchi, Payam; Jacob, Timo; Chen, Wenhua; Bartynski, Robert A

    2013-08-21

    We report adsorption and desorption of hydrogen on planar Ir(210) and faceted Ir(210), consisting of nanoscale {311} and (110) facets, by means of temperature programmed desorption (TPD) and density functional theory (DFT) in combination with the ab initio atomistic thermodynamics approach. TPD spectra show that only one H2 peak is seen from planar Ir(210) at all coverages whereas a single H2 peak is observed at around 440 K (F1) at fractional monolayer (ML) coverage and an additional H2 peak appears at around 360 K (F2) at 1 ML coverage on faceted Ir(210), implying structure sensitivity in recombination and desorption of hydrogen on faceted Ir(210) versus planar Ir(210), but no evidence is found for size effects in recombination and desorption of hydrogen on faceted Ir(210) for average facet sizes of 5-14 nm. Calculations indicate that H prefers to bind at the two-fold short-bridge sites of the Ir surfaces. In addition, we studied the stability of the Ir surfaces in the presence of hydrogen at different H coverages through surface free energy plots as a function of the chemical potential, which is also converted to a temperature scale. Moreover, the calculations revealed the origin of the two TPD peaks of H2 from faceted Ir(210): F1 from desorption of H2 on {311} facets while F2 from desorption of H2 on (110) facets.

  16. Kinetic Desorption and Sorption of U(VI) During Reactive Transport in a Contaminated Hanford Sediment

    SciTech Connect

    Qafoku, Nik; Zachara, John M.; Liu, Chongxuan; Gassman, Paul L.; Qafoku, Odeta; Smith, Steven C.

    2005-05-12

    Column experiments were conducted to investigate U(VI) desorption and sorption kinetics in a sand-textured, contaminated (22.7 µmol kg-1) capillary fringe sediment that had experienced long-term exposure to U(VI). The clay fraction mineralogy of the sediment was dominated by montmorillonite, muscovite, vermiculite, and chlorite. Saturated column experiments were performed under mildly alkaline/calcareous conditions representative of the Hanford site where uranyl–carbonate and calcium–uranyl–carbonate complexes dominate aqueous speciation. A U(VI) free solution was used to study U(VI) desorption in columns where different flow rates were applied. Uranium(VI) sorption was studied after the desorption of labile contaminant U(VI) using different U(VI) concentrations in the leaching solution. Strong kinetic behavior was observed for both U(VI) desorption and sorption. Although U(VI) is semi–mobile in mildly alkaline, calcareous subsurface environments, our results showed substantial U(VI) sorption, significant retardation during transport, and atypical breakthrough curves with extended tailing. A distributed rate model was applied to describe the effluent data and to allow comparisons between the desorption rate of contaminant U(VI) with the rate of short-term U(VI) sorption. Desorption was the slower process. Our results suggest that U(VI) release and transport in the vadose zone and aquifer system from which the sediment was obtained are kinetically controlled.

  17. 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.

  18. Kinetics of tetracycline, oxytetracycline, and chlortetracycline adsorption and desorption on two acid soils.

    PubMed

    Fernández-Calviño, David; Bermúdez-Couso, Alipio; Arias-Estévez, Manuel; Nóvoa-Muñoz, Juan Carlos; Fernández-Sanjurjo, Maria J; Álvarez-Rodríguez, Esperanza; Núñez-Delgado, Avelino

    2015-01-01

    The purpose of this work was to quantify retention/release of tetracycline, oxytetracycline, and chlortetracycline on two soils, paying attention to sorption kinetics and to implications of the adsorption/desorption processes on transfer of these pollutants to the various environmental compartments. We used the stirred flow chamber (SFC) procedure to achieve this goal. All three antibiotics showed high affinity for both soils, with greater adsorption intensity for soil 1, the one with the highest organic matter and Al and Fe oxides contents. Desorption was always <15%, exhibiting strong hysteresis in the adsorption/desorption processes. Adsorption was adequately modeled using a pseudo first-order equation with just one type of adsorption sites, whereas desorption was better adjusted considering both fast and slow sorption sites. The adsorption maximum (qmax) followed the sequence tetracycline > oxytetracycline > chlortetracycline in soil 1, with similar values for the three antibiotics and the sequence tetracycline > chlortetracycline > oxytetracycline in soil 2. The desorption sequences were oxytetracycline > tetracycline > chlortetracycline in soil 1 and oxytetracycline > chlortetracycline > tetracycline in soil 2. In conclusion, the SFC technique has yielded new kinetic data regarding tetracycline, oxytetracycline, and chlortetracycline adsorption/desorption on soils, indicating that it can be used to shed further light on the retention and transport processes affecting antibiotics on soils and other media, thus increasing knowledge on the behavior and evolution of these pharmaceutical residues in the environment.

  19. Theoretical and experimental studies of hydrogen adsorption and desorption on Ir surfaces

    DOE PAGES

    Kaghazchi, Payam; Jacob, Timo; Chen, Wenhua; ...

    2013-06-03

    Here, we report adsorption and desorption of hydrogen on planar Ir(210) and faceted Ir(210), consisting of nanoscale {311} and (110) facets, by means of temperature programmed desorption (TPD) and density functional theory (DFT) in combination with the ab initio atomistic thermodynamics approach. TPD spectra show that only one H2 peak is seen from planar Ir(210) at all coverages whereas a single H2 peak is observed at around 440 K (F1) at fractional monolayer (ML) coverage and an additional H2 peak appears at around 360 K (F2) at 1 ML coverage on faceted Ir(210), implying structure sensitivity in recombination and desorptionmore » of hydrogen on faceted Ir(210) versus planar Ir(210), but no evidence is found for size effects in recombination and desorption of hydrogen on faceted Ir(210) for average facet sizes of 5-14 nm. Calculations indicate that H prefers to bind at the two-fold short-bridge sites of the Ir surfaces. In addition, we studied the stability of the Ir surfaces in the presence of hydrogen at different H coverages through surface free energy plots as a function of the chemical potential, which is also converted to a temperature scale. Moreover, the calculations revealed the origin of the two TPD peaks of H2 from faceted Ir(210): F1 from desorption of H2 on {311} facets while F2 from desorption of H2 on (110) facets.« less

  20. Effects and Mechanisms of Mechanical Activation on Hydrogen Sorption/ Desorption of Nanoscale Lithium Nitrides

    SciTech Connect

    Shaw, Leon, L.; Yang, Gary, Z.; Crosby, Kyle; Wwan, Xufei. Zhong, Yang; Markmaitree, Tippawan; Osborn, William; Hu, Jianzhi; Kwak, Ja Hun

    2012-04-26

    The objective of this project is to investigate and develop novel, mechanically activated, nanoscale Li3N-based and LiBH4-based materials that are able to store and release {approx}10 wt% hydrogen at temperatures near 100 C with a plateau hydrogen pressure of less than 10 bar. Four (4) material systems have been investigated in the course of this project in order to achieve the project objective. These 4 systems are (i) LiNH2+LiH, (ii) LiNH2+MgH2, (iii) LiBH4, and (iv) LiBH4+MgH2. The key findings we have obtained from these 4 systems are summarized below. *The thermodynamic driving forces for LiNH2+LiH and LiBH4 systems are not adequate to enable H2 release at temperatures < 100 C. *Hydrogen release in the solid state for all of the four systems is controlled by diffusion, and thus is a slow process. *LiNH2+MgH2 and LiBH4+MgH2 systems, although possessing proper thermodynamic driving forces to allow for H2 release at temperatures < 100 C, have sluggish reaction kinetics because of their diffusion-controlled rate-limiting steps. *Reducing particles to the nanometer length scale (< 50 nm) can improve the thermodynamic driving force to enable H2 release at near ambient temperature, while simultaneously enhancing the reaction kinetics as well as changing the diffusion-controlled rate-limiting step to gas desorption-controlled rate-limiting step. This phenomenon has been demonstrated with LiBH4 and offers the hope that further work along this direction will make one of the material systems, i.e., LiBH4, LiBH4+MgH2 and LiNH2+MgH2, possess the desired thermodynamic properties and rapid H2 uptake/release kinetics for on-board applications. Many of the findings and knowledge gained from this project have been published in archival refereed journal articles [1-15] and are accessible by general public. Thus, to avoid a bulky final report, the key findings and knowledge gained from this project will be succinctly summarized, particularly for those findings and knowledge

  1. Long-term Kinetics of Uranyl Desorption from Sediments Under Advective Conditions

    SciTech Connect

    Shang, Jianying; Liu, Chongxuan; Wang, Zheming; Zachara, John M.

    2014-02-15

    Long-term (> 4 months) column experiments were performed to investigate the kinetics of uranyl (U(VI)) desorption in sediments collected from the Integrated Field Research Challenge (IFRC) site at the US Department of Energy (DOE) Hanford 300 Area. The experimental results were used to evaluate alternative multi-rate surface complexation reaction (SCR) approaches to describe the short- and long-term kinetics of U(VI) desorption under flow conditions. The SCR stoichiometry, equilibrium constants, and multi-rate parameters were independently characterized in batch and stirred flow-cell reactors. Multi-rate SCR models that were either additively constructed using the SCRs for individual size fractions (e.g., Shang et al., 2011), or composite in nature could effectively describe short-term U(VI) desorption under flow conditions. The long-term desorption results, however, revealed that using a labile U concentration measured by carbonate extraction under-estimated desorbable U(VI) and the long-term rate of U(VI) desorption. An alternative modeling approach using total U as the desorbable U(VI) concentration was proposed to overcome this difficulty. This study also found that the gravel size fraction (2-8 mm), which is typically treated as non-reactive in modeling U(VI) reactive transport because of low external surface area, can have an important effect on the U(VI) desorption in the sediment. This study demonstrates an approach to effectively extrapolate U(VI) desorption kinetics for field-scale application, and identifies important parameters and uncertainties affecting model predictions.

  2. Numerical comparison of hydrogen desorption behaviors of metal hydride beds based on uranium and on zirconium-cobalt

    SciTech Connect

    Kyoung, S.; Yoo, H.; Ju, H.

    2015-03-15

    In this paper, the hydrogen delivery capabilities of uranium (U) and zirconium-cobalt (ZrCo) are compared quantitatively in order to find the optimum getter materials for tritium storage. A three-dimensional hydrogen desorption model is applied to two identically designed cylindrical beds with the different materials, and hydrogen desorption simulations are then conducted. The simulation results show superior hydrogen delivery performance and easier thermal management capability for the U bed. This detailed analysis of the hydrogen desorption behaviors of beds with U and ZrCo will help to identify the optimal bed material, bed design, and operating conditions for the storage and delivery system in ITER. (authors)

  3. Plutonium desorption from mineral surfaces at environmental concentrations of hydrogen peroxide.

    PubMed

    Begg, James D; Zavarin, Mavrik; Kersting, Annie B

    2014-06-03

    Knowledge of Pu adsorption and desorption behavior on mineral surfaces is crucial for understanding its environmental mobility. Here we demonstrate that environmental concentrations of H2O2 can affect the stability of Pu adsorbed to goethite, montmorillonite, and quartz across a wide range of pH values. In batch experiments where Pu(IV) was adsorbed to goethite for 21 days at pH 4, 6, and 8, the addition of 5-500 μM H2O2 resulted in significant Pu desorption. At pH 6 and 8 this desorption was transient with readsorption of the Pu to goethite within 30 days. At pH 4, no Pu readsorption was observed. Experiments with both quartz and montmorillonite at 5 μM H2O2 desorbed far less Pu than in the goethite experiments highlighting the contribution of Fe redox couples in controlling Pu desorption at low H2O2 concentrations. Plutonium(IV) adsorbed to quartz and subsequently spiked with 500 μM H2O2 resulted in significant desorption of Pu, demonstrating the complexity of the desorption process. Our results provide the first evidence of H2O2-driven desorption of Pu(IV) from mineral surfaces. We suggest that this reaction pathway coupled with environmental levels of hydrogen peroxide may contribute to Pu mobility in the environment.

  4. Investigation of potential alternative hydrogen carrier, Mg supported zeolite with temperature programmed desorption of NH3.

    PubMed

    Cho, Sung June; Kim, Tak Hee; Jang, Young Bae; Lee, Jun

    2007-11-01

    Magnesium ion exchanged zeolite A was subject to the measurement of the temperature programmed desorption of NH3 to explore the possibility of the potential hydrogen carrier. The result suggested that the Mg supported NaA zeolite released a significant amount of ammonia corresponding to 1.4 Hwt% hydrogen at around 373 K. Under the same condition after the NH3 adsorption at ambient temperature, the MgCl2 sample released 1.0 Hwt% hydrogen at around 340 K. The present work suggests that the Mg supported zeolite can also be utilized as hydrogen carrier.

  5. Validation of a hybrid two-site gamma model for naphthalene desorption kinetics

    SciTech Connect

    Ahn, I.S.; Lion, L.W.; Shuler, M.L.

    1999-09-15

    Three models for sorption/desorption of polycyclic aromatic hydrocarbon (PAH) contaminants from soil were compared for their ability to predict the transport of PAH in soil: a gamma model, a two-site/two-region nonequilibrium model, and a hybrid model. In the hybrid model, soil organic matter was conceptually divided into two compartments; a fraction with rapid sorption/desorption kinetics and a compartment with mass-transfer-limited kinetics. Contaminant sorbed in the rapid compartment was assumed to be in instantaneous equilibrium with the aqueous phase, while the release of contaminant from the slow fraction was assumed to be governed by a gamma distribution of rate coefficients. The hybrid model successfully described the initial rapid release of a model PAH contaminant, naphthalene, from a sieved soil sample of moderate organic content ({approx_equal} 2.3%) as well as the following slow release observed over 25 days in batch desorption experiments. Other necessary model parameters, such as the hydrodynamic dispersion coefficient of naphthalene and the macropore porosity, were evaluated in separate experiments. A transport model incorporating the hybrid model for naphthalene sorption/desorption successfully predicted the elution profile of naphthalene in independent soil-column experiments with no adjustable parameters. The success of the hybrid model suggests that a wide array of rate controls govern PAH desorption. This conclusion is consistent with the view of soils as consisting of a mix of different sorptive constituents and heterogeneous physical constraints on PAH release.

  6. Surface diffusion and desorption kinetics for perfluoro-n-butane on Ru(001)

    NASA Astrophysics Data System (ADS)

    Arena, M. V.; Westre, E. D.; George, S. M.

    1991-03-01

    The surface diffusion and desorption kinetics for perfluoro-n-butane on Ru(001) were examined using laser-induced thermal desorption (LITD) and temperature programmed desorption (TPD) techniques. The surface diffusion displayed Arrhenius behavior and was coverage independent. The surface diffusion parameters for perfluoro-n-butane on Ru(001) were Edif=2.9±0.3 kcal/mol and D0=5.9×10-2±0.2 cm2/s. The desorption parameters for perfluoro-n-butane on Ru(001) were Edes=13.8±0.6 kcal/mol and νdes=2.8×1021±0.1 s-1. In comparison, the surface diffusion parameters for n-butane on Ru(001) were Edif=3.5±0.2 kcal/mol and D0=1.4×10-1±0.2 cm2/s. The desorption parameters for n-butane on Ru(001) were Edes=11.9±0.5 kcal/mol and νdes=3.6×1015±0.1 s-1. The corrugation ratio, defined as Ω≡Edif/Edes, was determined to be Ω=0.21 for perfluoro-n-butane on Ru(001). This corrugation ratio was substantially different than the corrugation ratio of Ω≊0.30 measured for n-butane and various other n-alkanes, cycloalkanes and branched alkanes on Ru(001). The comparison between perfluoro-n-butane and the other alkanes indicates that fluorination lowers the surface corrugation ratio on Ru(001). Likewise, fluorination significantly increases the preexponential for desorption from Ru(001). This study illustrates the magnitude of substituent effects on surface diffusion and desorption kinetics for a physisorbed molecule on a single-crystal metal surface.

  7. An investigation of the kinetics for hydrogen chemisorption on iron metal surfaces

    NASA Technical Reports Server (NTRS)

    Shanabarger, M. R.

    1980-01-01

    A quasi-isothermal approach was used to study the kinetics of hydrogen and hydrogen sulfide chemisorption onto iron film in an effort to understand the environmental degradation of steels. The coverage of chemisorbed hydrogen or chemisorbed sulfur was observed as a function of time for fixed conditions of substrate temperature. Auger electron spectroscopy was used to observe the sulfur and chemisorption-induced resistance change was employed to monitor hydrogen coverage. To compare the results obtained from studying the kinetics by two different techniques, the kinetics of oxygen chemisorption onto iron films was also studied. A reaction model utilized to interpret the H2/Fe2 chemisorption kinetics was applied to data from an earlier study on the desorption kinetics for H2 chemisorbed onto nicket films in the vicinity of the Curie temperature of the film. This analysis permitted a separation of the gross desorption process into individual components so that the influence of the magnetic phase transition on the rate constants could be determined.

  8. A general model for kinetics of heavy metal adsorption and desorption on soils.

    PubMed

    Shi, Zhenqing; Di Toro, Dominic M; Allen, Herbert E; Sparks, Donald L

    2013-04-16

    In this study, we propose a general kinetics model for heavy metal adsorption and desorption reactions in soils when soil organic matter (SOM) is the dominant adsorbent. The kinetics model, integrated with the equilibrium speciation model WHAM VI, specifically considers metal reactions with SOM and dissolved organic matter (DOM) and accounts for the variations of solution chemistry. Metal reactions with SOM are associated with two groups of sites, one from the monodentate sites and another one from the bidentate and tridentate sites. There are three model parameters, desorption rate coefficients of the two groups of SOM sites for each metal and reactive organic carbon (ROC) for each soil. The applicability of the kinetics model was mainly examined with three elements, Cu, Pb, and Zn, which demonstrate different binding ability with organic matter. The kinetic data were collected with a stirred-flow reactor covering a wide range of experimental conditions, including varying SOM, DOM, Ca, and metal concentrations, reaction pHs, and different flow rates. The kinetics model has been successfully applied to describe heavy metal adsorption and desorption on soils under various reaction conditions.

  9. The adsorption and desorption of hydrogen and carbon monoxide on bimetallic RePt(111) surfaces

    NASA Astrophysics Data System (ADS)

    Godbey, David J.; Somorjai, G. A.

    1988-10-01

    Bimetallic surfaces of rhenium on Pt(111) were prepared by vapor depositing rhenium on Pt(111). The adsorption and desorption behavior of CO and H 2 on bimetallic PtRe surfaces were studied using temperature programmed desorption, and compared to the behavior of CO and H 2 on the monometallic Pt(111) and Re(0001) counterparts. Depositing rhenium on a Pt(111) surface decreased the activation energy of desorption of hydrogen, and a surface composed of 0.37 monolayers of rhenium on Pt(111) showed an activation energy of hydrogen desorption that was 2.5 {kcal}/{mol} less than the 19 {kcal}/{mol} displayed by the monometallic Pt(111) surface. In contrast, the activation energy of desorption of CO from bimetallic surfaces depended very little on the bimetallic surface composition, and a value of 27 {kcal}/{mol} was observed for low CO coverages. At saturation exposures of both H 2 and CO, maximum adsorption capacities were obtained for bimetallic surfaces. A surface composed of 0.2 monolayers of rhenium on Pt(111) adsorbed 20% more hydrogen than did Pt(111) alone, while a surface composed of 0.3 monolayers of rhenium on Pt(111) adsorbed 40% more CO than did Pt(111) alone. The results obtained show that surfaces exposing both rhenium and platinum atoms show adsorption/desorption behavior towards hydrogen and CO that is different than the behavior shown by either monometallic platinum or rhenium surfaces. Since the chemisorption behavior cannot be explained as a simple combination of the two metallic components of the surface, it is concluded that an electronic interaction between the two metals at the platinum-rhenium interface modifies the bonding of adsorbates at the mixed metal sites.

  10. Theoretical and experimental studies of hydrogen adsorption and desorption on Ir surfaces

    SciTech Connect

    Kaghazchi, Payam; Jacob, Timo; Chen, Wenhua; Bartynski, Robert A.

    2013-06-03

    Here, we report adsorption and desorption of hydrogen on planar Ir(210) and faceted Ir(210), consisting of nanoscale {311} and (110) facets, by means of temperature programmed desorption (TPD) and density functional theory (DFT) in combination with the ab initio atomistic thermodynamics approach. TPD spectra show that only one H2 peak is seen from planar Ir(210) at all coverages whereas a single H2 peak is observed at around 440 K (F1) at fractional monolayer (ML) coverage and an additional H2 peak appears at around 360 K (F2) at 1 ML coverage on faceted Ir(210), implying structure sensitivity in recombination and desorption of hydrogen on faceted Ir(210) versus planar Ir(210), but no evidence is found for size effects in recombination and desorption of hydrogen on faceted Ir(210) for average facet sizes of 5-14 nm. Calculations indicate that H prefers to bind at the two-fold short-bridge sites of the Ir surfaces. In addition, we studied the stability of the Ir surfaces in the presence of hydrogen at different H coverages through surface free energy plots as a function of the chemical potential, which is also converted to a temperature scale. Moreover, the calculations revealed the origin of the two TPD peaks of H2 from faceted Ir(210): F1 from desorption of H2 on {311} facets while F2 from desorption of H2 on (110) facets.

  11. Film growth, adsorption and desorption kinetics of indigo on SiO2.

    PubMed

    Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

    2014-05-14

    Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.

  12. Film growth, adsorption and desorption kinetics of indigo on SiO{sub 2}

    SciTech Connect

    Scherwitzl, Boris Resel, Roland; Winkler, Adolf

    2014-05-14

    Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.

  13. Application of diffusion theory to the analysis of hydrogen desorption data at 25 deg C

    SciTech Connect

    Danford, M.D.

    1985-10-01

    The application of diffusion theory to the analysis of hydrogen desorption data (coulombs of H/sub 2/ desorbed versus time) has been studied. From these analyses, important information concerning hydrogen solubilities and the nature of the hydrogen distributions in the metal has been obtained. Two nickel base alloys, Rene' 41 and Waspaloy, and one ferrous alloy, 4340 steel, are studied in this work. For the nickel base alloys, it is found that the hydrogen distributions after electrolytic charging conforms closely to those which would be predicted by diffusion theory. For Waspaloy samples charged at 5,000 psi, it is found that the hydrogen distributions are essentially the same as those obtained by electrolytic charging. The hydrogen distributions in electrolytically charged 4340 steel, on the other hand, are essentially uniform in nature, which would not be predicted by diffusion theory. A possible explanation has been proposed. Finally, it is found that the hydrogen desorption is completely explained by the nature of the hydrogen distribution in the metal, and that the fast hydrogen is not due to surface and sub-surface hydride formation, as was originally proposed.

  14. Cubic metallic phase of aluminum hydride showing improved hydrogen desorption

    NASA Astrophysics Data System (ADS)

    Scheicher, R. H.; Kim, D. Y.; Lebègue, S.; Arnaud, B.; Alouani, M.; Ahuja, R.

    2008-05-01

    We report on our results calculated from density functional theory and GW of the dehydrogenation properties in a cubic phase of AlH3. The metallic nature of the electronic structure entails a more favorable hydrogen removal energy which is lowered by 75% compared to the insulating hexagonal phase. This remarkable reduction in the Al-H bond strength bears important consequences for feasible applications of AlH3 as an on-board hydrogen storage material for mobile applications. We suggest that the cubic phase could be prepared and stabilized experimentally at ambient pressure by off-board quenching.

  15. Adsorption-desorption kinetics and chemical potential of adsorbed and gas-phase particles

    NASA Astrophysics Data System (ADS)

    Zhdanov, V. P.

    2001-03-01

    In the literature, one can find two alternative ways of using the chemical potential of adsorbed and gas-phase particles, μa and μg, for describing the adsorption-desorption kinetics. According to the first approach, the desorption rate depends only on μa. The second approach, proposed by Ward et al. in a series of papers published in the Journal of Chemical Physics, predicts that the desorption rate is proportional to exp[(μa-μg)/kBT]. Scrutinizing the formalism used by Ward et al., we show that the latter dependence makes no sense because it contradicts the basic principles of the general theory of activated rate processes.

  16. Reaction pathways for hydrogen desorption from magnesium hydride/hydroxide composites: bulk and interface effects.

    PubMed

    Leardini, F; Ares, J R; Bodega, J; Fernández, J F; Ferrer, I J; Sánchez, C

    2010-01-21

    This manuscript investigates the thermal desorption behaviour of MgH(2)/Mg(OH)(2) composites by means of thermal desorption spectroscopy. Besides the H(2)O and H(2) desorption events due to Mg(OH)(2) dehydration and MgH(2) decomposition reactions, respectively, two additional H(2) desorption peaks arise at lower temperatures. These peaks are related to solid-state reactions between magnesium hydride and magnesium hydroxide through different channels. The low temperature H(2) peak ( approximately 150 degrees C) is related to reaction between a H atom diffusing from MgH(2) and a surface OH group, whereas the intermediate temperature H(2) peak ( approximately 350 degrees C) is due to an interface reaction between the hydride and the hydroxide. The present work supports the theory that the onset of the H(2) desorption coming from MgH(2) decomposition is controlled by an incubation process, consisting in the formation of catalytically active vacancies at the MgO/Mg(OH)(2) surface by dehydration. Possible ways to improve the H(2) desorption kinetics from MgH(2) are discussed in the light of the results obtained.

  17. Cubic Metallic Phase of Aluminum Hydride Showing Improved Hydrogen Desorption

    NASA Astrophysics Data System (ADS)

    Scheicher, Ralph H.; Kim, Duck Young; Ahuja, Rajeev

    2009-03-01

    AlH3 is of great interest for hydrogen storage applications, with a particularly attractive feature being its large hydrogen capacity of 10 wt.%. Here we report the results of our density functional theory study of the dehydrogenation properties in a cubic phase of AlH3. The metallic nature of the electronic structure entails a more favorable hydrogen removal energy which is lowered by 75% compared to the insulating hexagonal phase. This remarkable reduction in the Al--H bond strength might bear important consequences for feasible applications of AlH3 as an on-board hydrogen storage material for mobile applications. Suggestions are made how the cubic phase could be prepared and stabilized at ambient pressure by off-board quenching. See also: R. H. Scheicher, D. Y. Kim, S. Lebègue, B. Arnaud, M.Alouani, and R. Ahuja, Appl. Phys. Lett. 92, 201903 (2008) and D. Y. Kim, R. H. Scheicher, and R. Ahuja, Phys. Rev. B 78, 100102(R) (2008).

  18. In situ atomic force microscopy observation of hydrogen absorption/desorption by Palladium thin film

    NASA Astrophysics Data System (ADS)

    Matsumoto, Itoko; Sakaki, Kouji; Nakamura, Yumiko; Akiba, Etsuo

    2011-12-01

    Grain structure changes in Pd thin film during hydrogen absorption and desorption were observed by in situ atomic force microscopy. The as-sputtered film had a smooth flat surface with 20-30 nm grains. Film that absorbed hydrogen showed buckling, caused by the compressive stress due to lattice expansion as Pd metal reacted with hydrogen to form the hydride. Grains on the buckles were agglomerated and deformed unlike those on flat areas beside the buckles. Film that absorbed and then desorbed hydrogen still showed some buckling; however, many buckles shrank and flattened when the compressive stress of lattice expansion was released during desorption. On both the remaining and the shrunken buckles, grain agglomeration was retained; whereas, the deformed grains reverted back to their original form. X-ray diffraction indicated compressive residual stress in the as-sputtered film and tensile residual stress in the film after hydrogen absorption/desorption. These results indicate that irreversible grain agglomeration is related to residual tensile stress in the film although agglomeration occurs only on the buckled areas.

  19. Hydrogen kinetics in magnesium hydride: On different catalytic effects of niobium

    NASA Astrophysics Data System (ADS)

    Bazzanella, N.; Checchetto, R.; Miotello, A.; Sada, C.; Mazzoldi, P.; Mengucci, P.

    2006-07-01

    The hydrogen desorption kinetics from pure and Nb-doped MgH2 samples was studied as function of the Nb concentration (6×10-4<[Nb /Mg]<5×10-2). Structural and kinetics analyses indicate that Nb acts as catalyst both when Nb atoms aggregate forming NbH clusters dispersed in the MgH2 and also when Nb is contained as atomic impurity. It is suggested that the local atomic environment around the Nb atom acts as seed for h-Mg phase nucleation which constitutes the rate limiting step for the hydrogen kinetics while, when the Nb concentration exceeds about 1at.%, the rate limiting step is hydrogen diffusion.

  20. Film growth, adsorption and desorption kinetics of indigo on SiO2

    PubMed Central

    Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

    2015-01-01

    Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer des orption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption. PMID:24832297

  1. Description of time-varying desorption kinetics. Release of naphthalene from contaminated soils

    SciTech Connect

    Connaughton, D.F.; Stedinger, J.R.; Lion, L.W.; Shuler, M.L. )

    1993-11-01

    Release rates of naphthalene from suspensions of freshly contaminated (days to weeks) and aged (approximately 30 years) soil samples were obtained using a gas purge method. A continuously increasing resistance to desorption was observed with increasing purge time. Initial desorption rates were similar to those estimated using available empirical relationships, but subsequent desorption rates were lower by more than 1 order of magnitude. A model incorporating a continuum of compartments with a gamma ([Gamma]) distribution of rate coefficients was postulated to describe the experimental data. An analytical equation with two adjustable parameters was obtained for the mass fraction desorbed. Release profiles with this [open quotes][Gamma] model[close quotes] were able to describe the experimental release profiles for long term desorption experiments. An implication of the gamma model is that increased incubation time will allow organic compounds to be sorbed to compartments or regions in the sorbent that exhibit slow adsorption/desorption kinetics. This has important implications for the fate and remediation of sites that have been contaminated with hydrophobic organic compounds for extended time periods. 31 refs., 6 figs., 3 tabs.

  2. Radionuclide desorption kinetics on synthetic Zn/Ni-labeled montmorillonite nanoparticles

    NASA Astrophysics Data System (ADS)

    Huber, F. M.; Heck, S.; Truche, L.; Bouby, M.; Brendlé, J.; Hoess, P.; Schäfer, T.

    2015-01-01

    Sorption/desorption kinetics for selected radionuclides (99Tc(VII), 232Th(IV), 233U(VI), 237Np(V), 242Pu and 243Am(III)) under Grimsel (Switzerland) ground water conditions (pH 9.7 and ionic strength of ∼1 mM) in the presence of synthetic Zn or Ni containing montmorillonite nanoparticles and granodiorite fracture filling material (FFM) from Grimsel were examined in batch studies. The structurally bound Zn or Ni in the octahedral sheet of the synthetic colloids rendered them suitable as colloid markers. Only a weak interaction of the montmorillonite colloids with the fracture filling material occurs over the experimental duration of 10,000 h (∼13 months). The tri- and tetravalent radionuclides are initially strongly associated with nanoparticles in contrast to 99Tc(VII), 233U(VI) and 237Np(V) which showed no sorption to the montmorillonite colloids. Radionuclide desorption of the nanoparticles followed by sorption to the fracture filling material is observed for 232Th(IV), 242Pu and 243Am(III). Based on the conceptual model that the driving force for the kinetically controlled radionuclide desorption from nanoparticles and subsequent association to the FFM is the excess in surface area offered by the FFM, the observed desorption kinetics are related to the colloid/FFM surface area ratio. The observed decrease in concentration of the redox sensitive elements 99Tc(VII), 233U(VI) and 237Np(V) may be explained by reduction to lower oxidation states in line with Eh-pH conditions prevailing in the experiments and thermodynamic considerations leading to (i) precipitation of a sparingly soluble phase, (ii) sorption to the fracture filling material, (iii) possible formation of eigencolloids and/or (iv) sorption to the montmorillonite colloids. Subsequent to the sorption/desorption kinetics study, an additional experiment was conducted investigating the potential remobilization of radionuclides/colloids attached to the FFM used in the sorption/desorption kinetic

  3. Hydrogen adsorption and desorption with 3D silicon nanotube-network and film-network structures: Monte Carlo simulations

    SciTech Connect

    Li, Ming; Kang, Zhan; Huang, Xiaobo

    2015-08-28

    Hydrogen is clean, sustainable, and renewable, thus is viewed as promising energy carrier. However, its industrial utilization is greatly hampered by the lack of effective hydrogen storage and release method. Carbon nanotubes (CNTs) were viewed as one of the potential hydrogen containers, but it has been proved that pure CNTs cannot attain the desired target capacity of hydrogen storage. In this paper, we present a numerical study on the material-driven and structure-driven hydrogen adsorption of 3D silicon networks and propose a deformation-driven hydrogen desorption approach based on molecular simulations. Two types of 3D nanostructures, silicon nanotube-network (Si-NN) and silicon film-network (Si-FN), are first investigated in terms of hydrogen adsorption and desorption capacity with grand canonical Monte Carlo simulations. It is revealed that the hydrogen storage capacity is determined by the lithium doping ratio and geometrical parameters, and the maximum hydrogen uptake can be achieved by a 3D nanostructure with optimal configuration and doping ratio obtained through design optimization technique. For hydrogen desorption, a mechanical-deformation-driven-hydrogen-release approach is proposed. Compared with temperature/pressure change-induced hydrogen desorption method, the proposed approach is so effective that nearly complete hydrogen desorption can be achieved by Si-FN nanostructures under sufficient compression but without structural failure observed. The approach is also reversible since the mechanical deformation in Si-FN nanostructures can be elastically recovered, which suggests a good reusability. This study may shed light on the mechanism of hydrogen adsorption and desorption and thus provide useful guidance toward engineering design of microstructural hydrogen (or other gas) adsorption materials.

  4. Hydrogen adsorption and desorption with 3D silicon nanotube-network and film-network structures: Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Li, Ming; Huang, Xiaobo; Kang, Zhan

    2015-08-01

    Hydrogen is clean, sustainable, and renewable, thus is viewed as promising energy carrier. However, its industrial utilization is greatly hampered by the lack of effective hydrogen storage and release method. Carbon nanotubes (CNTs) were viewed as one of the potential hydrogen containers, but it has been proved that pure CNTs cannot attain the desired target capacity of hydrogen storage. In this paper, we present a numerical study on the material-driven and structure-driven hydrogen adsorption of 3D silicon networks and propose a deformation-driven hydrogen desorption approach based on molecular simulations. Two types of 3D nanostructures, silicon nanotube-network (Si-NN) and silicon film-network (Si-FN), are first investigated in terms of hydrogen adsorption and desorption capacity with grand canonical Monte Carlo simulations. It is revealed that the hydrogen storage capacity is determined by the lithium doping ratio and geometrical parameters, and the maximum hydrogen uptake can be achieved by a 3D nanostructure with optimal configuration and doping ratio obtained through design optimization technique. For hydrogen desorption, a mechanical-deformation-driven-hydrogen-release approach is proposed. Compared with temperature/pressure change-induced hydrogen desorption method, the proposed approach is so effective that nearly complete hydrogen desorption can be achieved by Si-FN nanostructures under sufficient compression but without structural failure observed. The approach is also reversible since the mechanical deformation in Si-FN nanostructures can be elastically recovered, which suggests a good reusability. This study may shed light on the mechanism of hydrogen adsorption and desorption and thus provide useful guidance toward engineering design of microstructural hydrogen (or other gas) adsorption materials.

  5. Finite-Temperature Hydrogen Adsorption/Desorption Thermodynamics Driven by Soft Vibration Modes

    SciTech Connect

    Woo, Sung-Jae; Lee, Eui-Sup; Yoon, Mina; Yong-Hyun, Kim

    2013-01-01

    It is widely accepted that room-temperature hydrogen storage on nanostructured or porous materials requires enhanced dihydrogen adsorption. In this work we reveal that room-temperature hydrogen storage is possible not only by the enhanced adsorption, but also by making use of the vibrational free energy from soft vibration modes. These modes exist for example in the case of metallo-porphyrin-incorporated graphenes (M-PIGs) with out-of-plane ( buckled ) metal centers. There, the in-plane potential surfaces are flat because of multiple-orbital-coupling between hydrogen molecules and the buckled-metal centers. This study investigates the finite-temperature adsorption/desorption thermodynamics of hydrogen molecules adsorbed on M-PIGs by employing first-principles total energy and vibrational spectrum calculations. Our results suggest that the current design strategy for room-temperature hydrogen storage materials should be modified by explicitly taking finite-temperature vibration thermodynamics into account.

  6. Kinetic modeling of antimony(V) adsorption-desorption and transport in soils.

    PubMed

    Zhang, Hua; Li, Lulu; Zhou, Shiwei

    2014-09-01

    Antimonate [Sb(V)] adsorption-desorption and transport in an acidic red soil (Yingtan) and a calcareous soil (Huanjiang) was investigated using kinetic batch and miscible displacement experiments. Different formulations of a multi-reaction model (MRM) were evaluated for their capabilities of describing the retention and transport mechanisms of Sb(V) in soils. The experimental results showed that adsorption of Sb(V) by two soils was kinetically controlled and largely irreversible. The Sb(V) adsorption capacity and kinetic rate of the acidic red soil was much higher than that of the calcareous soil. The asymmetrical breakthrough curves indicated the strong dominance of non-equilibrium retention of Sb(V). A four step sequential extraction procedure provided evidence that majority of applied Sb(V) was irreversibly retained. A formulation of MRM with two kinetic sorption sites (reversible and irreversible) successfully described Sb(V) adsorption-desorption data. The use of kinetic batch rate coefficients for predictions of breakthrough curves (BTCs) underestimated Sb(V) retention and overestimated its mobility. In an inverse mode with optimized rate coefficients, the MRM formulation was capable of simulating Sb(V) transport in soil columns. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Desorption kinetics of ciprofloxacin in municipal biosolids determined by diffusion gradient in thin films.

    PubMed

    D'Angelo, E; Starnes, D

    2016-12-01

    Ciprofloxacin (CIP) is a commonly-prescribed antibiotic that is largely excreted by the body, and is often found at elevated concentrations in treated sewage sludge (biosolids) at municipal wastewater treatment plants. When biosolids are applied to soils, they could release CIP to surface runoff, which could adversely affect growth of aquatic organisms that inhabit receiving water bodies. The hazard risk largely depends on the amount of antibiotic in the solid phase that can be released to solution (labile CIP), its diffusion coefficient, and sorption/desorption exchange rates in biosolids particles. In this study, these processes were evaluated in a Class A Exceptional Quality Biosolids using a diffusion gradient in thin films (DGT) sampler that continuously removed CIP from solution, which induced desorption and diffusion in biosolids. Mass accumulation of antibiotic in the sampler over time was fit by a diffusion transport and exchange model available in the software tool 2D-DIFS to derive the distribution coefficient of labile CIP (Kdl) and sorption/desorption rate constants in the biosolids. The Kdl was 13 mL g(-1), which equated to 16% of total CIP in the labile pool. Although the proportion of labile CIP was considerable, release rates to solution were constrained by slow desorption kinetics (desorption rate constant = 4 × 10(-6) s(-1)) and diffusion rate (effective diffusion coefficient = 6 × 10(-9) cm(2) s(-1). Studies are needed to investigate how changes in temperature, water content, pH and other physical and chemical characteristics can influence antibiotic release kinetics and availability and mobility in biosolid-amended soils.

  8. Desorption kinetics of fluoranthene and trifluralin from Lake Huron and Lake Erie, USA, sediments.

    PubMed

    Greenberg, Marc S; Burton, G Allen; Landrum, Peter F; Leppänen, Matti T; Kukkonen, Jussi V K

    2005-01-01

    Desorption kinetics were determined for fluoranthene (FLU) and trifluralin (TF) spiked onto Lake Erie and Lake Huron, USA, sediments at three concentrations (10, 40, 100 mg/kg dry wt). Following four months of equilibration, desorption was measured by extraction with Tenax and the data were fit to a first-order three-compartment kinetic model. The rate constants of the rapidly (k(rap)), slowly (k(slow)), and very slowly (k(vs)) desorbing fractions were on the order of 10(-1)/h, 10(-2-3)/h, and 10(-4)/h, respectively. The t99.9 (time required for 99.9% of the FLU and TF to desorb from each pool value) for each compartment indicated that FLU and TF desorption from rapid, slow, and very slow compartments were on the order of hours, days, and years, respectively. Higher rates of desorption were observed for FLU and TF from the Lake Huron sediments and this was not apparently related to the total organic carbon (TOC), particle size distribution, or polarity (carbon-to-nitrogen ratio) of the sediments. In general, the total fraction of the initial contaminant amounts that desorbed over the time course was directly related to concentration, which we hypothesized was due to the combined effects of saturation of high-energy (slow and very slow) binding sites in the organic carbon matrix and hysteresis. In extrapolations to field conditions, FLU and TF were predicted to persist in the sediments for years due to the very slow desorption of an estimated 31 to 53% of the bulk concentrations. Based on the rapidly desorbing fractions, the bioavailable amounts of the contaminants were predicted to be between 31 to 55% of bulk sediment concentrations.

  9. Sorption and desorption kinetics of diuron, fluometuron, prometryn and pyrithiobac sodium in soils.

    PubMed

    Baskaran, S; Kennedy, I R

    1999-11-01

    The sorption and desorption characteristics of four herbicides (diuron, fluometuron, prometryn and pyrithiobac-sodium) in three different cotton growing soils of Australia was investigated. Kinetics and equilibrium sorption and desorption isotherms were determined using the batch equilibrium technique. Sorption was rapid (> 80% in 2 h) and sorption equilibrium was achieved within a short period of time (ca 4 h) for all herbicides. Sorption isotherms of the four herbicides were described by Freundlich equation with an r2 value > 0.98. The herbicide sorption as measured by the distribution coefficient (Kd) values ranged from 3.24 to 5.71 L/kg for diuron, 0.44 to 1.13 L/kg for fluometuron, 1.78 to 6.04 L/kg for prometryn and 0.22 to 0.59 L/kg for pyrithiobac-sodium. Sorption of herbicides was higher in the Moree soil than in Narrabri and Wee Waa soils. When the Kd values were normalised to organic carbon content of the soils (Koc), it suggested that the affinity of the herbicides to the organic carbon increased in the order: pyrithiobac-sodium < fluometuron < prometryn < or = diuron. The desorption isotherms were also adequately described by the Freundlich equation. For desorption, all herbicides exhibited hysteresis and the hysteresis was stronger for highly sorbed herbicides (diuron and prometryn) than the weakly sorbed herbicides (fluometuron and pyrithiobac-sodium). Hysteresis was also quantified as the percentage of sorbed herbicides which is not released during the desorption step (omega = [nad/nde - 1] x 100). Soil type and initial concentration had significant effect on omega. The effect of sorption and desorption properties of these four herbicides on the off-site transport to contaminate surface and groundwater are also discussed in this paper.

  10. Effect of carboxylic and thiol ligands (oxalate, cysteine) on the kinetics of desorption of Hg(II) from kaolinite

    SciTech Connect

    Senevirathna, W. U.; Zhang, Hong; Gu, Baohua

    2010-01-01

    Sorption and desorption of Hg(II) on clay minerals can impact the biogeochemical cycle and bio-uptake of Hg in the environment. We studied the kinetics of the desorption of Hg(II) from kaolinite as affected by oxalate and cysteine, representing the ligands with carboxylic and thiol groups of different affinities for Hg(II). The effects of pH (3, 5, and 7), ligand concentration (0.25 and 1.0 mM), and temperature (15 C, 25 C, and 35 C) on the Hg(II) desorption were investigated through desorption kinetics. Our study showed that the Hg(II) desorption was pH dependent. In the absence of any organic ligand, >90% of the previously adsorbed Hg(II) desorbed at pH 3 within 2 h, compared to <10% at pH 7. Similar results were observed in the presence of oxalate, showing that it hardly affected the Hg(II) desorption. Cysteine inhibited the Hg(II) desorption significantly at all the pH tested, especially in the first 80 min with the desorption less than 20%, but the inhibition of the desorption appeared to be less prominent afterwards. The effect of the ligand concentration on the Hg(II) desorption was small, especially in the presence of oxalate. The effect of temperature on the Hg(II) desorption was nearly insignificant. The effect of the organic acids on the Hg(II) sorption and desorption is explained by the formation of the ternary surface complexes involving the mineral, ligand, and Hg(II). The competition for Hg(II) between the cysteine molecules adsorbed on the particle surfaces and in the solution phase probably can also affect the Hg(II) desorption.

  11. Absorption and desorption of hydrogen, deuterium, and tritium for Zr--V--Fe getter

    SciTech Connect

    Ichimura, K.; Inoue, N.; Watanabe, K.; Takeuchi, T.

    1984-07-01

    Nonevaporable getters have wide applicability for developing the tritium handling techniques for thermonuclear fusion devices. From this viewpoint, mechanisms of the absorption and desorption of hydrogen isotopes and the isotope effects were investigated for a Zr--V--Fe alloy (St-707) by means of the mass analyzed thermal desorption spectroscopy. It was observed that the absorption rate was proportional to the first power of the pressure, indicating that the rate limiting step is the dissociative adsorption of hydrogen isotopes on the surface. The activation energy was very small, in the order of magnitude of a few tens of calories per mole in a temperature range from -196 to 200 /sup 0/C. The desorption rate was proportional to the square of the amount of absorption, indicating that the rate limiting step is the associative desorption reaction of hydrogen atoms or ions diffused to the surface from the bulk. The rate constants for hydrogen and deuterium were determined as k/sub d/(H/sub 2/) = (5.3/sup +2.6//sub -1.7/)exp(-(28.0 +- 0.7) x 10/sup 3//RT) and k/sub d/(D/sub 2/) = (5.0/sup +2.7//sub -1.7/)exp(-(28.6 +- 0.8) x 10/sup 3//RT) in (1/Pa 1 s), respectively, where R is in (cal/mol deg). With regard to tritium, the rate constant was evaluated as k/sub d/(T/sub 2/) = (5.0/sup +20//sub -4.0/)exp(-(29.3 +- 3) x 10/sup 3//RT), however, the frequency factor will have to be corrected by knowing the relative sensitivity factor of the mass spectrometer for tritium (T/sub 2/).

  12. Desorption kinetics of radiocesium from subsurface sediments at Hanford Site, USA

    NASA Astrophysics Data System (ADS)

    Liu, Chongxuan; Zachara, John M.; Smith, Steve C.; McKinley, James P.; Ainsworth, Calvin C.

    2003-08-01

    The desorption of 137Cs + was investigated on sediments from the United States Hanford site. Pristine sediments and ones that were contaminated by the accidental release of alkaline 137Cs +-containing high level nuclear wastes (HLW, 2 × 10 6 to 6 × 10 7 pCi 137Cs +/g) were studied. The desorption of 137Cs + was measured in Na +, K +, Rb +, and NH 4+electrolytes of variable concentration and pH, and in presence of a strong Cs +-specific sorbent (self-assembled monolayer on a mesoporous support, SAMMS). 137Cs + desorption from the HLW-contaminated Hanford sediments exhibited two distinct phases: an initial instantaneous release followed by a slow kinetic process. The extent of 137Cs + desorption increased with increasing electrolyte concentration and followed a trend of Rb + ≥ K + > Na + at circumneutral pH. This trend followed the respective selectivities of these cations for the sediment. The extent and rate of 137Cs + desorption was influenced by surface armoring, intraparticle diffusion, and the collapse of edge-interlayer sites in solutions containing K +, Rb +, or NH 4+. Scanning electron microscopic analysis revealed HLW-induced precipitation of secondary aluminosilicates on the edges and basal planes of micaceous minerals that were primary Cs + sorbents. The removal of these precipitates by acidified ammonium oxalate extraction significantly increased the long-term desorption rate and extent. X-ray microprobe analyses of Cs +-sorbed micas showed that the 137Cs + distributed not only on mica edges, but also within internal channels parallel to the basal plane, implying intraparticle diffusive migration of 137Cs +. Controlled desorption experiments using Cs +-spiked pristine sediment indicated that the 137Cs + diffusion rate was fast in Na +-electrolyte, but much slower in the presence of K + or Rb +, suggesting an effect of edge-interlayer collapse. An intraparticle diffusion model coupled with a two-site cation exchange model was used to interpret the

  13. Role of desorption kinetics in the rhamnolipid-enhanced biodegradation of polycyclic aromatic hydrocarbons.

    PubMed

    Congiu, Eleonora; Ortega-Calvo, José-Julio

    2014-09-16

    The main aim of this study was to investigate the effect of a rhamnolipid biosurfactant on biodegradation of (14)C-labeled phenanthrene and pyrene under desorption-limiting conditions. The rhamnolipid caused a significant solubilization and enhanced biodegradation of PAHs sorbed to soils. The enhancement was, however, negatively influenced by experimental conditions that caused an enrichment of slow desorption fractions. These conditions included aging, a higher organic matter content in soil, and previous extraction with Tenax to remove the labile-desorbing chemical. The decline in bioavailability caused by aging on sorbed (14)C-pyrene was partially reversed by rhamnolipids, which enhanced mineralization of the aged compound, although not so efficiently like with the unaged chemical. This loss in biosurfactant efficiency in promoting biodegradation can be explained by intra-aggregate diffusion of the pollutant during aging. We suggest that rhamnolipid can enhance biodegradation of soil-sorbed PAHs by micellar solubilization, which increase the cell exposure to the chemicals in the aqueous phase, and partitioning into soil organic matter, thus enhancing the kinetics of slow desorption. Our study show that rhamnolipid can constitute a valid alternative to chemical surfactants in promoting the biodegradation of slow desorption PAHs, which constitutes a major bottleneck in bioremediation.

  14. Abstraction and desorption kinetics in the reaction of H+D/Si(100) and the relation to surface structure

    NASA Astrophysics Data System (ADS)

    Kubo, Atsushi; Ishii, Yasuhiro; Kitajima, Masahiro

    2002-12-01

    Kinetics of HD and D2 desorption from D/Si(100)-2×1 surfaces induced by H atoms has been investigated at temperature range of 97-685 K. Desorption rates of HD and D2 are measured in real-time by using mass spectrometers during the exposure of D/Si(100) to H atom beam. HD and D2 rates are not fitted by a hot atom kinetics, but are explained well in terms of adjacent double di-hydrides (DDI)-thermal desorption plus abstraction mechanism. For Ts⩾480 K, the pre-adsorbed D atoms are desorbed as D2 via DDI-desorption (˜22%), as HD via DDI-desorption (˜28%), and HD via abstraction (˜50%). For Ts⩽310 K, DDI-desorption does not occur, whereas the abstraction proceeds at a constant rate. The yield of DDI-desorption decreases as the surface structure of H/Si(100) changes from 2×1 to 1×1, suggesting the DDI-desorption is associated with a re-formation reaction of a mono-hydride dimer from adjacent two di-hydrides. The activation energy (Ea) for DDI-desorption is ˜0.2 eV. The rate of abstraction does not show Arrhenius-type temperature dependence. The abstraction probability PHD is estimated at 0.03±0.015 (cross section σHD=0.4±0.2 Å2) for Ts⩽310 K.

  15. Molecular Hydrogen Formation on Low Temperature Surfaces in Temperature Programmed Desorption Experiments

    NASA Astrophysics Data System (ADS)

    Vidali, G.; Pirronello, V.; Li, L.; Roser, J.; Manico, G.; Mehl, R.; Lederhendler, A.; Perets, H. B.; Brucato, J. R.; Biham, O.

    The study of the formation of molecular hydrogen on low temperature surfaces is of interest both because it allows to explore elementary steps in the heterogeneous catalysis of a simple molecule and because of the applications in astrochemistry. Here we report results of experiments of molecular hydrogen formation on amorphous silicate surfaces using temperature-programmed desorption (TPD). In these experiments beams of H and D atoms are irradiated on the surface of an amorphous silicate sample. The desorption rate of HD molecules is monitored using a mass spectrometer during a subsequent TPD run. The results are analyzed using rate equations and the activation energies of the processes leading to molecular hydrogen formation are obtained from the TPD data. We show that a model based on a single isotope provides the correct results for the activation energies for diffusion and desorption of H atoms. These results can thus be used to evaluate the formation rate of H_2 on dust grains under the actual conditions present in interstellar clouds.

  16. Adsorption-desorption of oxytetracycline on marine sediments: Kinetics and influencing factors.

    PubMed

    Li, Jia; Zhang, Hua

    2016-12-01

    To reveal the kinetics and mechanisms of antibiotic adsorption/desorption processes, batch and stirred flow chamber (SFC) experiments were carried out with oxytetracycline (OTC) on two marine sediments. The OTC adsorption capacities of the marine sediments were relatively weak and related to their organic carbon (OC) and contents of fine particles. Sorption isotherms of OTC on marine sediment can be well described by both the Langmuir and Freundlich models. Langmuir adsorption maxima (qmax) and Freundlich distribution coefficients (Kf) increased with the decrease of salinity and pH, which indicated the importance of variable charged sites on sediment surfaces. A second order kinetic model successfully described adsorption and desorption kinetics of OTC and well reproduced the concentration change during stop-flow. The adsorption kinetic rates (ka) for OTC under different experimental conditions ranged from 2.00 × 10(-4) to 1.97 × 10(-3) L (mg min)(-1). Results of SFC experiments indicated that diffusive mass transfer was the dominant mechanism of the time-dependent adsorption of OTC and its release from marine sediment was mildly hysteretic. The high desorption percentage (43-75% for LZB and 58-75% for BHB) implied that binding strength of OTC on two marine sediments was weak. In conclusion, marine sediment characteristics and environmental factors such as salinity, pH, and flow rate are critical factors determine extent of OTC sorption on marine sediment and need to be incorporated in modeling fate and transport of OTC in marine environment.

  17. Hydrogenation of CO-bearing species on grains: unexpected chemical desorption of CO

    NASA Astrophysics Data System (ADS)

    Minissale, M.; Moudens, A.; Baouche, S.; Chaabouni, H.; Dulieu, F.

    2016-05-01

    The amount of methanol in the gas phase and the CO depletion from the gas phase are still open problems in astrophysics. In this work, we investigate solid-state hydrogenation of CO-bearing species via H-exposure of carbon monoxide, formaldehyde, and methanol-thin films deposited on cold surfaces, paying attention to the possibility of a return to the gas phase. The products are probed via infrared spectroscopy (reflection absorption infrared spectroscopy), and two types of mass spectroscopy protocols: temperature-programmed desorption, and during-exposure desorption techniques. In the case of the [CO+H] reactive system, we have found that chemical desorption of CO is more efficient than H-addition reactions and HCO and H2CO formation; the studies of the [H2CO +H] reactive system show a strong competition between all surface processes, chemical desorption of H2CO, H-addition (CH3OH formation) and H-abstraction (CO formation); finally, [CH3OH + H] seems to be a non-reactive system and chemical desorption of methanol is not efficient. CO-bearing species present a see-saw mechanism between CO and H2CO balanced by the competition of H-addition and H2-abstraction that enhances the CO chemical desorption. The chemical network leading to methanol has to be reconsidered. The methanol formation on the surface of interstellar dust grain is still possible through CO+H reaction; nevertheless, its consumption of adsorbed H atoms should be higher than previously expected.

  18. A thermal desorption study of the kinetics of uranium hydride decomposition

    NASA Astrophysics Data System (ADS)

    Lillard, R. S.; Taylor, C. D.; Wermer, J. R.; Mara, N. A.; Cooley, J. C.

    2014-01-01

    The decomposition of uranium hydride powder was studied using thermal desorption spectroscopy (TDS). In the TDS spectra, three distinct decomposition peaks were observed. However, only the high temperature peak was associated with an activation energy, calculated to be 43 kJ/mol H. This activation energy was used to construct outgassing diagrams that can be used to estimate the temperature and time dependence of UH3 decomposition. Potential models for explaining the three decomposition peaks and, thus, the decomposition mechanism are also presented and compared with H desorption energies calculated from first principles. Additional experiments on α-U coupons containing UH3 corrosion pits were also performed. In those samples in excess of 6 peaks are observed. It is shown that the first three hydrogen peaks are related to the decomposition of UH3.

  19. Desorption of Hydrogen from Si(111) by Resonant Excitation of the Si-H Vibrational Stretch Mode

    SciTech Connect

    Liu, Zhiheng; Feldman, Leonard C.; Tolk, Norman; Zhang, Zhenyu; Cohen, Philip I

    2006-01-01

    Past efforts to achieve selective bond scission by vibrational excitation have been thwarted by energy thermalization. Here we report resonant photodesorption of hydrogen from a Si(111) surface using tunable infrared radiation. The wavelength dependence of the desorption yield peaks at 0.26 electron volt: the energy of the Si-H vibrational stretch mode. The desorption yield is quadratic in the infrared intensity. A strong H/D isotope effect rules out thermal desorption mechanisms, and electronic effects are not applicable in this low-energy regime. A molecular mechanism accounting for the desorption event remains elusive.

  20. Kinetics of catalytic transfer hydrogenation of soybean lecithin

    SciTech Connect

    Naglic, M.; Smidovnik, A.; Koloini, T.

    1997-12-01

    Catalytic transfer hydrogenation of soybean lecithin has been studied using aqueous sodium formate solution as hydrogen donor and palladium on carbon as catalyst. Kinetic constants and selectivity have been determined at intensive stirring. Hydrogenation reactions followed the first-order kinetics with respect to fatty acids. In addition to short reaction time, this method offers safe and easy handling. Hydrogenated soybean lecithin provides products with increased stability with respect to oxidation.

  1. Kinetic Monte Carlo simulations of temperature programed desorption of O/Rh(111).

    PubMed

    Franz, T; Mittendorfer, F

    2010-05-21

    We present a kinetic Monte Carlo simulation based on ab initio calculations for the thermal desorption of oxygen from a Rh(111) surface. Several models have been used for the parametrization of the interaction between the adsorbed atoms. We find that models based on a parametrization with only pairwise interactions have a relatively large error in the predicted adsorption energies. This error can be significantly reduced by including three- and four-body interactions. In addition, we find that a significant amount of atoms adsorb in a second adsorption site - the hcp-hollow site - at an elevated temperature. Consequently, only a many-body multisite model of the oxygen interactions yields appropriate desorption spectra for the full coverage range, while more simple models only capture the correct shape in the low-coverage case. Our parametrization allows us to predict the adsorption energies of an arbitrary configuration of adsorbates with a mean average error of less than 6 meV/atom.

  2. Diffusion barriers in the kinetics of water vapor adsorption/desorption on activated carbons

    SciTech Connect

    Harding, A.W.; Foley, N.J.; Thomas, K.M.; Norman, P.R.; Francis, D.C.

    1998-07-07

    The adsorption of water vapor on a highly microporous coconut-shell-derived carbon and a mesoporous wood-derived carbon was studied. These carbons were chosen as they had markedly different porous structures. The adsorption and desorption characteristics of water vapor on the activated carbons were investigated over the relative pressure range p/p{degree} = 0--0.9 for temperatures in the range 285--313 K in a static water vapor system. The adsorption isotherms were analyzed using the Dubinin-Serpinski equation, and this provided an assessment of the polarity of the carbons. The kinetics of water vapor adsorption and desorption were studied with different amounts of preadsorbed water for set changes in pressure relative to the saturated vapor pressure (p/p{degree}). The adsorption kinetics for each relative pressure step were compared and used to calculate the activation energies for the vapor pressure increments. The kinetic results are discussed in relation to their relative position on the equilibrium isotherm and the adsorption mechanism of water vapor on activated carbons.

  3. Laser temperature jump relaxation measurements of adsorption/desorption kinetics at liquid/solid interfaces

    SciTech Connect

    Waite, S.W.; Harris, J.M.; Holzwarth, J.F.

    1995-04-15

    The iodine laser temperature jump method is used to study adsorption/desorption kinetics at a methylated silica/solution interface. A suspension of C1-derivatized fumed silica is used for the kinetic measurements. The colloidal silica does not significantly change the attenuation of near-IR radiation from the iodine laser and allows the surface site concentration to be varied so that adsorption and desorption rates can be determined. The temperature jump relaxation method was used to investigate the effect of electrolyte on adsorption of a charged solute (ANS) on a C1 silica surface. Adsorption equilibrium conditions were optimized to observe a maximum relaxation signal. Without electrolyte, the relaxation signal is biexponential, which is also reflected in a broad chromatographic peak shape and a two-site sorption isotherm. When electrolyte is added, the relaxation signal is primarily single exponential, which agrees with the linear adsorption isotherm. The adsorption rate and equilibrium constant were found to increase significantly with added electrolyte, which showed that adsorption kinetics can influence both band broadening and retention. 28 refs., 7 figs., 4 tab.

  4. Kinetic isotope effect for H2 and D2 quantum molecular sieving in adsorption/desorption on porous carbon materials.

    PubMed

    Zhao, Xuebo; Villar-Rodil, Silvia; Fletcher, Ashleigh J; Thomas, K Mark

    2006-05-25

    Adsorption and desorption of H(2) and D(2) from porous carbon materials, such as activated carbon at 77 K, are usually fully reversible with very rapid adsorption/desorption kinetics. The adsorption and desorption of H(2) and D(2) at 77 K on a carbon molecular sieve (Takeda 3A), where the kinetic selectivity was incorporated by carbon deposition, and a carbon, where the pore structure was modified by thermal annealing to give similar pore structure characteristics to the carbon molecular sieve substrate, were studied. The D(2) adsorption and desorption kinetics were significantly faster (up to x1.9) than the corresponding H(2) kinetics for specific pressure increments/decrements. This represents the first experimental observation of kinetic isotope quantum molecular sieving in porous materials due to the larger zero-point energy for the lighter H(2), resulting in slower adsorption/desorption kinetics compared with the heavier D(2). The results are discussed in terms of the adsorption mechanism.

  5. Kinetics of desorption of KCL from polyvinyl alcohol-borate hydrogel in aqueous-alcoholic solvents at different temperatures

    NASA Astrophysics Data System (ADS)

    Saeed, Rehana; Abdeen, Zain Ul

    2015-11-01

    Desorption kinetics of adsorbed KCl from Polyvinyl alcohol borate hydrogel was studied by conductivity method in aqueous system and aqueous binary solvent system using 50% aqueous-methanol, aqueous- ethanol and aqueous-propanol at different temperature ranging from 293 to 313 K. Desorption process follows pseudo first order and intra particle diffusion kinetics was analyzed on the basis of linear regression coefficient R 2 and chi square test χ2 values. The process of desorption of KCl from hydrogel was favorable in aqueous system, the study reveals the fact that the polarity of solvent influenced the kinetics of desorption, on decrement of polarity of solvent rate, rate constant and intra particle rate constant decreases. Based on intra particle kinetic equation fitting it was concluded that desorption was initiated by removal of ions from surface of hydrogel later on ions interacted inside the cross linked unit was also become free. Temperature enhances the rate, rate constant and intra particle rate constant. Thermodynamic parameters attributed towards the fact that the process of desorption of KCl from hydrogel is non-spontaneous in nature.

  6. Adsorption and desorption kinetics of (60)Co and (137)Cs in fresh water rivers.

    PubMed

    Fiengo Pérez, Fabricio; Sweeck, Lieve; Bauwens, Willy; Van Hees, May; Elskens, Marc

    2015-11-01

    Radionuclides released in water systems--as well as heavy metals and organic toxicants--sorb to both the suspended solid particles and the bed sediments. Sorption is usually represented mathematically by the distribution coefficient. This approach implies equilibrium between phases and instantaneous fixation (release) of the pollutant onto (from) the surface of the soil particle. However, empirical evidence suggests that for some radionuclides the fixation is not achieved instantaneously and that the reversibility of the process can be slow. Here the adsorption/desorption kinetics of (60)Co and (137)Cs in fresh water environments were simulated experimentally and later on modelled mathematically, while the influence of the most relevant factors affecting the sorption were taken into account. The experimental results suggest that for adsorption and the desorption more than 24 h are needed to reach equilibrium, moreover, It was observed that the desorption rate constants for (60)Co and (137)Cs lie within ranges which are of two to three orders of magnitude lower than the adsorption rate constants.

  7. Hydrogen diffusion kinetics and structural integrity of superhigh pressure Mg-5 wt%Ni alloys with dendrite interface

    NASA Astrophysics Data System (ADS)

    Fu, Hui; Wu, Wenshi; Dou, Yang; Liu, Baozhong; Li, Hanning; Peng, Qiuming

    2016-07-01

    A strategy of low-angle orientation dendrite interface-high index planes-which prepared by super-high pressure (SHP) technique, is proposed and successfully improved the hydrogen storage properties of Mg based materials for the first time, wherein a simple binary Mg-Ni alloy is used as a sample to elucidate its related mechanisms. The phase composition, morphology variation and hydrogen storage properties of the as-cast and SHP Mg-5Ni alloys in the temperature range of 1100-1600 °C are systemically investigated. The reversible hydrogen storage capacities and plateau hydrogen pressure of the as-cast and SHP alloys are close due to the same hydrogen storage phases (Mg and Mg2Ni). Note that although SHP treatment at 1600 °C has a large weight fraction of Mg6Ni compound, it still effectively reduces the onset temperature of dehydriding (∼262 °C), as well as improves the hydrogen desorption kinetics at low temperatures and structural integrity. The low onset temperature and outstanding hydrogen sorption/desorption kinetics are mainly associated with the formation of a large number of dendrite interface, in which the hydrogen atoms readily occur "zig-zag" jumps along {11-20} prismatic planes. This dendrite interface of high index planes which prepared by SHP technique paves a new pathway to enhance the hydrogen storage performances of magnesium based alloys.

  8. Hydrogen reduction kinetics of electrometallurgical slime

    NASA Astrophysics Data System (ADS)

    Teplov, O. A.; Voropaev, I. G.; Dyubanov, V. G.; Leont'ev, L. I.

    2007-08-01

    The interaction of hydrogen with the zinc-containing electrometallurgical slime of the Severstal’ metallurgical works has been studied. The sequence of transformations in the slime heated to 1100°C in hydrogen or air has been established. The experimental and calculated weight losses coincide. Some of the carbonates are shown to decompose in the temperature range 300 700°C, and most iron and zinc oxides are reduced to a metal. In the temperature range 650 850°C, zinc is almost completely sublimated. At temperatures above 800°C, complex oxides are reduced and calcium and magnesium carbonates and sulfates are likely to decompose. Experimental digital data on the zinc sublimation rate are processed by the least squares method with approximating equations used in thermal analysis. The kinetics of nonisothermal zinc sublimation is comprehensively analyzed using a unique procedure developed for taking into account the background of a peak and the effect of accompanying processes. An equation for the calculation of the zinc sublimation rate under experimental conditions (fluidized bed) is given and tested.

  9. Hydrogen atom kinetics in capacitively coupled plasmas

    NASA Astrophysics Data System (ADS)

    Nunomura, Shota; Katayama, Hirotaka; Yoshida, Isao

    2017-05-01

    Hydrogen (H) atom kinetics has been investigated in capacitively coupled very high frequency (VHF) discharges at powers of 16-780 mW cm-2 and H2 gas pressures of 0.1-2 Torr. The H atom density has been measured using vacuum ultra violet absorption spectroscopy (VUVAS) with a micro-discharge hollow cathode lamp as a VUV light source. The measurements have been performed in two different electrode configurations of discharges: conventional parallel-plate diode and triode with an intermediate mesh electrode. We find that in the triode configuration, the H atom density is strongly reduced across the mesh electrode. The H atom density varies from ˜1012 cm-3 to ˜1010 cm-3 by crossing the mesh with 0.2 mm in thickness and 36% in aperture ratio. The fluid model simulations for VHF discharge plasmas have been performed to study the H atom generation, diffusion and recombination kinetics. The simulations suggest that H atoms are generated in the bulk plasma, by the electron impact dissociation (e + H2 \\to e + 2H) and the ion-molecule reaction (H2 + + H2 \\to {{{H}}}3+ + H). The diffusion of H atoms is strongly limited by a mesh electrode, and thus the mesh geometry influences the spatial distribution of the H atoms. The loss of H atoms is dominated by the surface recombination.

  10. Adsorption kinetics, thermodynamics and desorption of natural dissolved organic matter by multiwalled carbon nanotubes.

    PubMed

    Su, Fengsheng; Lu, Chungsying

    2007-09-01

    Multiwalled carbon nanotubes (CNTs) were thermally treated and were employed as adsorbents to study their adsorption kinetics and thermodynamics of natural dissolved organic matter (NDOM) from aqueous solutions. The adsorption kinetics follows the first-order rate law while the adsorption thermodynamics indicates the exothermic and spontaneous nature. A comparative study on the adsorption/desorption properties of NDOM between CNTs and granular activated carbon (GAC) was also conducted and revealed that the CNTs possess more NDOM adsorption capacities and show less weight loss through 10 cycles of water treatment and reactivation than the GAC. This suggests that the CNTs are promising NDOM adsorbents for preventing the microbiological degradation of drinking water quality as well as the formation of disinfection by products in water treatment.

  11. Investigation of molecule-adsorption kinetics by a pulsed laser desorption technique

    NASA Astrophysics Data System (ADS)

    Varakin, V. N.; Lozovskii, A. D.; Panesh, A. M.; Simonov, A. P.

    1987-02-01

    The laser thermal desorption technique is used to measure the adsorption kinetics of SO2 and CO molecules on stainless steel with the aim of investigating the initial stage of oxidation of the steel by adsorbed CO molecules. Attention is given to the dependence of the rate of establishment of the equilibrium concentration of adsorbed molecules on SO2-gas pressure; CO adsorption kinetics on stainless steel at a gas pressure of 9 x 10 to the -8th torr; and the dependence of the concentration of adsorbed CO molecules on exposure in the gas at a pressure of 9 x 10 to the -8th torr under irradiation by laser pulses with repetition periods of 1-2, 2-4, 3-6, and 4-8 min.

  12. Uncertainty analysis of multi-rate kinetics of uranium desorption from sediments

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoying; Liu, Chongxuan; Hu, Bill X.; Zhang, Guannan

    2014-01-01

    Multi-rate surface complexation models have been proposed to describe the kinetics of uranyl (U(VI) surface complexation reactions (SCR) rate-limited by diffusive mass transfer to and from intragranular sorption sites in subsurface sediments. In this study, a Bayesian-based, Differential Evolution Markov Chain method was used to assess the uncertainty and to identify factors controlling the uncertainties of the multi-rate SCR model. The rate constants in the multi-rate SCR were estimated with and without assumption of a specified lognormal distribution to test the lognormal assumption typically used to minimize the number of the rate constants in the multi-rate model. U(VI) desorption under variable chemical conditions from a contaminated sediment at US Hanford 300 Area, Washington was used as an example. The results indicated that the estimated rate constants without a specified lognormal assumption approximately followed a lognormal distribution, indicating that the lognormal is an effective assumption for the rate constants in the multi-rate SCR model. However, those rate constants with their corresponding half-lives longer than the experimental durations for model characterization had larger uncertainties and could not be reliably estimated. The uncertainty analysis revealed that the time-scale of the experiments for calibrating the multi-rate SCR model, the assumption for the rate constant distribution, the geochemical conditions involved in predicting U(VI) desorption, and equilibrium U(VI) speciation reaction constants were the major factors contributing to the extrapolation uncertainties of the multi-rate SCR model. Overall, the results from this study demonstrated that the multi-rate SCR model with a lognormal distribution of its rate constants is an effective approach for describing rate-limited U(VI) desorption; however, the model contains uncertainties, especially for those smaller rate constants, that require careful consideration for predicting U

  13. Kinetics of degradation and adsorption-desorption isotherms of thiobencarb and oxadiargyl in calcareous paddy fields.

    PubMed

    Mahmoudi, Mojtaba; Rahnemaie, Rasoul; Es-haghi, Ali; Malakouti, Mohammad J

    2013-05-01

    Herbicides are an important source of contamination in paddy fields. Monitoring their fate and chemical interactions is therefore imperative for sustaining the environment and human health. To meet this purpose, field experiments were conducted to investigate kinetics of thiobencarb and oxadiargyl dissipation in soil and water of two paddy fields. Their adsorption and desorption isotherms were also determined in the soil samples. Variation in concentration was monitored for 60d in soil solution phase and for 315d in soil solid phase. In soil solution, concentrations of both herbicides were rapidly reduced within 5d and reached steady state within 20-30d. Analysis of experimental data resolved a half-life ≈2-4d for both herbicides. In soil solid phase, adsorption reaction played a dominant role in the first 10d. Afterwards, degradation reactions regulated the process. Variation in concentration was minimized after about 150d for thiobencarb and 80d for oxadiargyl. The half-lives were calculated ≈50d for thiobencarb and ≈20d for oxadiargyl, indicating that association with soil particles protect them effectively against degradation reactions. Adsorption isotherms confirmed that both herbicides were strongly adsorbed on soil particles. Furthermore, desorption data indicated that after four successive desorption steps, less than 9% thiobencarb and 1% oxadiargyl were released. This denotes that electrolyte ions in solution cannot adequately compete with and replace adsorbed thiobencarb and oxadiargyl molecules. This would lead to a considerable hysteresis between adsorption and desorption isotherms as was observed experimentally. Overall, it was concluded that both herbicides are among non-persistent and immobile herbicides in the paddy soils.

  14. Phase diagram and adsorption-desorption kinetics of CO on Ru(0001) from first principles.

    PubMed

    McEwen, J-S; Eichler, A

    2007-03-07

    A kinetic lattice gas model is used to study the equilibrium properties and the desorption kinetics of CO on Ru(0001). The authors compute all relevant on-site binding and interaction energies of CO molecules within density functional theory and import them in two different models. The first model allows the CO molecules to adsorb upright on top and hollow sites. The authors calculate the phase diagram, coverage isobars, and temperature programed desorption spectra. Up to a coverage of 1/3 ML, very good agreement is obtained between theory and experiment when considering top sites only. For coverages beyond 1/3 ML, hollow sites are included and disagreement between theory and experiment occurs. The second model allows adsorption on top sites only but allows them to tilt and shift from their upright positions. The authors show that this model resolves many of the deficiencies of their first one. Furthermore, the authors demonstrate that this model is more consistent with experiment since it is the only model that is able to explain the results from IR-spectroscopy experiments.

  15. Effect of fulvic acid surface coatings on plutonium sorption and desorption kinetics on goethite.

    PubMed

    Tinnacher, Ruth M; Begg, James D; Mason, Harris; Ranville, James; Powell, Brian A; Wong, Jennifer C; Kersting, Annie B; Zavarin, Mavrik

    2015-03-03

    The rates and extent of plutonium (Pu) sorption and desorption onto mineral surfaces are important parameters for predicting Pu mobility in subsurface environments. The presence of natural organic matter, such as fulvic acid (FA), may influence these parameters. We investigated the effects of FA on Pu(IV) sorption/desorption onto goethite in two scenarios: when FA was (1) initially present in solution or (2) found as organic coatings on the mineral surface. A low pH was used to maximize FA coatings on goethite. Experiments were combined with kinetic modeling and speciation calculations to interpret variations in Pu sorption rates in the presence of FA. Our results indicate that FA can change the rates and extent of Pu sorption onto goethite at pH 4. Differences in the kinetics of Pu sorption were observed as a function of the concentration and initial form of FA. The fraction of desorbed Pu decreased in the presence of FA, indicating that organic matter can stabilize sorbed Pu on goethite. These results suggest that ternary Pu-FA-mineral complexes could enhance colloid-facilitated Pu transport. However, more representative natural conditions need to be investigated to quantify the relevance of these findings.

  16. Effect of fulvic acid surface coatings on plutonium sorption and desorption kinetics on goethite

    SciTech Connect

    Tinnacher, Ruth M.; Begg, James D.; Mason, Harris; Ranville, James; Powell, Brian A.; Wong, Jennifer C.; Kersting, Annie B.; Zavarin, Mavrik

    2015-01-21

    The rates and extent of plutonium (Pu) sorption and desorption onto mineral surfaces are important parameters for predicting Pu mobility in subsurface environments. The presence of natural organic matter, such as fulvic acid (FA), may influence these parameters. We investigated the effects of FA on Pu(IV) sorption/desorption onto goethite in two scenarios: when FA was (1) initially present in solution or (2) found as organic coatings on the mineral surface. A low pH was used to maximize FA coatings on goethite. Experiments were combined with kinetic modeling and speciation calculations to interpret variations in Pu sorption rates in the presence of FA. Our results indicate that FA can change the rates and extent of Pu sorption onto goethite at pH 4. Differences in the kinetics of Pu sorption were observed as a function of the concentration and initial form of FA. The fraction of desorbed Pu decreased in the presence of FA, indicating that organic matter can stabilize sorbed Pu on goethite. These results suggest that ternary Pu–FA–mineral complexes could enhance colloid-facilitated Pu transport. In conclusion, more representative natural conditions need to be investigated to quantify the relevance of these findings.

  17. Effect of fulvic acid surface coatings on plutonium sorption and desorption kinetics on goethite

    DOE PAGES

    Tinnacher, Ruth M.; Begg, James D.; Mason, Harris; ...

    2015-01-21

    The rates and extent of plutonium (Pu) sorption and desorption onto mineral surfaces are important parameters for predicting Pu mobility in subsurface environments. The presence of natural organic matter, such as fulvic acid (FA), may influence these parameters. We investigated the effects of FA on Pu(IV) sorption/desorption onto goethite in two scenarios: when FA was (1) initially present in solution or (2) found as organic coatings on the mineral surface. A low pH was used to maximize FA coatings on goethite. Experiments were combined with kinetic modeling and speciation calculations to interpret variations in Pu sorption rates in the presencemore » of FA. Our results indicate that FA can change the rates and extent of Pu sorption onto goethite at pH 4. Differences in the kinetics of Pu sorption were observed as a function of the concentration and initial form of FA. The fraction of desorbed Pu decreased in the presence of FA, indicating that organic matter can stabilize sorbed Pu on goethite. These results suggest that ternary Pu–FA–mineral complexes could enhance colloid-facilitated Pu transport. In conclusion, more representative natural conditions need to be investigated to quantify the relevance of these findings.« less

  18. Remediation and desorption kinetics of pyrene from kaolinite co-contaminated with heavy metals at various organic matter contents

    NASA Astrophysics Data System (ADS)

    Saeedi, Mohsen; Li, Loretta Y.; Grace, John R.

    2017-04-01

    Soils co-contaminated with polycyclic aromatic hydrocarbons (PAHs) and heavy metals are challenging for remediation. In the present study desorption of pyrene in kaolinite, co-contaminated by Ni, Pb and Zn, was examined by combinations of surfactants and chelating agents such as Triton X-100, Tween 80, Ethylene diamine tetra acetic acid (EDTA) and citric acid. Results showed that a combination of Triton X-100 (7.5 % w/w) + EDTA (0.01 M) and Tween 80 (7.5 % w/w) + EDTA (0.01 M) were effective in simultaneously desorbing both types of contaminants. Batch desorption tests were conducted using single and combined enhancing agents containing Triton X-100 and Tween 80 as non-ionic surfactants, EDTA as a chelating agent, and citric acid as an organic acid. The solution with the highest removal efficiency was the combined solution containing Triton X-100 (7.5 % w/w) + EDTA (0.01M). Triton X-100 (7.5% w/w) + EDTA (0.01M) led to removal efficiencies of 88% for pyrene in base kaolinite. Batch desorption kinetic experiments were performed using Triton X-100 (7.5% w/w) + EDTA (0.01M). During the first 24 h, desorption was rapid. Organic matter content in the kaolinite led to a reduction in the desorption rate of the contaminants. The desorption kinetic data were well fitted by a pseudo-second-order kinetic model.

  19. Desorption Kinetics of Ar, Kr, Xe, N2, O2, CO, Methane, Ethane, and Propane from Graphene and Amorphous Solid Water Surfaces

    SciTech Connect

    Smith, R. Scott; May, Robert A.; Kay, Bruce D.

    2016-03-03

    The desorption kinetics for Ar, Kr, Xe, N2, O2, CO, methane, ethane, and propane from grapheme covered Pt(111) and amorphous solid water (ASW) surfaces are investigated using temperature programmed desorption (TPD). The TPD spectra for all of the adsorbates from graphene have well-resolved first, second, third, and multi- layer desorption peaks. The alignment of the leading edges is consistent the zero-order desorption for all of the adsorbates. An Arrhenius analysis is used to obtain desorption energies and prefactors for desorption from graphene for all of the adsorbates. In contrast, the leading desorption edges for the adsorbates from ASW do not align (for coverages < 2 ML). The non-alignment of TPD leading edges suggests that there are multiple desorption binding sites on the ASW surface. Inversion analysis is used to obtain the coverage dependent desorption energies and prefactors for desorption from ASW for all of the adsorbates.

  20. Effects of cerium on the hydrogen absorption-desorption properties of rare earth-Mg-Ni hydrogen-absorbing alloys

    NASA Astrophysics Data System (ADS)

    Yasuoka, Shigekazu; Ishida, Jun; Kishida, Kyosuke; Inui, Haruyuki

    2017-04-01

    The influence of Ce addition on the phase constitution, microstructure, hydrogen absorption/desorption properties and battery performances of newly developed rare earth (RE)-Mg-Ni hydrogen-absorbing superlattice alloys for negative electrode materials in Ni-metal hydride (MH) batteries were investigated. The partial substitution of RE (La and Nd) with Ce results in a higher discharge performance and a lower cycle life in the battery. The Ce addition greatly affects the phase constitution, which is mainly characterized by increased formation of the AB2 phase (A = RE or Mg and B = Ni or Al). The existence of the AB2 phase is found to accelerate alloy pulverization and oxidation when the alloys are used as negative electrode materials in Ni-MH model cells. The accelerated pulverization and oxidation are considered to be responsible for the observed higher discharge performance and lower cycle life in the batteries, respectively.

  1. Hydrogen storage material and process using graphite additive with metal-doped complex hydrides

    DOEpatents

    Zidan, Ragaiy; Ritter, James A.; Ebner, Armin D.; Wang, Jun; Holland, Charles E.

    2008-06-10

    A hydrogen storage material having improved hydrogen absorbtion and desorption kinetics is provided by adding graphite to a complex hydride such as a metal-doped alanate, i.e., NaAlH.sub.4. The incorporation of graphite into the complex hydride significantly enhances the rate of hydrogen absorbtion and desorption and lowers the desorption temperature needed to release stored hydrogen.

  2. Vacancy-mediated hydrogen desorption in NaAl H4

    NASA Astrophysics Data System (ADS)

    Araújo, C. Moysés; Li, S.; Ahuja, R.; Jena, P.

    2005-10-01

    First-principles calculations based on density functional theory are carried out to understand the mechanisms responsible for hydrogen desorption from Ti-doped sodium-alanate (NaAlH4) . While the energy needed to remove a hydrogen atom from NaAlH4 with Ti substituted either at the Na site or at Al site is found to be significantly lower than that from the pristine NaAlH4 , the presence of Na vacancies is shown to play an even larger role: It is not only an order of magnitude smaller than that from Ti-doped sodium-alanate, but the removal of hydrogen associated with a Na vacancy is exothermic with respect to formation of H2 molecule. Furthermore, we show that the unusual stabilization of the magic AlH3 cluster in the vacancy containing sodium-alanate is responsible for this diminished value of the hydrogen-removal energy. It is suggested that this role of vacancies can be exploited in the design and synthesis of complex light-metal hydrides suitable for hydrogen storage.

  3. Characterizing particle-scale equilibrium adsorption and kinetics of uranium(VI) desorption from U-contaminated sediments

    USGS Publications Warehouse

    Stoliker, Deborah L.; Liu, Chongxuan; Kent, Douglas B.; Zachara, John M.

    2013-01-01

    Rates of U(VI) release from individual dry-sieved size fractions of a field-aggregated, field-contaminated composite sediment from the seasonally saturated lower vadose zone of the Hanford 300-Area were examined in flow-through reactors to maintain quasi-constant chemical conditions. The principal source of variability in equilibrium U(VI) adsorption properties of the various size fractions was the impact of variable chemistry on adsorption. This source of variability was represented using surface complexation models (SCMs) with different stoichiometric coefficients with respect to hydrogen ion and carbonate concentrations for the different size fractions. A reactive transport model incorporating equilibrium expressions for cation exchange and calcite dissolution, along with rate expressions for aerobic respiration and silica dissolution, described the temporal evolution of solute concentrations observed during the flow-through reactor experiments. Kinetic U(VI) desorption was well described using a multirate SCM with an assumed lognormal distribution for the mass-transfer rate coefficients. The estimated mean and standard deviation of the rate coefficients were the same for all <2 mm size fractions but differed for the 2–8 mm size fraction. Micropore volumes, assessed using t-plots to analyze N2 desorption data, were also the same for all dry-sieved <2 mm size fractions, indicating a link between micropore volumes and mass-transfer rate properties. Pore volumes for dry-sieved size fractions exceeded values for the corresponding wet-sieved fractions. We hypothesize that repeated field wetting and drying cycles lead to the formation of aggregates and/or coatings containing (micro)pore networks which provided an additional mass-transfer resistance over that associated with individual particles. The 2–8 mm fraction exhibited a larger average and standard deviation in the distribution of mass-transfer rate coefficients, possibly caused by the abundance of

  4. Analysis of the adsorption state and desorption kinetics of NO(2) over Fe-zeolite catalyst by FT-IR and temperature-programmed desorption.

    PubMed

    Iwasaki, Masaoki; Shinjoh, Hirofumi

    2010-03-14

    States of NO(2) adsorption and kinetics of NO(2) desorption over a Fe-loaded ZSM-5 type zeolite were investigated using Fourier transform infrared (FT-IR) spectroscopy and temperature-programmed desorption (TPD). The FT-IR spectra in NO(2)/N(2) flows showed that several adsorption species (NO(2), nitrite, nitrate, and NO(+)) existed; except for NO(2), these were considered to be formed via NO(2) dimerization and disproportionation reactions. The TPD spectra showed two distinct peaks, a low-temperature (LT) peak that can be assigned to weakly adsorbed NO(x) in the zeolite channel and a high-temperature (HT) peak that can be assigned to chemisorbed NO(x) bonded to ion-exchanged Fe sites. By varying flow rates and heating rates in TPD measurements, the peak maximum temperatures in the both peaks were found to be constant with the former, but shifted to higher temperatures with the latter; this suggests that desorption is not controlled by an adsorption/desorption equilibrium, i.e., in the no-readsorption limit. Furthermore, it was found that desorption at both LT and HT peaks proceeds at second order; this implies that the reverse reaction of NO(2) dimerization and disproportionation and/or some sort of lateral interaction between NO(2) molecules might be occurring. The desorption energies and the pre-exponential factors were estimated to be 67 +/- 1 kJ mol(-1) and 10(5.5+/-0.2) s(-1) for the LT peak and 138 +/- 4 kJ mol(-1) and 10(9.8+/-0.3) s(-1) for the HT peak. These values show that interaction strengths between adsorbed NO(x) and Fe sites are relatively large.

  5. Enhanced hydrogen desorption properties of magnesium hydride by coupling non-metal doping and nano-confinement

    NASA Astrophysics Data System (ADS)

    He, Daliang; Wang, Yulong; Wu, Chengzhang; Li, Qian; Ding, Weizhong; Sun, Chenghua

    2015-12-01

    Magnesium hydride (MgH2) offers excellent capacity to store hydrogen, but it suffers from the high desorption temperature (>283 °C for starting release hydrogen). In this work, we calculated the hydrogen desorption energy of Mg76H152 clusters with/without non-metal dopants by density functional theory method. Phosphorus (P), as identified as the best dopant, can reduce the reaction energy for releasing one hydrogen molecule from 0.75 eV (bulk MgH2) to 0.20 eV. Inspired by the calculation, P-doped ordered mesoporous carbon (CMK-3) was synthesized by one-step method and employed as the scaffold for loading MgH2 nanoparticles, forming MgH2@P/CMK-3. Element analysis shows that phosphorus dopants have been incorporated into the CMK-3 scaffold and magnesium and phosphorus elements are well-distributed in carbon scaffold hosts. Tests of hydrogen desorption confirmed that P-doping can remarkably enhance the hydrogen release properties of nanoconfined MgH2 at low temperature, specifically ˜1.5 wt. % H2 released from MgH2@P/CMK-3 below 200 °C. This work, based on the combination of computational calculations and experimental studies, demonstrated that the combined approach of non-metal doping and nano-confinement is promising for enhancing the hydrogen desorption properties of MgH2, which provides a strategy to address the challenge of hydrogen desorption from MgH2 at mild operational conditions.

  6. Effect of the Surface on Charge Reduction and Desorption Kinetics of Soft Landed Peptide Ions

    SciTech Connect

    Hadjar, Omar; Wang, Peng; Futrell, Jean H.; Laskin, Julia

    2009-06-01

    Charge reduction and desorption kinetics of ions and neutral molecules produced by soft-landing of mass-selected singly and doubly protonated Gramicidin S (GS) on different surfaces was studied using time dependant in situ secondary ion mass spectrometry (SIMS) integrated in a specially designed Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) research instrument. Soft-landing targets utilized in this study included inert self-assembled monolayers (SAMs) of 1-dodecane thiol (HSAM) and its fluorinated analog (FSAM) on gold and hydrophilic carboxyl-terminated (COOH-SAM) and amine-terminated (NH2-SAM) SAM surfaces. We observed efficient neutralization of soft-landed ions on the COOH-SAM surface, partial retention of only one proton on the HSAM surface and efficient retention of two protons on the FSAM surface. Slow desorption rates measured experimentally indicate fairly strong binding between peptide molecules and SAM surfaces with the binding energy of 20-25 kcal/mol.

  7. Kinetics of Hg(II) adsorption and desorption in calcined mussel shells.

    PubMed

    Peña-Rodríguez, Susana; Fernández-Calviño, David; Nóvoa-Muñoz, Juan Carlos; Arias-Estévez, Manuel; Núñez-Delgado, Avelino; Fernández-Sanjurjo, María José; Alvarez-Rodríguez, Esperanza

    2010-08-15

    The potential use of calcined mussel shells to purify water contaminated with mercury was evaluated. The Hg(II) adsorption and desorption kinetics were studied in batch-type and stirred-flow chamber experiments. The adsorption/desorption experiments revealed some differences between the batches of shells used. The batch of shells that displayed the greatest capacity to adsorb Hg(II), via a highly irreversible reaction, also contained more Fe and Al than the other batches. The results of the stirred-flow chamber experiments indicated a high degree of irreversibility in the process of Hg(II) adsorption in the mussel shell, and that Hg(II) was rapidly retained. The results of these experiments also revealed that the efficiency of depuration differed depending on the length of time that the system was used: when the system was operated for 55 min, depurating 162 mL of inflowing water g(-1) mussel shell, a 90% reduction in the initial concentration of Hg(II) was obtained; use of the system for 90 min, depurating 265 mL water g(-1) mussel shell, produced a 75% reduction in the initial Hg(II), and use of the system for 162.5 min, depurating 487 mL of water g(-1) mussel shell, resulted in a 50% reduction in the initial Hg(II).

  8. Influence of hydrogen oxidation kinetics on hydrogen environment embrittlement

    NASA Technical Reports Server (NTRS)

    Walter, R. J.; Kendig, M. W.; Meisels, A. P.

    1992-01-01

    Results are presented from experiments performed to determine the roles of hydrogen absorption and hydrogen electron transfer on the susceptibility of Fe- and Ni-base alloys to ambient-temperature hydroen embrittlement. An apparent independence is noted between hydrogen environment embrittlement and internal hydrogen embrittlement. The experiments were performed on Inconel 718, Incoloy 903, and A286. The electrochemical results obtained indicate that Inconel 718 either adsorbs hydrogen more rapidly and/or the electrochemical oxidation of the adsorbed hydrogen occurred more rapidly than in the other two materials.

  9. Thermodynamics and Kinetics of Phase Transformations in Hydrogen Storage Materials

    SciTech Connect

    Ceder, Gerbrand; Marzari, Nicola

    2011-08-31

    The aim of this project is to develop and apply computational materials science tools to determine and predict critical properties of hydrogen storage materials. By better understanding the absorption/desorption mechanisms and characterizing their physical properties it is possible to explore and evaluate new directions for hydrogen storage materials. Particular emphasis is on the determination of the structure and thermodynamics of hydrogen storage materials, the investigation of microscopic mechanisms of hydrogen uptake and release in various materials and the role of catalysts in this process. As a team we have decided to focus on a single material, NaAlH{sub 4}, in order to fully be able to study the many aspects of hydrogen storage. We have focused on phase stability, mass transport and size-dependent reaction mechanisms in this material.

  10. Laboratory investigation of the role of desorption kinetics on americium transport associated with bentonite colloids.

    PubMed

    Dittrich, Timothy Mark; Boukhalfa, Hakim; Ware, Stuart Douglas; Reimus, Paul William

    2015-10-01

    Understanding the parameters that control colloid-mediated transport of radionuclides is important for the safe disposal of used nuclear fuel. We report an experimental and reactive transport modeling examination of americium transport in a groundwater-bentonite-fracture fill material system. A series of batch sorption and column transport experiments were conducted to determine the role of desorption kinetics from bentonite colloids in the transport of americium through fracture materials. We used fracture fill material from a shear zone in altered granodiorite collected from the Grimsel Test Site (GTS) in Switzerland and colloidal suspensions generated from FEBEX bentonite, a potential repository backfill material. The colloidal suspension (100 mg L(-1)) was prepared in synthetic groundwater that matched the natural water chemistry at GTS and was spiked with 5.5 × 10(-10) M (241)Am. Batch characterizations indicated that 97% of the americium in the stock suspension was adsorbed to the colloids. Breakthrough experiments conducted by injecting the americium colloidal suspension through three identical columns in series, each with mean residence times of 6 h, show that more than 95% of the bentonite colloids were transported through each of the columns, with modeled colloid filtration rates (k(f)) of 0.01-0.02 h(-1). Am recoveries in each column were 55-60%, and Am desorption rate constants from the colloids, determined from 1-D transport modeling, were 0.96, 0.98, and 0.91 h(-1) in the three columns, respectively. The consistency in Am recoveries and desorption rate constants in each column indicates that the Am was not associated with binding sites of widely-varying strengths on the colloids, as one binding site with fast kinetics represented the system accurately for all three sequential columns. Our data suggest that colloid-mediated transport of Am in a bentonite-fracture fill material system is unlikely to result in transport over long distance scales because

  11. Laboratory investigation of the role of desorption kinetics on americium transport associated with bentonite colloids

    SciTech Connect

    Dittrich, Timothy Mark; Boukhalfa, Hakim; Ware, Stuart Douglas; Reimus, Paul William

    2015-07-13

    Understanding the parameters that control colloid-mediated transport of radionuclides is important for the safe disposal of used nuclear fuel. We report an experimental and reactive transport modeling examination of americium transport in a groundwater–bentonite–fracture fill material system. A series of batch sorption and column transport experiments were conducted to determine the role of desorption kinetics from bentonite colloids in the transport of americium through fracture materials. We used fracture fill material from a shear zone in altered granodiorite collected from the Grimsel Test Site (GTS) in Switzerland and colloidal suspensions generated from FEBEX bentonite, a potential repository backfill material. The colloidal suspension (100 mg L–1) was prepared in synthetic groundwater that matched the natural water chemistry at GTS and was spiked with 5.5 × 10–10 M241Am. Batch characterizations indicated that 97% of the americium in the stock suspension was adsorbed to the colloids. Breakthrough experiments conducted by injecting the americium colloidal suspension through three identical columns in series, each with mean residence times of 6 h, show that more than 95% of the bentonite colloids were transported through each of the columns, with modeled colloid filtration rates (kf) of 0.01–0.02 h–1. Am recoveries in each column were 55–60%, and Am desorption rate constants from the colloids, determined from 1-D transport modeling, were 0.96, 0.98, and 0.91 h–1 in the three columns, respectively. The consistency in Am recoveries and desorption rate constants in each column indicates that the Am was not associated with binding sites of widely-varying strengths on the colloids, as one binding site with fast kinetics represented the system accurately for all three sequential columns. As a result, our data suggest that colloid-mediated transport of Am in a bentonite-fracture fill

  12. Laboratory investigation of the role of desorption kinetics on americium transport associated with bentonite colloids

    DOE PAGES

    Dittrich, Timothy Mark; Boukhalfa, Hakim; Ware, Stuart Douglas; ...

    2015-07-13

    Understanding the parameters that control colloid-mediated transport of radionuclides is important for the safe disposal of used nuclear fuel. We report an experimental and reactive transport modeling examination of americium transport in a groundwater–bentonite–fracture fill material system. A series of batch sorption and column transport experiments were conducted to determine the role of desorption kinetics from bentonite colloids in the transport of americium through fracture materials. We used fracture fill material from a shear zone in altered granodiorite collected from the Grimsel Test Site (GTS) in Switzerland and colloidal suspensions generated from FEBEX bentonite, a potential repository backfill material. Themore » colloidal suspension (100 mg L–1) was prepared in synthetic groundwater that matched the natural water chemistry at GTS and was spiked with 5.5 × 10–10 M241Am. Batch characterizations indicated that 97% of the americium in the stock suspension was adsorbed to the colloids. Breakthrough experiments conducted by injecting the americium colloidal suspension through three identical columns in series, each with mean residence times of 6 h, show that more than 95% of the bentonite colloids were transported through each of the columns, with modeled colloid filtration rates (kf) of 0.01–0.02 h–1. Am recoveries in each column were 55–60%, and Am desorption rate constants from the colloids, determined from 1-D transport modeling, were 0.96, 0.98, and 0.91 h–1 in the three columns, respectively. The consistency in Am recoveries and desorption rate constants in each column indicates that the Am was not associated with binding sites of widely-varying strengths on the colloids, as one binding site with fast kinetics represented the system accurately for all three sequential columns. As a result, our data suggest that colloid-mediated transport of Am in a bentonite-fracture fill material system is unlikely to result in transport over long

  13. An investigation of the desorption of hydrogen from lithium oxide using temperature programmed desorption and diffuse reflectance infrared spectroscopy

    SciTech Connect

    Kopasz, J.P.; Johnson, C.E.; Ortiz-Villafuerte, J.

    1995-04-01

    The addition of hydrogen to the purge stream has been shown to enhance tritium release from ceramic breeder materials; however, this added hydrogen can lead to increased costs in the tritium purification system. The objective of this work is to develop an understanding of the interactions between hydrogen and lithium oxide surfaces so that the authors can take full advantage of the observed enhancement of tritium release caused by hydrogen addition without incurring high costs in the tritium purification plant.

  14. The dissociation kinetics of NO on Rh(111) as studied by temperature programmed static secondary ion mass spectrometry and desorption

    NASA Astrophysics Data System (ADS)

    Borg, H. J.; Reijerse, J. F. C.-J. M.; van Santen, R. A.; Niemantsverdriet, J. W.

    1994-12-01

    Temperature programmed static secondary ion mass spectrometry (TPSSIMS) and temperature programmed desorption (TPD) have been used to study the kinetics of adsorption, dissociation, and desorption of NO on Rh(111). At 100 K, NO adsorption is molecular and proceeds via mobile precursor state kinetics with a high initial sticking probability. SSIMS indicates the presence of two distinct NO adsorption states, indicative of threefold adsorption at low coverage, and occupation of bridge sites at higher coverages. Three characteristic coverage regimes appear with respect to NO dissociation. At low coverages θNO<0.25 ML, NO dissociates completely at temperatures between 275 and 340 K. If we neglect lateral interactions and assume pure first order dissociation kinetics, we find effective values for the activation barrier and preexponential factor of 40±6 kJ/mol and 106±1 s-1 for the dissociation of 0.15-0.20 ML NO. However, if we assume that a NO molecule needs an ensemble of three to four vacant sites in order to dissociate, the preexponential factor and activation energy are ˜1011 s-1 and 65 kJ/mol, in better agreement with transition state theory expectations. The Nads and Oads dissociation products desorb as N2 and O2, respectively, with desorption parameters Edes=118±10 kJ/mol and νdes=1010.1±1.0 s-1 for N2 in the zero coverage limit. At higher coverages, the desorption kinetics of N2 is strongly influenced by the presence of coadsorbed oxygen. In the medium coverage range 0.25<θNO<0.50 ML, part of the NO desorbs molecularly, with an estimated desorption barrier of 113±10 kJ/mol and a preexponential of 1013.5±1.0 s-1. Dissociation of NO becomes progressively inhibited due to site blocking, the onset shifting from 275 K at 0.25 ML to 400 K, coinciding with the NO desorption temperature, at a coverage of 0.50 ML. The accumulation of nitrogen and oxygen atoms on the highly covered surface causes a destabilization of the nitrogen atoms, which results in an

  15. Eriobotrya japonica seed biocomposite efficiency for copper adsorption: Isotherms, kinetics, thermodynamic and desorption studies.

    PubMed

    Mushtaq, Mehwish; Bhatti, Haq Nawaz; Iqbal, Munawar; Noreen, Saima

    2016-07-01

    Adsorption techniques are widely used to remove pollutants from wastewater; however, composites are gaining more importance due to their excellent adsorption properties. Bentonite composite with Eriobotrya japonica seed was prepared and used for the adsorption of copper (Cu) metal from aqueous media. The process variables such as pH, Cu(II) ions initial concentration, adsorbent dose, contact time and temperature were optimized for maximum Cu(II) adsorption. At pH 5, adsorbent dose 0.1 g, contact time 45 min, Cu(II) ions initial concentration 75 mg/L and temperature 45 °C, maximum Cu(II) adsorption was achieved. Desorption studies revealed that biocomposite is recyclable. Langmuir, Freundlich and Harkins-Jura isotherms as well as pseudo-first and pseudo-second-order kinetics models were applied to understand the adsorption mechanism. Thermodynamic parameters (ΔG(0), ΔH(0) and ΔS(0)) suggest that the adsorption process was spontaneous and endothermic in nature. The pseudo-second-order kinetic model and Langmuir isotherm fitted well to the adsorption data. Results showed that biocomposite was more efficient for Cu(II) adsorption in comparison to individuals native Eriobotrya japonica seed biomass and Na-bentonite.

  16. Desorption isotherms and mathematical modeling of thin layer drying kinetics of tomato

    NASA Astrophysics Data System (ADS)

    Belghith, Amira; Azzouz, Soufien; ElCafsi, Afif

    2016-03-01

    In recent years, there is an increased demand on the international market of dried fruits and vegetables with significant added value. Due to its important production, consumption and nutrient intake, drying of tomato has become a subject of extended and varied research works. The present work is focused on the drying behavior of thin-layer tomato and its mathematical modeling in order to optimize the drying processes. The moisture desorption isotherms of raw tomato were determined at four temperature levels namely 45, 50, 60 and 65 °C using the static gravimetric method. The experimental data obtained were modeled by five equations and the (GAB) model was found to be the best-describing these isotherms. The drying kinetics were experimentally investigated at 45, 55 and 65 °C and performed at air velocities of 0.5 and 2 m/s. In order to investigate the effect of the exchange surface on drying time, samples were dried into two different shapes: tomato halves and tomato quarters. The impact of various drying parameters was also studied (temperature, air velocity and air humidity). The drying curves showed only the preheating period and the falling drying rate period. In this study, attention was paid to the modeling of experimental thin-layer drying kinetics. The experimental results were fitted with four different models.

  17. Enzyme kinetics by directly imaging a porous silicon microfluidic reactor using desorption/ionization on silicon mass spectrometry.

    PubMed

    Nichols, Kevin P; Azoz, Seyla; Gardeniers, Han J G E

    2008-11-01

    Enzyme kinetics were obtained in a porous silicon microfluidic channel by combining an enzyme and substrate droplet, allowing them to react and deposit a small amount of residue on the channel walls, and then analyzing this residue by directly ionizing the channel walls using a matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) laser source. The porous silicon of the channel walls functions in a manner analogous to the matrix in MALDI-MS, and is referred to as a desorption/ionization on silicon mass spectrometry (DIOS-MS) target when used in this configuration. Mass spectrometry signal intensity of substrate residue correlates with relative concentration, and position in the microchannel correlates with time, thus allowing determination of kinetic parameters. The system is especially suitable for initial reaction velocity determination. This microreactor is broadly applicable to time-resolved kinetic assays as long as at least one substrate or product of the reaction is ionizable by DIOS-MS.

  18. Kinetics of hydrogen release from lunar soil

    NASA Technical Reports Server (NTRS)

    Bustin, Roberta

    1990-01-01

    With increasing interest in a lunar base, there is a need for extensive examination of possible lunar resources. Hydrogen will be needed on a lunar base for many activities including providing fuel, making water, and serving as a reducing agent in the extraction of oxygen from its ores. Previous studies have shown the solar wind has implanted hydrogen in the lunar regolith and that hydrogen is present not only in the outer layer of soil but to considerable depths, depending on the sampling site. If this hydrogen is to be mined and used on the lunar surface, a number of questions need to be answered. How much energy must be expended in order to release the hydrogen from the soil. What temperatures must be attained, and how long must the soil be heated. This study was undertaken to provide answers to practical questions such as these. Hydrogen was determined using a Pyrolysis/GC technique in which hydrogen was released by heating the soil sample contained in a quartz tube in a resistance wire furnace, followed by separation and quantitative determination using a gas chromatograph with a helium ionization detector. Heating times and temperatures were varied, and particle separates were studied in addition to bulk soils. The typical sample size was 10 mg of lunar soil. All of the soils used were mature soils with similar hydrogen abundances. Pre-treatments with air and steam were used in an effort to find a more efficient way of releasing hydrogen.

  19. Absorption/desorption of hydrogen isotopes and isotopic waters by Zr-alloy getters

    SciTech Connect

    Ichimura, K.; Matsuyama, M.; Watanabe, K.; Takeuchi, T.

    1988-07-01

    Zr-alloy getters have been applied to tritium handling and vacuum conditioning for fusion devices. Some of their properties, however, should be improved to apply them in future devices. From this viewpoint, we have studied the effects of alloying on the getter properties of Zr alloys. We found that the activation energy of absorption and desorption of hydrogen varied considerably with alloying. The activation energy for hydrogen absorption was 0.74 for Zr/sub 61/Al/sub 39/, 0.01 for Zr/sub 57/V/sub 36/Fe/sub 7/, 0.63 for Zr/sub 67/Ni/sub 33/, and 2.8 kcal/mol for Zr/sub 85/Ni/sub 15/, whereas that for Zr was 2.6 kcal/mol. The heat of hydrogen absorption was 27.8 kcal/mol for Zr: it changed with alloying as 32.0--33.4 (Zr/sub 61/Al/sub 39/), 27.8--28.4 (Zr/sub 57/V/sub 36/Fe/sub 7/), 29.0 (Zr/sub 67/Ni/sub 33/), and 28.0 (Zr/sub 85/Ni/sub 15/). In addition, the ratio of the pumping speed of water vapor to that of hydrogen at room temperature varied with alloying element: for example, 1/40 for Zr/sub 57/V/sub 36/Fe/sub 7/ and 1/4 for Zr/sub 67/Ni/sub 33/. The alloying effects mentioned above are considered due to modification of the electronic and/or geometric structure of Zr with alloying.

  20. Catalytic reduction of CO with hydrogen sulfide. 4. Temperature-programmed desorption of methanethiol on anatase, rutile, and sulfided rutile

    SciTech Connect

    Beck, D.D.; White, J.M.; Ratcliffe, C.T.

    1986-07-03

    The interaction of methanethiol with anatase, rutile, and sulfided rutile was studied by temperature-programmed desorption. Dissociative adsorption occurs on rutile but is insignificant on anatase. Decomposition products are dominated by H/sub 2/ on rutile and by CH/sub 4/ on sulfided rutile. In both cases desorption occurs between 500 and 775 K. The 5- and 4-coordinate sites on the (110) face of rutile are proposed as the active sites for decomposition. The dominance of methane on a sulfided surface is attributed to the relatively large supply of highly mobile surface hydrogen atoms.

  1. Charge transfer and adsorption-desorption kinetics in carbon nanotube and graphene gas sensing

    NASA Astrophysics Data System (ADS)

    Liang, Sang-Zi; Chen, Gugang; Harutyunyan, Avetik; Cole, Milton; Sofo, Jorge

    2014-03-01

    Detection of molecules in the gas phase by carbon nanotube and graphene has great application potentials due to the high sensitivity and surface-to-volume ratio. In chemiresistor, the conductance of the materials has been proposed to change as a result of charge transfer from the adsorbed molecules. Due to self-interaction errors, calculations using LDA or GGA density functionals have an innate disadvantage in dealing with charge transfer situations. A model which takes into consideration the dielectric interaction between the graphene surface and the molecule is employed to estimate the distance where charge transfer becomes favorable. Adsorption-desorption kinetics is studied with a modified Langmuir model, including sites from which the molecules do not desorb within the experimental time. Assuming a constant mobility, the model reproduces existing experimental conductance data. Its parameters provide information about the microscopic process during the detection and varying them allows optimization of aspects of sensor performance, including sensitivity, detection limit and response time. This work is supported by Honda Research Institute USA, Inc.

  2. Effect of thermal desorption kinetics on vapor injection peak irregularities by a microscale gas chromatography preconcentrator.

    PubMed

    Seo, Jung Hwan; Liu, Jing; Fan, Xudong; Kurabayashi, Katsuo

    2012-08-07

    Microscale gas chromatography (μGC) is an emerging analytical technique for in situ analysis and on-site monitoring of volatile organic compounds (VOCs) in moderately complex mixtures. One of the critical subcomponents in a μGC system is a microfabricated preconcentrator (μ-preconcentrator), which enables detection of compounds existing in indoor/ambient air at low (~sub ppb) concentrations by enhancing their signals. The prevailing notion is that elution peak broadening and tailing phenomena resulting from undesirable conditions of a microfabricated separation column (μ-column) are the primary sources of poor chromatographic resolution. However, previous experimental results indicate that the resolution degradation still remains observed for a μ-column integrated with other μGC subcomponents even after setting optimal separation conditions. In this work, we obtain the evidence that the unoptimized μ-preconcentrator vapor release/injection performance significantly contributes to decrease the fidelity of μGC analysis using our state-of-the-art passive preconcentrator microdevice. The vapor release/injection performance is highly affected by the kinetics of the thermal desorption of compounds trapped in the microdevice. Decreasing the heating rate by 20% from the optimal rate of 90 °Cs(-1) causes a 340% increase in peak tailing as well as 70% peak broadening (30% peak height reduction) to the microscale vapor injection process.

  3. Desorption kinetics of PAHs from aged industrial soils for availability assessment.

    PubMed

    Barnier, Christophe; Ouvrard, Stéphanie; Robin, Christophe; Morel, Jean Louis

    2014-02-01

    Persistent organic pollutants (POPs), such as polycyclic aromatic hydrocarbons (PAHs), may be found in high concentrations in soils of former industrial sites including manufactured gas plants or coking plants. Techniques using moderate solvent extraction, biological tests or solid phase extraction have proved useful for pollution availability estimation. However, more accurate and reliable measurement tools specifically adapted to low concentrations are still needed. Based on a solid-liquid extraction using a Tenax® resin, we suggest a protocol to assess the bioavailability of PAHs, dedicated to aged industrial wasteland soils. Desorption kinetics were measured on three representative contaminated industrial soils. Results were modeled using a first order two-compartment model that provided an estimate of the rapidly desorbing fraction, which was considered to be available, over a 30 h extraction period. In conclusion, this method, allowing the measurement of the available fraction, might prove more relevant than the total concentration value when assessing soil contamination related risks. It may also predict achievable bioremediation performances. © 2013.

  4. CO adsorption on W(100) during temperature-programmed desorption: A combined density functional theory and kinetic Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Albao, Marvin A.; Padama, Allan Abraham B.

    2017-02-01

    Using a combined density functional theory (DFT) and kinetic Monte Carlo (KMC) simulations, we study the adsorption at 800 K and subsequent desorption of CO on W(100) at higher temperatures. The resulting TPD profiles are known experimentally to exhibit three desorption peaks β1, β2, and β3 at 930 K, 1070 K, and 1375 K, respectively. Unlike more recent theoretical studies that propose that all three aforementioned peaks are molecularly rather than associatively desorbed, our KMC analyses are in support of the latter, since at 800 K dissociation is facile and that CO exists as dissociation fragments C and O. We show that these peaks arise from desorption from the same adsorption site but whose binding energy varies depending on local environment, that is, the presence of CO as well as dissociation fragments C and O nearby. Furthermore we show that several key parameters, such as desorption, dissociation and recombination barriers all play a key role in the TPD spectra-these parameter effectively controls not only the location of the TPD peaks but the shape and width of the desorption peaks as well. Moreover, our KMC simulations reveal that varying the heating rate shifts the peaks but leaves their shape intact.

  5. Effect of humic acid on the adsorption/desorption behavior of glyphosate on goethite. Isotherms and kinetics.

    PubMed

    Arroyave, Jeison Manuel; Waiman, Carolina C; Zanini, Graciela P; Avena, Marcelo J

    2016-02-01

    The effects of humic acid (HA) on the adsorption/desorption of glyphosate (Gly) on goethite were investigated under pseudo equilibrium conditions by adsorption isotherms and under kinetic conditions by ATR-FTIR spectroscopy. Isotherms reveal that the attachment of Gly is almost completely inhibited by HA molecules. The opposite effect is not observed: HA adsorption is not affected by the presence of Gly. ATR-FTIR allowed the simultaneous detection of adsorbed HA and Gly during kinetic runs, revealing that HA at the surface decreases markedly the adsorption rate of Gly likely as a result of a decreased availability of sites for Gly adsorption and because of electrostatic repulsion. In addition, HA in solution increases the desorption rate of Gly. The rate law for Gly desorption could be determined giving important insights on the desorption mechanism. The herbicide is desorbed by two parallel processes: i) a direct detachment from the surface, which is first order in adsorbed Gly; and ii) a ligand exchange with HA molecules, which is first order in adsorbed Gly and first order in dissolved HA. Rate constants for both processes were quantified, leading to half-lives of 3.7 h for the first process, and 1.4 h for the second process in a 400 mg L(-1) HA solution. These data are important for modeling the dynamics of glyphosate in environmentally relevant systems, such as soils and surface waters.

  6. Molecular Beam-Thermal Desorption Spectrometry (MB-TDS) Monitoring of Hydrogen Desorbed from Storage Fuel Cell Anodes.

    PubMed

    Lobo, Rui F M; Santos, Diogo M F; Sequeira, Cesar A C; Ribeiro, Jorge H F

    2012-02-06

    Different types of experimental studies are performed using the hydrogen storage alloy (HSA) MlNi3.6Co0.85Al0.3Mn0.3 (Ml: La-rich mischmetal), chemically surface treated, as the anode active material for application in a proton exchange membrane fuel cell (PEMFC). The recently developed molecular beam-thermal desorption spectrometry (MB-TDS) technique is here reported for detecting the electrochemical hydrogen uptake and release by the treated HSA. The MB-TDS allows an accurate determination of the hydrogen mass absorbed into the hydrogen storage alloy (HSA), and has significant advantages in comparison with the conventional TDS method. Experimental data has revealed that the membrane electrode assembly (MEA) using such chemically treated alloy presents an enhanced surface capability for hydrogen adsorption.

  7. Molecular Beam-Thermal Desorption Spectrometry (MB-TDS) Monitoring of Hydrogen Desorbed from Storage Fuel Cell Anodes

    PubMed Central

    Lobo, Rui F. M.; Santos, Diogo M. F.; Sequeira, Cesar A. C.; Ribeiro, Jorge H. F.

    2012-01-01

    Different types of experimental studies are performed using the hydrogen storage alloy (HSA) MlNi3.6Co0.85Al0.3Mn0.3 (Ml: La-rich mischmetal), chemically surface treated, as the anode active material for application in a proton exchange membrane fuel cell (PEMFC). The recently developed molecular beam—thermal desorption spectrometry (MB-TDS) technique is here reported for detecting the electrochemical hydrogen uptake and release by the treated HSA. The MB-TDS allows an accurate determination of the hydrogen mass absorbed into the hydrogen storage alloy (HSA), and has significant advantages in comparison with the conventional TDS method. Experimental data has revealed that the membrane electrode assembly (MEA) using such chemically treated alloy presents an enhanced surface capability for hydrogen adsorption. PMID:28817043

  8. Complex surface analytical investigations on hydrogen absorption and desorption processes of a TiMn2-based alloy.

    PubMed

    Schülke, Mark; Kiss, Gábor; Paulus, Hubert; Lammers, Martin; Ramachandran, Vaidyanath; Sankaran, Kannan; Müller, Karl-Heinz

    2009-04-01

    Metal hydrides are one of the most promising technologies in the field of hydrogen storage due to their high volumetric storage density. Important reaction steps take place at the very surface of the solid during hydrogen absorption. Since these reaction steps are drastically influenced by the properties and potential contamination of the solid, it is very important to understand the characteristics of the surface, and a variety of analytical methods are required to achieve this. In this work, a TiMn(2)-type metal hydride alloy is investigated by means of high-pressure activation measurements, X-ray photoelectron spectroscopy (XPS), secondary neutral mass spectrometry (SNMS) and thermal desorption mass spectrometry (TDMS). In particular, TDMS is an analytical tool that, in contrast to SIMS or SNMS, allows the hydrogen content in a metal to be quantified. Furthermore, it allows the activation energy for desorption to be determined from TDMS profiles; the method used to achieve this is presented here in detail. In the results section, it is shown that the oxide layer formed during manufacture and long-term storage prevents any hydrogen from being absorbed, and so an activation process is required. XPS measurements show the oxide states of the main alloy elements, and a layer 18 nm thick is determined via SNMS. Furthermore, defined oxide layers are produced and characterized in UHV using XPS. The influence of these thin oxide layers on the hydrogen sorption process is examined using TDMS. Finally, the activation energy of desorption is determined for the investigated alloy using the method presented here, and values of 46 kJ/mol for hydrogen sorbed in UHV and 103 kJ/mol for hydrogen originating from the manufacturing process are obtained.

  9. Understanding the role of vanadium in enhancing the low-temperature hydrogenation kinetics of an Mg thin film.

    PubMed

    Zheng, Shiyou; Li, Zhi-Peng; Bendersky, Leonid A

    2013-08-14

    Mg100-xVx (x = 0 to 15) thin films capped with Pd were prepared by electron beam codeposition and studied for their hydrogenation/dehydrogenation kinetics and cycling properties at 140 °C under hydrogenation pressures of 0.1 MPa. It has been found that the Mg100-xVx thin films show significantly higher reversible hydrogen-storage capacity and faster kinetics in comparison with a pure Mg thin film; for instance, the maximum hydrogen absorption (3.7% mass fraction hydrogen) can be obtained in the fifth cycle for Mg90V10 in less than 5 min. The addition of V clearly plays a favorable role in improving the reversible hydrogen-storage capacity of an Mg film; however, with increasing hydrogenation/dehydrogenation cycles the hydrogen-storage capacity gradually deteriorates. To explore the origin of the effect of V on the improved hydrogenation of an Mg thin film, in this work we focused on studying the structural variations of the Mg90V10 thin film before and after hydrogenation at different stages of cycling; the films were investigated by X-ray diffraction as well as scanning and transmission electron microscopy. We concluded that (1) early in the absorption/desorption cycling the as-deposited structure of percolating layers of nanocrystalline V throughout a Mg matrix is preserved; (2) the percolating V layers envelope fine Mg grains and act as (a) dispersers that isolate small Mg grains, (b) fast diffusers of hydrogen, and (c) hydrogen catalysts at the Mg/V interface to form MgH2; and (3) with progressive cycling, the continuous layers of V aggregate to spherical nanoparticles, which interrupts the continuity of fast hydrogen diffusion through V.

  10. Two-step kinetic study on the adsorption and desorption of reactive dyes at cationic polymer/bentonite.

    PubMed

    Li, Qian; Yue, Qin-Yan; Su, Yuan; Gao, Bao-Yu; Li, Jing

    2009-06-15

    The adsorption kinetics of two reactive dyes, namely, Reactive Blue K-GL and Reactive Yellow K-4G onto the new cationic polymer/bentonite, i.e., polyepicholorohydrin-dimethylamine/bentonite (EPI-DMA/bentonite), were studied under different conditions. The result indicated that the adsorption processes were found to follow the two-step kinetic rate equation with two different adsorption rate constants (k(1) and k(2)) and also to follow the intraparticle diffusion model with two different diffusion rate constants (k(int,1) and k(int,2)). The corresponding values of energies of activation of adsorption, enthalpies of activation and entropies of activation for both the two adsorption kinetic steps have been calculated, suggesting that the adsorption processes were endothermic and physical. The desorption kinetics of two dyes from EPI-DMA/bentonite were studied in NaOH solution with different concentrations, which were also found to obey the two-step kinetic rate equation with two different desorption rate constants (k(d,1) and k(d,2)).

  11. Ti-based catalytic effect on hydrogen desorption in crystalline NaBH4: an ab initio investigation

    NASA Astrophysics Data System (ADS)

    Moysés Araújo, C.; Jena, Puru

    2005-03-01

    The application of hydrogen fuel cell technology in portable electronic devices and transportation vehicles has led to a great deal of interest in the study of complex alkali hydrides (MXH4 with M=Na, Li and X=Al,B) primarily due to their high gravimetric hydrogen density (eg.18.5% in LiBH4). In particular, NaBH4 slurry has been suggested as the most promising system for applications in fuel cell technology (1) as it provides one of the simplest ways of generating hydrogen. Additionally, the NaBH4 itself is also a promising hydrogen storage material since it has one of the highest gravimetric hydrogen density (13.0 wt%) among the alkali metal hydrides. However, its irreversibility with respect to hydrogen absorpton/desorption cycle limits its practical application for hydrogen storage. To overcome this limitation we have explored the role of Ti on the electronic and crystalline structures of NaBH4. Using density functional calculations we show that Ti prefers to occupy the Na site in sodium borohydride. In addition, Ti weakens the strength of the covalent bond between B and H atoms and the hydrogen removal energy is reduced from 5.64 eV in pure sodium borohydride to 4.70 eV when doped with Ti. Thus, Ti might work as a catalytic agent allowing hydrogen to desorb at a lower temperature. Calculations are underway to examine if other dopants may be even better candidates for hydrogen desorption from sodium borohydride. 1. Z. P. Li, B. H. Liu, K. Arai, K. Asaba and S. Suda Journal of Power Sources 126, 28 (2004).

  12. Kinetics of Leucine-Lysine Peptide Adsorption and Desorption at –CH3 and –COOH Terminated Alkylthiolate Monolayers

    PubMed Central

    Apte, Julia S.; Gamble, Lara J.; Castner, David G.; Campbell, Charles T.

    2013-01-01

    The kinetics of adsorption and desorption of two highly asymmetrical model peptides were studied at methyl- and carboxylic acid-terminated alkylthiolate self assembled monolayer (SAM) surfaces on gold. The model peptides were leucine-lysine α-helical (LKα14) and β-strand (LKβ15) peptides that have a well-defined secondary structure with the leucines localized on one side and the lysines on the other side. These secondary structures previously were shown to be maintained after adsorption and to control LK peptide orientation on these surfaces. The kinetics of peptide adsorption were analyzed by surface plasmon resonance (SPR) as a function of peptide solution concentrations at pH 7.4. Peptide desorption was measured by rinsing with buffer at various times along the adsorption curve. Both peptides had a saturation coverage of approximately one monolayer on the carboxyl SAM. Both peptides exhibited mostly irreversible binding on both surfaces, but the LKα14 peptide showed some, limited reversible binding. Reversibly bound peptides could be in the second adlayer interacting only with peptides in the first layer, or peptides interacting with a partially-covered adsorption site and therefore not able to fully bind to the SAM surface. The near complete lack of reversible binding for LKβ15 is possibly due to strong peptide-peptide hydrogen bonding in β-sheet structures within the adsorbed layer. For a given dose of either peptide, much less peptide adsorbed on the methyl SAMs. The adsorption rate of irreversibly-bound LKα14 on carboxylic acid SAMs was first-order with respect to solution concentration. Both peptides showed nucleation-like adsorption kinetics on the carboxylic acid SAM, indicating that peptide-peptide bonding is needed to stabilize the adsorbed layer. Adsorption on the methyl SAM was much lower in quantity for both peptides, and seemed to require prior aggregation of the proteins in solution, at least for LKβ15. PMID:21219030

  13. Determining the Desorption Kinetics of U(VI) from Contaminated Sediments Under Complex and Changing Solution Conditions

    NASA Astrophysics Data System (ADS)

    Hay, M. B.; Curtis, G. P.; Johnson, K. J.; Greskowiak, J.; Davis, J. A.

    2009-12-01

    Uranium(VI) transport in contaminated sediments is strongly controlled by the thermodynamics and kinetics of adsorption on mineral surfaces. Many studies on natural sediments and synthetic mineral phases have demonstrated the dependence of U(VI) sorption equilibrium on aqueous chemical conditions, with alkalinity, pH, ionic strength, and Ca concentration of particular importance in many natural systems. Desorption of U(VI) from contaminated sediments from DOE sites in Hanford, WA, Rifle, CO, and Naturita, CO also exhibits a significant kinetic limitation, with timescales of several weeks to months required to reach desorption equilibrium in some cases. This kinetic limitation is believed to be due to diffusion in intragranular pore space, which includes small fractures within grains and pores within clay aggregates and grain coatings. Development of appropriate reactive transport models that can be applied to predict the fate and transport of U(VI) in contaminated aquifers relies on accurately quantifying sorption equilibrium and kinetics at the grain scale, which vary from site to site based on sediment characteristics. This analysis typically involves laboratory batch- and column-scale adsorption/desorption experiments performed under a variety of chemical conditions to fully constrain surface complexation and kinetic models, requiring a constant set of chemical conditions over the duration of the experiment. In practice, however, this can be difficult in experiments aiming to quantify long-term kinetics (weeks to months time scale), due to slow ion exchange, mineral dissolution/precipitation, and redox processes. Long-term changes in solution conditions affect U(VI) sorption equilibrium, making it necessary to determine model parameters for U(VI) surface complexation, diffusion kinetics, and chemical weathering/ion exchange processes simultaneously from a given data set. We will present kinetic surface complexation model results obtained for size

  14. Desorption of hydrogen from light metal hydrides: concerted electronic rearrangement and role of H···H interactions.

    PubMed

    Wolstenholme, David J; Roy, Matthew M D; Thomas, Michael E; McGrady, G Sean

    2014-04-14

    A theoretical study of the desorption of hydrogen from rhombic Group 1 metal hydride dimers reveals a concerted reorganisation of the electron density for the M-H and H-H moieties as the reaction coordinate is traversed and a closed-shell H···H interaction evolves into a covalent H2 bond. The central role played by homopolar dihydrogen bonding in this process is revealed and analysed.

  15. Characterizing particle-scale equilibrium adsorption and kinetics of uranium(VI) desorption from U-contaminated sediments

    SciTech Connect

    Stoliker, Deborah L.; Liu, Chongxuan; Kent, Douglas B.; Zachara, John M.

    2013-02-12

    Rates of contaminant U(VI) release from individual size fractions of a composite sediment from the seasonally saturated lower vadose zone of the Hanford 300-Area were examined in flow-through batch reactors to maintain quasi-constant chemical conditions. Variability in equilibrium adsorption among the various size fractions was determined in static batch reactors and analyzed using the surface complexation modeling approach. The estimated stoichiometric coefficients of U(VI) surface complexation reactions with respect to pH and carbonate concentrations varied with size fractions. This source of variability significantly increased the uncertainty in U(VI) conditional equilibrium constants over that estimated from experimental errors alone. A minimum difference between conditional equilibrium constants was established in order to evaluate statistically significant differences between sediment adsorption properties. A set of equilibrium and kinetic expressions for cation exchange, calcite dissolution, aerobic respiration, and silica dissolution were incorporated in a reaction-rate model to describe the temporal evolution of solute concentrations observed during the flow-through batch experiments. Parameters in the reaction-rate model, calibrated using experimental data for select size fractions, predicted the changes in solute concentrations for the bulk, <2 mm, sediment sample. Kinetic U(VI) desorption was well described using a multi-rate surface complexation model with an assumed lognormal distribution for the rate constants. The estimated mean and standard deviation were the same for all < 2mm size fractions, but differed in the 2-8mm size fraction. Micropore volumes in the varied size fractions were also similar as assessed using t-plots to analyze N2 desorption data. These findings provide further support for the link between microporosity and particle-scale mass transfer rates controlling kinetic U(VI) adsorption/desorption and for the utility of N2 desorption

  16. Kinetics of front-end acetylene hydrogenation in ethylene production

    SciTech Connect

    Schbib, N.S.; Garcia, M.A.; Gigola, C.E.; Errazu, A.F.

    1996-05-01

    The kinetics of acetylene hydrogenation in the presence of a large excess of ethylene was studied in a laboratory flow reactor. Experiments were carried out using a Pd/{alpha}-Al{sub 2}O{sub 3} commercial catalyst and a simulated cracker gas mixture (H{sub 2}/C{sub 2}H{sub 2} = 50; 60% C{sub 2}H{sub 4}; 30% H{sub 2}, and traces of CO), at varying temperature (293--393 K) and pressure (2--35 atm). Competing mechanisms for acetylene and ethylene hydrogenation were formulated and the corresponding kinetic equations derived by rate-determining step methods. A criterion based upon statistical analysis was used to discriminate between rival kinetic models. The selected equations are consistent with the adsorption of C{sub 2}H{sub 2} and C{sub 2}H{sub 4} in the same active sites followed by reaction with adsorbed hydrogen atoms to form C{sub 2}H{sub 4} and C{sub 2}H{sub 6} in a one-step process. Good agreement between computed and experimental results was obtained using a nonisothermal reactor model that takes into account the existence of external temperature and concentration gradients. The derived kinetic equations together with a pseudohomogeneous model of an integral adiabatic flow reactor were employed to simulate the conversion and the temperature profiles for a commercial hydrogenation unit.

  17. Role of desorption kinetics in determining marangoni flows generated by using electrochemical methods and redox-active surfactants.

    PubMed

    Bai, Guiyu; Graham, Michael D; Abbott, Nicholas L

    2005-03-15

    We report quantitative measurements of Marangoni flows generated at the surfaces of aqueous solutions by using water-soluble redox-active surfactants in combination with electrochemical methods. These measurements are interpreted within the framework of a simple model that is based on lubrication theory and the proposition that the kinetics of the desorption of redox-active surfactants from the surfaces of aqueous solutions plays a central role in determining the strength of the Marangoni flow. The model predicts that the leading edge velocity of the Marangoni flow will decay exponentially with time and that the rate constant for the decay of the velocity can yield an estimate of the surfactant desorption rate constant. Good agreement between theory and experiments was found. By interpreting experimental measurements of electrochemically generated Marangoni flows within the framework of the model, we conclude that the desorption rate constant of the redox-active surfactant Fc(CH(2))(11)-N(+)(CH(3))(3)Br(-), where Fc is ferrocene, is 0.07 s(-)(1). We also conclude that the ionic strength of the aqueous solution has little effect on the desorption rate constant of the ferrocenyl surfactant.

  18. Effects of particle size on the desorption kinetics of water from Beulah-Zap lignite coal: Differential scanning calorimetry results

    SciTech Connect

    Dang, Yuhong; Malhotra, V.M.; Vorres, K.S.

    1996-03-01

    The drying kinetics of water from three particle-sized Beulah-Zap lignite coal samples were probed using the differential scanning calorimetry technique at 295 < T < 480 K. The measurements undertaken under flowing N{sub 2} gas environment indicate that water is lost from this coal by two independent but simultaneously operative kinetic mechanisms. Our results suggest that the unimolecular decay kinetics are obeyed by those water molecules which are near the mouths of large pores and/or surround the coal particles. Most of the water, about 80% of the water lost in our experiments, was removed via a 2nd-order diffusion mechanism. As expected, the desorption activation energies of the 2nd-order diffusion kinetics were much larger than the decay mechanism`s activation energies. Our results also suggest, at least for particle sizes < 841 {mu}m, < 106 {mu}m, and < 37 {mu}m, that the coal particle size has little effect on the desorption activation barriers.

  19. Kinetics of Hydrogen Reduction of Chalcopyrite Concentrate

    NASA Astrophysics Data System (ADS)

    Chatterjee, Ritayan; Ghosh, Dinabandhu

    2015-12-01

    A Ghatshila chalcopyrite concentrate (average particle size, 50 μm) containing primarily CuFeS2 and SiO2 (Cu 16 pct) was reduced by a stream of hydrogen in a thermogravimetric analyzer (TGA) at selected temperatures [1173 K to 1323 K (900 °C to 1050 °C)], hydrogen flow rates, partial pressures of hydrogen (0.33 × 101.3 to 101.3 kPa), and sample bed heights. The product was a mixture of Cu (26 pct), SiO2, CuFeO2, and Fe. The rate equations for the three typical controlling mechanisms, namely, gas film diffusion (mass transfer), pore diffusion, and interfacial reaction, have been derived for the system geometry under study and applied to identify the rate-controlling steps. The first stage of the reduction, which extended up to the first 13 minutes, was rate controlled by the interfacial reaction. The last stage, which spanned over the last 60 to 120 minutes and accounted for a small percentage of reduction, was controlled by pore diffusion through the built-up Cu (and Fe) layer. The activation energy in the first stage was 101 kJ mol-1 and that in the second stage was 76 kJ mol-1. Subsequent acid leaching with 1 M HCl solution of the reduction product removed all soluble species, leaving a Cu (53.3 pct) + SiO2 mixture, with a small concentration (2.7 pct) of Cu2O in it. This result compares well with the predicted final mixture of Cu (59 pct)-SiO2 based on a mass balance on the starting concentrate. A follow-up heating at 1523 K (1250 °C) produced a sintered Cu-SiO2 composite with spherical copper particles of 400 µm diameter embedded in a silica matrix. Elemental chemical analyses were carried out by energy-dispersive X-ray spectroscopy/atomic absorption spectroscopy. The phase identification and microstructural characterization of Cu-SiO2 mixtures were carried out by X-ray powder diffraction and optical microscopy.

  20. Kinetics of hydrogen peroxide decomposition by catalase: hydroxylic solvent effects.

    PubMed

    Raducan, Adina; Cantemir, Anca Ruxandra; Puiu, Mihaela; Oancea, Dumitru

    2012-11-01

    The effect of water-alcohol (methanol, ethanol, propan-1-ol, propan-2-ol, ethane-1,2-diol and propane-1,2,3-triol) binary mixtures on the kinetics of hydrogen peroxide decomposition in the presence of bovine liver catalase is investigated. In all solvents, the activity of catalase is smaller than in water. The results are discussed on the basis of a simple kinetic model. The kinetic constants for product formation through enzyme-substrate complex decomposition and for inactivation of catalase are estimated. The organic solvents are characterized by several physical properties: dielectric constant (D), hydrophobicity (log P), concentration of hydroxyl groups ([OH]), polarizability (α), Kamlet-Taft parameter (β) and Kosower parameter (Z). The relationships between the initial rate, kinetic constants and medium properties are analyzed by linear and multiple linear regression.

  1. Experimental study of water desorption isotherms and thin-layer convective drying kinetics of bay laurel leaves

    NASA Astrophysics Data System (ADS)

    Ghnimi, Thouraya; Hassini, Lamine; Bagane, Mohamed

    2016-12-01

    The aim of this work is to determine the desorption isotherms and the drying kinetics of bay laurel leaves ( Laurus Nobilis L.). The desorption isotherms were performed at three temperature levels: 50, 60 and 70 °C and at water activity ranging from 0.057 to 0.88 using the statistic gravimetric method. Five sorption models were used to fit desorption experimental isotherm data. It was found that Kuhn model offers the best fitting of experimental moisture isotherms in the mentioned investigated ranges of temperature and water activity. The Net isosteric heat of water desorption was evaluated using The Clausius-Clapeyron equation and was then best correlated to equilibrium moisture content by the empirical Tsami's equation. Thin layer convective drying curves of bay laurel leaves were obtained for temperatures of 45, 50, 60 and 70 °C, relative humidity of 5, 15, 30 and 45 % and air velocities of 1, 1.5 and 2 m/s. A non linear regression procedure of Levenberg-Marquardt was used to fit drying curves with five semi empirical mathematical models available in the literature, The R2 and χ2 were used to evaluate the goodness of fit of models to data. Based on the experimental drying curves the drying characteristic curve (DCC) has been established and fitted with a third degree polynomial function. It was found that the Midilli Kucuk model was the best semi-empirical model describing thin layer drying kinetics of bay laurel leaves. The bay laurel leaves effective moisture diffusivity and activation energy were also identified.

  2. Enhanced Hydrogen Storage Kinetics of Nanocrystalline and Amorphous Mg2Ni-type Alloy by Melt Spinning

    PubMed Central

    Zhang, Yang-Huan; Li, Bao-Wei; Ren, Hui-Ping; Li, Xia; Qi, Yan; Zhao, Dong-Liang

    2011-01-01

    Mg2Ni-type Mg2Ni1−xCox (x = 0, 0.1, 0.2, 0.3, 0.4) alloys were fabricated by melt spinning technique. The structures of the as-spun alloys were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The hydrogen absorption and desorption kinetics of the alloys were measured by an automatically controlled Sieverts apparatus. The electrochemical hydrogen storage kinetics of the as-spun alloys was tested by an automatic galvanostatic system. The results show that the as-spun (x = 0.1) alloy exhibits a typical nanocrystalline structure, while the as-spun (x = 0.4) alloy displays a nanocrystalline and amorphous structure, confirming that the substitution of Co for Ni notably intensifies the glass forming ability of the Mg2Ni-type alloy. The melt spinning treatment notably improves the hydriding and dehydriding kinetics as well as the high rate discharge ability (HRD) of the alloys. With an increase in the spinning rate from 0 (as-cast is defined as spinning rate of 0 m/s) to 30 m/s, the hydrogen absorption saturation ratio (R5a) of the (x = 0.4) alloy increases from 77.1 to 93.5%, the hydrogen desorption ratio (R20d) from 54.5 to 70.2%, the hydrogen diffusion coefficient (D) from 0.75 × 10−11 to 3.88 × 10−11 cm2/s and the limiting current density IL from 150.9 to 887.4 mA/g. PMID:28879988

  3. Kinetics of Platinum-Catalyzed Decomposition of Hydrogen Peroxide

    NASA Astrophysics Data System (ADS)

    Vetter, Tiffany A.; Colombo, D. Philip, Jr.

    2003-07-01

    CIBA Vision Corporation markets a contact lens cleaning system that consists of an AOSEPT disinfectant solution and an AOSEPT lens cup. The disinfectant is a buffered 3.0% m/v hydrogen peroxide solution and the cup includes a platinum-coated AOSEPT disc. The hydrogen peroxide disinfects by killing bacteria, fungi, and viruses found on the contact lenses. Because the concentration of hydrogen peroxide needed to disinfect is irritating to eyes, the hydrogen peroxide needs to be neutralized, or decomposed, before the contact lenses can be used again. A general chemistry experiment is described where the kinetics of the catalyzed decomposition of the hydrogen peroxide are studied by measuring the amount of oxygen generated as a function of time. The order of the reaction with respect to the hydrogen peroxide, the rate constant, and the energy of activation are determined. The integrated rate law is used to determine the time required to decompose the hydrogen peroxide to a concentration that is safe for eyes.

  4. Highly hydrogen-sensitive thermal desorption spectroscopy system for quantitative analysis of low hydrogen concentration (˜1 × 1016 atoms/cm3) in thin-film samples

    NASA Astrophysics Data System (ADS)

    Hanna, Taku; Hiramatsu, Hidenori; Sakaguchi, Isao; Hosono, Hideo

    2017-05-01

    We developed a highly hydrogen-sensitive thermal desorption spectroscopy (HHS-TDS) system to detect and quantitatively analyze low hydrogen concentrations in thin films. The system was connected to an in situ sample-transfer chamber system, manipulators, and an rf magnetron sputtering thin-film deposition chamber under an ultra-high-vacuum (UHV) atmosphere of ˜10-8 Pa. The following key requirements were proposed in developing the HHS-TDS: (i) a low hydrogen residual partial pressure, (ii) a low hydrogen exhaust velocity, and (iii) minimization of hydrogen thermal desorption except from the bulk region of the thin films. To satisfy these requirements, appropriate materials and components were selected, and the system was constructed to extract the maximum performance from each component. Consequently, ˜2000 times higher sensitivity to hydrogen than that of a commercially available UHV-TDS system was achieved using H+-implanted Si samples. Quantitative analysis of an amorphous oxide semiconductor InGaZnO4 thin film (1 cm × 1 cm × 1 μm thickness, hydrogen concentration of 4.5 × 1017 atoms/cm3) was demonstrated using the HHS-TDS system. This concentration level cannot be detected using UHV-TDS or secondary ion mass spectroscopy (SIMS) systems. The hydrogen detection limit of the HHS-TDS system was estimated to be ˜1 × 1016 atoms/cm3, which implies ˜2 orders of magnitude higher sensitivity than that of SIMS and resonance nuclear reaction systems (˜1018 atoms/cm3).

  5. Desorption of hydrogen from Ni—Cu—Cr catalyst on (θ + α-Al2O3 sorbent modified with cerium

    NASA Astrophysics Data System (ADS)

    Dossumov, K.; Popova, N. M.; Salakhova, R. Kh.; Tungatarova, S. A.; Shapovalov, A. A.; Umbetkaliev, A. K.

    2010-03-01

    We present the results of thermal desorption studies of H2 interactions with 8.9% Ni—Cu—Cr (1:3:0.1)/(θ+α)-Al2O3+2% Ce. It was demonstrated that three forms of hydrogen with different desorption temperatures and Tmax peak values are formed in the catalyst at 673 K: H2(ads), H(ads), and dissolved hydrogen. It was found that upon an increase in the adsorption temperature from 673 to 1173 K, H2(ads) and H(ads) remain on the surface (Edes = 14.4 kcal/mol, first order desorption reaction, H: Ni = 1.6—1.88) while hydrogen dissolution in the Ni lattice and its copper alloy increases (Edes= 32.9 kcal/mol, second order desorption reaction, H: Ni = 2.0).

  6. Structural and kinetic studies of metal hydride hydrogen storage materials using thin film deposition and characterization techniques

    NASA Astrophysics Data System (ADS)

    Kelly, Stephen Thomas

    absorption and desorption kinetics and degrades the material texture. Cycling the films to greater hydrogen loading accelerates the changes to the kinetics and material texture. In addition to in situ XRD experiments, in situ neutron reflectivity experiments on epitaxial Mg films exposed to hydrogen gas reveal details about the microstructural development of the growing hydride layer as the film absorbs and releases hydrogen. Small (10 wt%) additions of Ti to epitaxial Mg films during growth result in metastable solid solution films of Ti in Mg that deposit epitaxially on (001) Al2O3 substrates with epitaxy similar to the pure Mg films. These metastable alloy films absorb hydrogen faster than pure Mg films under identical conditions. Subsequent film cycling results in altered reaction kinetics and a transition to a different kinetic mechanism during desorption than for pure Mg films.

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

    SciTech Connect

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

    2014-07-17

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

  8. Improvement in hydrogen desorption from β- and γ-MgH2 upon transition-metal doping.

    PubMed

    Hussain, Tanveer; Maark, Tuhina Adit; Chakraborty, Sudip; Ahuja, Rajeev

    2015-08-24

    A thorough study of the structural, electronic, and hydrogen-desorption properties of β- and γ-MgH2 phases substituted by selected transition metals (TMs) is performed through first-principles calculations based on density functional theory (DFT). The TMs considered herein include Sc, V, Fe, Co, Ni, Cu, Y, Zr, and Nb, which substitute for Mg at a doping concentration of 3.125 % in both the hydrides. This insertion of TMs causes a variation in the cell volumes of β- and γ-MgH2 . The majority of the TM dopants decrease the lattice constants, with Ni resulting in the largest reduction. From the formation-energy calculations, it is predicted that except for Cu and Ni, the mixing of all the selected TM dopants with the MgH2 phases is exothermic. The selected TMs also influence the stability of both β- and γ-MgH2 and cause destabilization by weakening the MgH bonds. Our results show that doping with certain TMs can facilitate desorption of hydrogen from β- and γ-MgH2 at much lower temperatures than from their pure forms. The hydrogen adsorption strengths are also studied by density-of-states analysis.

  9. The development of microstructure during hydrogenation-disproportionation-desorption-recombination treatment of sintered neodymium-iron-boron-type magnets

    NASA Astrophysics Data System (ADS)

    Sheridan, R. S.; Harris, I. R.; Walton, A.

    2016-03-01

    The hydrogen absorption and desorption characteristics of the hydrogenation disproportionation desorption and recombination (HDDR) process on scrap sintered neodymium-iron-boron (NdFeB) type magnets have been investigated. At each stage of the process, the microstructural changes have been studied using high resolution scanning electron microscopy. It was found that the disproportionation reaction initiates at grain boundaries and triple points and then propagates towards the centre of the matrix grains. This process was accelerated at particle surfaces and at free surfaces produced by any cracks in the powder particles. However, the recombination reaction appeared to initiate randomly throughout the particles with no apparent preference for particle surfaces or internal cracks. During the hydrogenation of the grain boundaries and triple junctions, the disproportionation reaction was, however, affected by the much higher oxygen content of the sintered NdFeB compared with that of the as-cast NdFeB alloys. Throughout the entire HDDR reaction the oxidised triple junctions (from the sintered structure) remained unreacted and hence, remained in their original form in the fine recombined microstructure. This resulted in a very significant reduction in the proportion of cavitation in the final microstructure and this could lend to improved consolidation in the recycled magnets.

  10. The Effects of Added Hydrogen on Noble Gas Discharges Used as Ambient Desorption/Ionization Sources for Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Ellis, Wade C.; Lewis, Charlotte R.; Openshaw, Anna P.; Farnsworth, Paul B.

    2016-09-01

    We demonstrate the effectiveness of using hydrogen-doped argon as the support gas for the dielectric barrier discharge (DBD) ambient desorption/ionization (ADI) source in mass spectrometry. Also, we explore the chemistry responsible for the signal enhancement observed when using both hydrogen-doped argon and hydrogen-doped helium. The hydrogen-doped argon was tested for five analytes representing different classes of molecules. Addition of hydrogen to the argon plasma gas enhanced signals for gas-phase analytes and for analytes coated onto glass slides in positive and negative ion mode. The enhancements ranged from factors of 4 to 5 for gas-phase analytes and factors of 2 to 40 for coated slides. There was no significant increase in the background. The limit of detection for caffeine was lowered by a factor of 79 using H2/Ar and 2 using H2/He. Results are shown that help explain the fundamental differences between the pure-gas discharges and those that are hydrogen-doped for both argon and helium. Experiments with different discharge geometries and grounding schemes indicate that observed signal enhancements are strongly dependent on discharge configuration.

  11. The Effects of Added Hydrogen on Noble Gas Discharges Used as Ambient Desorption/Ionization Sources for Mass Spectrometry.

    PubMed

    Ellis, Wade C; Lewis, Charlotte R; Openshaw, Anna P; Farnsworth, Paul B

    2016-09-01

    We demonstrate the effectiveness of using hydrogen-doped argon as the support gas for the dielectric barrier discharge (DBD) ambient desorption/ionization (ADI) source in mass spectrometry. Also, we explore the chemistry responsible for the signal enhancement observed when using both hydrogen-doped argon and hydrogen-doped helium. The hydrogen-doped argon was tested for five analytes representing different classes of molecules. Addition of hydrogen to the argon plasma gas enhanced signals for gas-phase analytes and for analytes coated onto glass slides in positive and negative ion mode. The enhancements ranged from factors of 4 to 5 for gas-phase analytes and factors of 2 to 40 for coated slides. There was no significant increase in the background. The limit of detection for caffeine was lowered by a factor of 79 using H2/Ar and 2 using H2/He. Results are shown that help explain the fundamental differences between the pure-gas discharges and those that are hydrogen-doped for both argon and helium. Experiments with different discharge geometries and grounding schemes indicate that observed signal enhancements are strongly dependent on discharge configuration. Graphical Abstract ᅟ.

  12. Control of Uniform and Interconnected Macroporous Structure in PolyHIPE for Enhanced CO2 Adsorption/Desorption Kinetics.

    PubMed

    Wang, Quanyong; Liu, Yao; Chen, Jian; Du, Zhongjie; Mi, Jianguo

    2016-07-19

    The highly uniform and interconnected macroporous polymer materials were prepared within the high internal phase hydrosol-in-oil emulsions (HIPEs). Impregnated with polyethylenimine (PEI), the polyHIPEs were then employed as solid adsorbents for CO2 capture. Thermodynamic and kinetic capture-and-release tests were performed with pure CO2, 10% CO2/N2, and moist CO2, respectively. It has shown that the polyHIPE with suitable surface area and PEI impregnation exhibits high CO2 adsorption capacity, remarkable CO2/N2 selectivity, excellent adsorption/desorption kinetics, enhanced efficiency in the presence of water, and admirable stability in capture and release cycles. The results demonstrate the superior comprehensive performance of the present PEI-impregnated polyHIPE for CO2 capture from the postcombustion flue gas.

  13. DESORPTION KINETICS OF NEUTRAL HYDROPHOBIC ORGANIC COMPOUNDS FROM FIELD CONTAMINATED SEDIMENT. (R825513C024)

    EPA Science Inventory

    The chemical release rates from a field-contaminated sediment (Lake Charles, LA) using Tenax desorption were studied. Two dichlorobenzenes (m-, p-), hexachlorobutadiene, and hexachlorobenzene were investigated. Contrary to reports that sorption rates are inversel...

  14. Desorption Kinetics of H2O, H2, CO, and CO2 from Silica Reinforced Polysiloxane

    SciTech Connect

    Dinh, L.; Balooch, M.

    1999-08-11

    We performed temperature programmed desorption up to 500K on silica-reinforced polysiloxane in both solid and foamed forms (M9787 and M9750 respectively). Our data show that H{sub 2}O was the dominant desorbing species in both forms of silicone (on the order of 100 {micro}g of physisorbed water and 900 {micro}g of chemisorbed water per gram of polymer), which are expected to be very hydrophilic when dehydrated. Detailed studies of the TPD spectra of H{sub 2}O from the silicones and from the fumed silica fillers suggest that H{sub 2}O molecules preferentially adsorbed on the surface of silica particles contained in the silicones with activation energies of desorption of 15 {+-} 3 kcal/mol and 50 {+-} 10 kcal/mol. There was strong evidence of H{sub 2} desorption below 400K from the silicones. The equivalent concentration of H{sub 2} in the silicones was 0.44 {micro}g of H{sub 2} per gram of silicone. Other species desorbing from the silicones were CO, and CO{sub 2} with concentrations on the order of 2.5 {micro}g, and 1.6 {micro}g per gram of silicone and activation energies of desorption of 10 {+-} 2 kcal/mol and 9.5 {+-} 1.5 kcal/mol, respectively.

  15. Uncertainty analysis of multi-rate kinetics of uranium desorption from sediments

    SciTech Connect

    Zhang, Xiaoying; Liu, Chongxuan; Hu, Bill X.; Zhang, Guannan

    2014-01-01

    A multi-rate expression for uranyl [U(VI)] surface complexation reactions has been proposed to describe diffusion-limited U(VI) sorption/desorption in heterogeneous subsurface sediments. An important assumption in the rate expression is that its rate constants follow a certain type probability distribution. In this paper, a Bayes-based, Differential Evolution Markov Chain method was used to assess the distribution assumption and to analyze parameter and model structure uncertainties. U(VI) desorption from a contaminated sediment at the US Hanford 300 Area, Washington was used as an example for detail analysis. The results indicated that: 1) the rate constants in the multi-rate expression contain uneven uncertainties with slower rate constants having relative larger uncertainties; 2) the lognormal distribution is an effective assumption for the rate constants in the multi-rate model to simualte U(VI) desorption; 3) however, long-term prediction and its uncertainty may be significantly biased by the lognormal assumption for the smaller rate constants; and 4) both parameter and model structure uncertainties can affect the extrapolation of the multi-rate model with a larger uncertainty from the model structure. The results provide important insights into the factors contributing to the uncertainties of the multi-rate expression commonly used to describe the diffusion or mixing-limited sorption/desorption of both organic and inorganic contaminants in subsurface sediments.

  16. Highly improved hydrogen storage capacity and kinetics of the nanocrystalline and amorphous PrMg12-type alloys by mechanical milling

    NASA Astrophysics Data System (ADS)

    Zhang, Y. H.; Shang, H. W.; Li, Y. Q.; Yuan, Z. M.; Yang, T.; Zhao, D. L.

    2017-01-01

    Nanocrystalline and amorphous PrMg11Ni + x wt.% Ni (x = 100, 200) alloys were synthesized by mechanical milling. Effects of Ni content and milling duration on the structures, hydrogen storage capacity and kinetics of the as-milled alloys were investigated systematically. The structures were characterized by XRD and HRTEM. The hydrogen desorption activation energy was calculated by using Kissinger method. The results show that increasing Ni content dramatically improves the electrochemical discharge capacity of the as-milled alloys. Furthermore, the variation of milling time has a significant impact on the kinetics of the alloys. As the milling time increased, the high-rate discharge ability (HRD), gaseous hydrogen absorption capacity and hydrogenation rate increased at first but decreased finally, while the dehydrogenation rate always increased.

  17. Kinetic desorption of fluoride in a granitic soil column: Experiments and reactive transport modeling

    NASA Astrophysics Data System (ADS)

    Padhi, S.; Tokunaga, T.

    2016-12-01

    The transport of fluoride or other contaminants in subsurface largely depends on their interaction with mineral surfaces of contact. Hence, the methods to evaluate and predict the extent of these interactions are of great importance. The commonly used distribution coefficient (Kd) model does not account for temporally and spatially variable geochemical conditions (Curtis et al., 2006). This study aims to investigate the reactive transport of fluoride in a natural soil column by laboratory experiments and solute transport modeling by introducing surface complexation of fluoride to the transport simulation. For our purpose, column experiments for fluoride sorption and desorption under saturated conditions were conducted in the laboratory on a granitic soil from Tsukuba, Japan. Stable isotopes of water (δ18O and δ2H) were used as conservative tracers to evaluate the flow and transport properties. Existence of physical and chemical nonequilibrium during fluoride transport was evaluated by applying stop flow events. Long tailing during fluoride desorption was observed, and the linear Kd model failed to explain this phenomenon. Hence, a geochemical model considering fluoride sorption in soil by surface complexation was developed to explain fluoride transport in the column. The intrinsic surface complexation constants for fluoride sorption reactions and surface site protonation and deprotonation reactions were corrected from that of the optimized results from batch experiments based as suggested by Sverjensky (2003). The model with fluoride sorption defined by surface complexation explained the observed fluoride desorption data quite satisfactorily, especially the long tailing. An overshoot in the breakthrough curve observed by the simulation during early period of desorption could be due to competitive desorption, which need to be further analyzed. References: (1) Curtis, JP, Davis, JA, Nafiz, DL 2006. Wat. Res. Res., 42, W04404, doi:10.1029/2005WR003979; (2

  18. Thermo-kinetics study of laser-induced desorption of self-assembled monolayers from gold: case of laser micropatterning.

    PubMed

    Shadnam, Mohammad R; Kirkwood, Sean E; Fedosejevs, Robert; Amirfazli, A

    2005-06-23

    Laser-induced desorption of self-assembled monolayers (SAMs) from gold surfaces within context of the direct laser patterning methodology was investigated through combining results of a heat diffusion thermal model with desorption kinetics of alkanethiol SAMs. It was found that contrast plots of experimental scanning electron microscopy (SEM) images, which are correlated to surface coverage of SAMs desorbed after laser irradiation, agreed with the theoretically predicted surface composition of SAMs. The surface composition of SAM was then interpreted in terms of the wetting property of the resulting surface. The effect of incident laser beam power and size on the final spatial coverage of SAMs on the surface and feature sizes was investigated both experimentally and by modeling. Theoretical modeling and experimental evidence showed that the resulting feature sizes are wider when the surface is heated by a laser of higher power. Increasing the laser beam size results in broadening of feature sizes. Considering the correlation of the theoretical and experimental results, we concluded that the feature sizes are controllable in a predictable way (using the presented thermal-kinetics model) through varying laser beam power and beam size.

  19. Simultaneous quantification of soil phosphorus labile pool and desorption kinetics using DGTs and 3D-DIFS

    NASA Astrophysics Data System (ADS)

    Menezes-Blackburn, Daniel; Sun, Jiahui; Lehto, Niklas; Zhang, Hao; Stutter, Marc; Giles, Courtney D.; Darch, Tegan; George, Timothy S.; Shand, Charles; Lumsdon, David; Blackwell, Martin; Wearing, Catherine; Cooper, Patricia; Wendler, Renate; Brown, Lawrie; Haygarth, Philip M.

    2017-04-01

    The phosphorus (P) labile pool and desorption kinetics were simultaneously evaluated in ten representative UK soils using the technique of Diffusive gradients in thin films (DGT). The DGT-induced fluxes in soil and sediments model (DIFS) was fitted to the time series of DGT deployment (1h to 240h). The desorbable P concentration (labile P) was obtained by multiplying the fitted Kd by the soil solution P concentration obtained using Diffusive Equilibration in Thin Films (DET) devices. The labile P was then compared to several soil P extracts including Olsen P, Resin P, FeO-P and water extractable P, in order to assess if these analytical procedures can be used to represent the labile P across different soils. The Olsen P, commonly used as a representation of the soil labile P pool, overestimated the desorbable P concentration by a seven fold factor. The use of this approach for the quantification of soil P desorption kinetics parameters was somewhat unprecise, showing a wide range of equally valid solutions for the response of the system P equilibration time (Tc). Additionally, the performance of different DIFS model versions (1D, 2D and 3D) was compared. Although these models had a good fit to experimental DGT time series data, the fitted parameters showed a poor agreement between different model versions. The limitations of the DIFS model family are associated with the assumptions taken in the modelling approach and the 3D version is here considered to be the most precise among them.

  20. Desorption kinetics of chlorobenzenes, polycyclic aromatic hydrocarbons, and polychlorinated biphenyls: Sediment extraction with Tenax{reg_sign} and effects of contact time and solute hydrophobicity

    SciTech Connect

    Cornelissen, G.; Noort, P.C.M. van; Govers, H.A.J.

    1997-07-01

    A technique using Tenax TA{reg_sign} beads as sink for desorbed solute was employed to measure the kinetics of desorption of chlorobenzenes, polychlorinated biphenyls, and polycyclic aromatic hydrocarbons from laboratory-contaminated sediment. First-order rate constants of rapid and slow desorption were in the order of 10{sup {minus}1}/h and 10{sup {minus}3}/h, respectively. The rate constants of slow desorption correlate well with the molecular volumes of the compounds used and decrease between 2 and 34 d of equilibration. Slowly desorbing fractions increase with both increasing solute hydrophobicity and increasing equilibration time.

  1. The electrocatalytic hydrogenation of glucose; 1: Kinetics of hydrogen evolution and glucose hydrogenation on Raney nickel powder

    SciTech Connect

    Anantharaman, V.; Pintauro, P.N. . Dept. of Chemical Engineering)

    1994-10-01

    The kinetics of H[sub 2] evolution and glucose reduction to sorbitol was investigated using a batch slurry reactor containing Raney nickel powder catalyst. In the presence and absence of glucose, hydrogen evolution proceeds via a Volmer-Heyrovsky mechanism, with both steps simultaneously rate controlling at low overpotentials and the Volmer reaction rate limiting at high cathodic overvoltages. A kinetic model for the electrocatalytic hydrogenation of glucose with simultaneous H[sub 2] generation was developed and tested. The model contains rate equations for the individual Volmer, Heyrovsky, and glucose hydrogenation steps, a Langmuir adsorption isotherm for glucose, an equation describing the shift in open-circuit potential due to glucose adsorption on the nickel catalyst, and steady-state atomic hydrogen and charge balance relationships. The theory accurately predicted potentiostatic polarization data and glucose hydrogenation rates. The results indicate that the mechanism for sorbitol formation with electrogenerated atomic hydrogen on Raney nickel is the same as that for the high temperature and pressure chemical catalytic hydrogenation process.

  2. Chemical kinetic performance losses for a hydrogen laser thermal thruster

    NASA Technical Reports Server (NTRS)

    Mccay, T. D.; Dexter, C. E.

    1985-01-01

    Projected requirements for efficient, economical, orbit-raising propulsion systems have generated investigations into several potentially high specific impulse, moderate thrust, advanced systems. One of these systems, laser thermal propulsion, utilizes a high temperature plasma as the enthalpy source. The plasma is sustained by a focused laser beam which maintains the plasma temperature at levels near 20,000 K. Since such temperature levels lead to total dissociation and high ionization, the plasma thruster system potentially has a high specific impulse decrement due to recombination losses. The nozzle flow is expected to be sufficiently nonequilibrium to warrant concern over the achievable specific impluse. This investigation was an attempt at evaluation of those losses. The One-Dimensional Kinetics (ODK) option of the Two-Dimensional Kinetics (TDK) Computer Program was used with a chemical kinetics rate set obtained from available literature to determine the chemical kinetic energy losses for typical plasma thruster conditions. The rates were varied about the nominal accepted values to band the possible losses. Kinetic losses were shown to be highly significant for a laser thermal thruster using hydrogen. A 30 percent reduction in specific impulse is possible simply due to the inability to completely extract the molecular recombination energy.

  3. Kinetic modelling of molecular hydrogen transport in microporous carbon materials.

    PubMed

    Hankel, Marlies; Zhang, Hong; Nguyen, Thanh X; Bhatia, Suresh K; Gray, Stephen K; Smith, Sean C

    2011-05-07

    The proposal of kinetic molecular sieving of hydrogen isotopes is explored by employing statistical rate theory methods to describe the kinetics of molecular hydrogen transport in model microporous carbon structures. A Lennard-Jones atom-atom interaction potential is utilized for the description of the interactions between H(2)/D(2) and the carbon framework, while the requisite partition functions describing the thermal flux of molecules through the transition state are calculated quantum mechanically in view of the low temperatures involved in the proposed kinetic molecular sieving application. Predicted kinetic isotope effects for initial passage from the gas phase into the first pore mouth are consistent with expectations from previous modeling studies, namely, that at sufficiently low temperatures and for sufficiently narrow pore mouths D(2) transport is dramatically favored over H(2). However, in contrast to expectations from previous modeling, the absence of any potential barrier along the minimum energy pathway from the gas phase into the first pore mouth yields a negative temperature dependence in the predicted absolute rate coefficients-implying a negative activation energy. In pursuit of the effective activation barrier, we find that the minimum potential in the cavity is significantly higher than in the pore mouth for nanotube-shaped models, throwing into question the common assumption that passage through the pore mouths should be the rate-determining step. Our results suggest a new mechanism that, depending on the size and shape of the cavity, the thermal activation barrier may lie in the cavity rather than at the pore mouth. As a consequence, design strategies for achieving quantum-mediated kinetic molecular sieving of H(2)/D(2) in a microporous membrane will need, at the very least, to take careful account of cavity shape and size in addition to pore-mouth size in order to ensure that the selective step, namely passage through the pore mouth, is also

  4. Kinetic modelling of molecular hydrogen transport in microporous carbon materials.

    SciTech Connect

    Hankel, M.; Zhang, H.; Nguyen, T. X.; Bhatia, S. K.; Gray, S. K.; Smith, S. C.

    2011-01-01

    The proposal of kinetic molecular sieving of hydrogen isotopes is explored by employing statistical rate theory methods to describe the kinetics of molecular hydrogen transport in model microporous carbon structures. A Lennard-Jones atom-atom interaction potential is utilized for the description of the interactions between H{sub 2}/D{sub 2} and the carbon framework, while the requisite partition functions describing the thermal flux of molecules through the transition state are calculated quantum mechanically in view of the low temperatures involved in the proposed kinetic molecular sieving application. Predicted kinetic isotope effects for initial passage from the gas phase into the first pore mouth are consistent with expectations from previous modeling studies, namely, that at sufficiently low temperatures and for sufficiently narrow pore mouths D{sub 2} transport is dramatically favored over H{sub 2}. However, in contrast to expectations from previous modeling, the absence of any potential barrier along the minimum energy pathway from the gas phase into the first pore mouth yields a negative temperature dependence in the predicted absolute rate coefficients - implying a negative activation energy. In pursuit of the effective activation barrier, we find that the minimum potential in the cavity is significantly higher than in the pore mouth for nanotube-shaped models, throwing into question the common assumption that passage through the pore mouths should be the rate-determining step. Our results suggest a new mechanism that, depending on the size and shape of the cavity, the thermal activation barrier may lie in the cavity rather than at the pore mouth. As a consequence, design strategies for achieving quantum-mediated kinetic molecular sieving of H{sub 2}/D{sub 2} in a microporous membrane will need, at the very least, to take careful account of cavity shape and size in addition to pore-mouth size in order to ensure that the selective step, namely passage

  5. Properties of hydrogenation-disproportionation-desorption-recombination NdFeB powders prepared from recycled sintered magnets

    NASA Astrophysics Data System (ADS)

    Périgo, E. A.; da Silva, S. C.; Martin, R. V.; Takiishi, H.; Landgraf, F. J. G.

    2012-04-01

    The effects of the hydrogenation-disproportionation-desorption-recombination (HDDR) processing conditions on the microstructure and magnetic properties of NdFeB powders prepared from recycling sintered N42 grade magnets were evaluated. Temperatures below 840 oC and above 900 oC are deleterious to HDDR powders' properties. The hydrogen pressure, ranging from 60 to 135 kPa, has a major influence on the remanence compared to that on the intrinsic coercivity. The best magnetic properties (Jr = 0.58 T and μ0Hc = 1.15 T) were obtained with Trecomb = 860 °C, PH2 = 135 kPa, and trecomb = 330 s. Such coercivity value corresponds to 93% of the starting material, not achieved yet by optimizing the HDDR process and without using Dy.

  6. Synthesis and crystal structure of a Pr5Ni19 superlattice alloy and its hydrogen absorption-desorption property.

    PubMed

    Iwase, Kenji; Sakaki, Kouji; Matsuda, Junko; Nakamura, Yumiko; Ishigaki, Toru; Akiba, Etsuo

    2011-05-16

    The intermetallic compound Pr(5)Ni(19), which is not shown in the Pr-Ni binary phase diagram, was synthesized, and the crystal structure was investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Two superlattice reflections with the Sm(5)Co(19)-type structure (002 and 004) and the Pr(5)Co(19)-type structure (003 and 006) were observed in the 2θ region between 2° and 15° in the XRD pattern using Cu Kα radiation. Rietveld refinement provided the goodness-of-fit parameter S = 6.7 for the Pr(5)Co(19)-type (3R) structure model and S = 1.7 for the Sm(5)Co(19)-type (2H) structure model, indicating that the synthesized compound has a Sm(5)Co(19) structure. The refined lattice parameters were a = 0.50010(9) nm and c = 3.2420(4) nm. The high-resolution TEM image also clearly revealed that the crystal structure of Pr(5)Ni(19) is of the Sm(5)Co(19) type, which agrees with the results from Rietveld refinement of the XRD data. The P-C isotherm of Pr(5)Ni(19) in the first absorption was clearly different from that in the first desorption. A single plateau in absorption and three plateaus in desorption were observed. The maximum hydrogen storage capacity of the first cycle reached 1.1 H/M, and that of the second cycle was 0.8 H/M. The 0.3 H/M of hydrogen remained in the metal lattice after the first desorption process.

  7. Kinetic Method for Hydrogen-Deuterium-Tritium Mixture Distillation Simulation

    SciTech Connect

    Sazonov, A.B.; Kagramanov, Z.G.; Magomedbekov, E.P.

    2005-07-15

    Simulation of hydrogen distillation plants requires mathematical procedures suitable for multicomponent systems. In most of the present-day simulation methods a distillation column is assumed to be composed of theoretical stages, or plates. However, in the case of a multicomponent mixture theoretical plate does not exist.An alternative kinetic method of simulation is depicted in the work. According to this method a system of mass-transfer differential equations is solved numerically. Mass-transfer coefficients are estimated with using experimental results and empirical equations.Developed method allows calculating the steady state of a distillation column as well as its any non-steady state when initial conditions are given. The results for steady states are compared with ones obtained via Thiele-Geddes theoretical stage technique and the necessity of using kinetic method is demonstrated. Examples of a column startup period and periodic distillation simulations are shown as well.

  8. Isotherms and Kinetics of Water Vapor Sorption/Desorption for Surface Films of Polyion-Surfactant Ion Complex Salts.

    PubMed

    Gustavsson, Charlotte; Piculell, Lennart

    2016-07-14

    Thin films of "complex salts" (CS = ionic surfactants with polymeric counterions) have recently been shown to respond to humidity changes in ambient air by changing their liquid crystalline structure. We here report isotherms and kinetics of water sorption/desorption for ∼10-100 μm films of alkyltrimethylammonium polyacrylate CS, measured in a dynamic gravimetric vapor sorption instrument over a 0-95% relative humidity (RH) range. The sorption per ion pair was similar to that observed for common ionomers. A kinetic model for the water exchange is presented, assuming that the "external" transport between the vapor reservoir and the film surface is rate-determining. The model predicts that the water content, after a small stepwise change of the reservoir RH, should vary exponentially with time, with a time constant proportional to both the slope of the sorption isotherm and the film thickness. These predictions were confirmed for our films over large RH ranges, and the external mass transfer coefficient in our setup was calculated from the experimental data. Expressions derived for the Biot number (ratio of characteristic times for internal and external water transport) for the considered limiting case strongly indicate that external water transport should quite generally affect, or even dominate, the measured kinetics for similarly thin hydrated films.

  9. Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on Forsterite, Mg2SiO4(011)

    SciTech Connect

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

    2014-12-18

    We have examined the adsorbate-substrate interaction kinetics of CO2 and H2O on a natural forsterite crystal surface, Mg2SiO4(011), with 10-15% of substitutional Fe2+. We use temperature programmed desorption (TPD) and molecular beam techniques to determine the adsorption, desorption, and displacement kinetics for H2O and CO2. Neither CO2 nor H2O has distinct sub-monolayer desorption peaks but instead both have a broad continuous desorption feature that evolve smoothly into multilayer desorption. Inversion of the monolayer coverage spectra for both molecules reveals that the corresponding binding energies for H2O are greater than that for CO2 on all sites. The relative strength of these interactions is the dominant factor in the competitive adsorption/displacement kinetics. In experiments where the two adsorbates are co-dosed, H2O always binds to the highest energy binding sites available and displaces CO2. The onset of CO2 displacement by H2O occurs between 65 and 75 K.

  10. Influence of bisolute competition on the desorption kinetics of polycyclic aromatic hydrocarbons in soil

    SciTech Connect

    White, J.C.; Pignatello, J.J.

    1999-12-01

    The dual-mode (partition/hole-filling) model of soil organic matter (SOM) as a heterogeneous polymerlike sorbent of hydrophobic compounds predicts that a competing solute will accelerate diffusion of the primary solute by blocking the holes, allowing the principal solute to move faster through the SOM matrix. The authors tested this hypothesis with phenanthrene as the primary solute and pyrene as the competing solute in two sterile soils of widely different organic carbon content. Two- and 33-d isotherms of phenanthrene in both soil were nonlinear indicating a heterogeneous distribution of sites. Pyrene suppressed phenanthrene sorption and increased the linearity of its isotherm. Uptake (adsorption) rates were measured in batch systems after preincubating with pyrene. Desorption was measured by the sequential dilution technique at constant pyrene concentration in the supernatant. The design of the experiment precluded comparison of adsorption rates, but desorption rates increased significantly (but not dramatically) as a function of pyrene concentration. Moreover, the effect was noticeable even at low and roughly equimolar concentrations of the two compounds. The effect was qualitatively similar in the two soils, implicating SOM as the matrix in which the effect takes place. The results suggest that the competing solute excludes the primary solute from less mobile sorption domains in SOM. Interpreted according to the polymer model, this exclusion is postulated to occur by a hole-plugging (competitive displacement) mechanism possibly in concert with penetrant-induced plasticization of SOM which leads to destruction of holes.

  11. Sorption and desorption kinetics and isotherms of volatile methylsiloxanes with atmospheric aerosols.

    PubMed

    Kim, Jaeshin; Xu, Shihe

    2016-02-01

    This study investigated sorption and desorption behaviors of airborne volatile methylsiloxanes (VMS) such as octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) on nine major primary and secondary atmospheric aerosols at a relative humidity (RH) of 30%. It was found that sorption and desorption of VMS took place via a two-phase process, which included an initial rapid step, followed by slower subsequent step. The initial rapid step was favored especially at low concentrations. Equilibrium sorption isotherms were slightly better fitted to Polanyi-Manes sorption model than Langmuir model except D4 on black carbon and D5 on sea salt. Values of apparent aerosol-air partition coefficients ranged 0.09-50.4 L/m(2) for D4 and 2.1-284 L/m(2) for D5 with carbon black having the largest values. Some of aerosols such as carbon black and sea salts reversibly interacted with D4 and D5 whereas other aerosols such as kaolinite and sulfates showed highly irreversible sorption for the VMS, especially at low concentrations. As sorption density of D4 and D5 on kaolinite was decreased from 1100 to 250 µg/m(2), the irreversible fraction was increased from 27% to 80%.The mechanism responsible for these differences is essential for a better understanding and prediction of atmospheric chemistry of VMS as affected by the presence of atmospheric aerosols.

  12. Ultra high vacuum high precision low background setup with temperature control for thermal desorption mass spectroscopy (TDA-MS) of hydrogen in metals.

    PubMed

    Merzlikin, Sergiy V; Borodin, S; Vogel, D; Rohwerder, M

    2015-05-01

    In this work, a newly developed UHV-based high precision low background setup for hydrogen thermal desorption analysis (TDA) of metallic samples is presented. Using an infrared heating with a low thermal capacity enables a precise control of the temperature and rapid cool down of the measurement chamber. This novel TDA-set up is superior in sensitivity to almost every standard hydrogen analyzer available commercially due to the special design of the measurement chamber, resulting in a very low hydrogen background. No effects of background drift characteristic as for carrier gas based TDA instruments were observed, ensuring linearity and reproducibility of the analysis. This setup will prove to be valuable for detailed investigations of hydrogen trapping sites in steels and other alloys. With a determined limit of detection of 5.9×10(-3)µg g(-1) hydrogen the developed instrument is able to determine extremely low hydrogen amounts even at very low hydrogen desorption rates. This work clearly demonstrates the great potential of ultra-high vacuum thermal desorption mass spectroscopy instrumentation. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Desorption kinetics of N,N-dimethylformamide vapor from granular activated carbon and hydrophobic zeolite

    SciTech Connect

    Ching-Yuan Chang; Wen-Tien Tsai; Horng-Chia Lee

    1996-07-01

    Such thermodynamic properties as enthalpy, free energy, and entropy of adsorption have been computed for N,N-dimethylformamide (DMF) vapor on two commercial adsorbents: coconut shell Type PCB of activated carbon and Type DAY of hydrophobic zeolite. The computation is based on the Langmuir adsorption isotherms obtained at 293, 303, and 313 K as reported by Tsai et al. The laden adsorbents were regenerated with hot inert nitrogen gas and studied by thermal gravimetric analysis at three different heating rates. The apparent activation energies (E{sub des}) of thermal desorption were determined by using the Friedman method. The zeolite DAY has an adsorption potential higher than that of activated carbon PCB as indicated by the more negative value of the adsorption enthalpy of DMF vapor. The average value of E{sub des} of zeolite DAY is larger than that of activated carbon PCB.

  14. The kinetics of hydrogen diffusion in single crystal orthopyroxene

    NASA Astrophysics Data System (ADS)

    Carpenter, Susan Jean

    The kinetics of hydrogen diffusion in single crystals of orthopyroxene were investigated parallel to the [100], [010] and [001] crystallographic directions during dehydration and hydrogenation. The two groups of samples investigated spanned a range of metal composition, most notably iron, 4.5--8.5 wt % FeO, and aluminum, 2.1--3.5 wt % Al2O3; the aluminum was bound in both regular metal sites (AlVI) and in tetrahedral sites (AlIV). Xenolithic crystals from the San Carlos, Arizona, region contain on average, about 5.3 wt % FeO and 2.4 wt % Al2O3, and the gem-quality crystals from Sri Lanka contain between 4.5 and 8.5 wt % FeO, and between 2.1 and 3.6 wt % Al 2O3. Dehydration was performed in a 1 atm gas-mixing furnace at temperatures between 800 and 1100°C, using mixtures of CO and CO 2 to maintain the oxygen fugacity at 10-14 atm, close to the nickel/nickel oxide (NNO) solid buffer. Hydrogenation was performed in a piston-cylinder apparatus at 1 GPa within the same range of temperatures, using welded platinum capsules to contain the samples, water and NNO solid buffer. After a heating event, samples were polished so that the central region of the crystal could be analyzed. Changes in hydrogen concentration as a function of heating time were plotted as hydroxyl concentration profiles across the central sections of the samples, obtained by using polarized FTIR spectroscopy with the electric vector E, oriented parallel to the c crystallographic direction, the direction in which hydroxyl dipoles in clinopyroxene are primarily oriented. Hydrogen diffusivities were obtained by fitting the hydroxyl concentration profiles to theoretical profiles generated by finite solution numerical modeling for diffusion within a finite slab to/from an infinite source. During dehydration, hydrogen diffusion was found to be anisotropic in San Carlos enstatite and isotropic in the Sri Lankan samples, with more rapid hydrogen diffusion occurring in the Sri Lankan samples that contain

  15. The desorption and reactivity of butanol adsorbed on lithium iron phosphate (LISICON) activated in a hydrogen plasma

    NASA Astrophysics Data System (ADS)

    Pylinina, A. I.; Mikhalenko, I. I.; Yagodovskaya, T. V.; Yagodovskii, V. D.

    2010-12-01

    The reactivity and desorption of butanol-2 adsorbed on Li3Fe2(PO4)3 not subjected and subjected to treatment in a glow discharge hydrogen plasma were studied under flow conditions with a gas chromatographic analysis of products. X-ray photoelectron spectroscopy data showed that the number of phosphate groups on the surface of the phosphate was two times larger than the stoichiometric number and increased after plasma chemical treatment. The strength of butanol-phosphate bonds also increased, and the selectivity of alcohol decomposition with the formation of an olefin (dehydration) and ketone (dehydrogenation) changed. After plasma treatment, dehydrogenation centers were deactivated. The selectivities of alcohol transformations in the adsorbed state and under vapor phase conditions were different. Ketone was formed from adsorbed alcohol because the activation energies of dehydrogenation were equal for the two reaction variants.

  16. Magnetization processes in two different types of anisotropic, fully dense NdFeB hydrogenation, disproportionation, desorption, and recombination magnets

    NASA Astrophysics Data System (ADS)

    Gutfleisch, O.; Eckert, D.; Schäfer, R.; Müller, K. H.; Panchanathan, V.

    2000-05-01

    Two types of textured, fully dense NdFeB hydrogenation, disproportionation, desorption, and recombination (HDDR) magnets were produced. The first type was produced by hot pressing isotropic HDDR powder followed by die upsetting; the second, by hot pressing prealigned, anisotropic HDDR powder (MQA-T). Studies of the magnetization processes revealed that for isotropic HDDR powder and its hot pressed and die-upset magnets a much larger initial susceptibility is found after thermal demagnetization than after reverse dc-field demagnetization. Prealigned, hot pressed magnets made from MQA-T material showed a different virgin magnetization curve, indicating a unique coercivity mechanism. Interaction domains larger than the average grain size can be observed in both cases by Kerr microscopy, with the MQA-T type showing significantly broader interaction domains.

  17. 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

    2014-10-09

    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.

  18. Kinetics of quinoline biodegradation, sorption and desorption in a clay-coated model soil containing a quinoline-degrading bacterium

    NASA Astrophysics Data System (ADS)

    McBride, J. F.; Brockman, F. J.; Szecsody, J. E.; Streile, G. P.

    1992-01-01

    Kinetics of quinoline biodegradation, sorption and desorption in a clay-coated model soil containing a quinoline-degrading bacterium. Studies were initiated to compare the kinetics of quinoline sorption/desorption and biodegradation in order to predict the relative importance of abiotic and biotic processes in the transport of quinoline in columns containing a model soil. Initial biodegradation studies were conducted in a 1-cm-long column containing a quinoline-degrading bacterium (10 9 colony-forming units g -1 porous medium) attached to 100- to 150-μm-diameter glass beads that did not sorb quinoline. At a 155-nmol mL -1 quinoline influent concentration, the maximum consumption rate was 104.7 nmol quinoline min -1 cm -3 pore volume. In contrast, the maximum consumption rate of the first metabolite ( 2-hydroxyquinoline) was 24.8 nmol mL -1 cm -3 pore volume. In a second experiment, bacteria were mixed with a model soil, consisting of montmorillonite bound to alumina particles (75- to 180-μm diameter). In a 1-cm-long column of the model soil, the quinoline consumption rate at a 155-nmol mL -1 quinoline influent concentration was similar to that obtained in the glass-bead column, showing that the clay does not substantially affect quinoline biodegradation at equilibrium conditions. In a third series of experiments, sorption to the model soil was examined in the absence of microorganisms. The observed desorption rate coefficient for quinoline averaged 1.1·10 -3 s -1, which was one to three orders of magnitude smaller than was observed for 45Ca. The slow ion exchange of quinoline on the clay surface is controlled by a site-specific quinoline/montmorillonite interaction and not a larger-scale physical step (i.e. interparticle diffusion). Equilibrium first-order forward (sorption) and reverse (desorption) mass fluxes were 1160 nmol cm -1 cm -3 pore volume with a 155-nmol mL -1 quinoline influent concentration. The initial quinoline mass flux to the clay was estimated

  19. Kinetics of thermoneutral intermolecular hydrogen migration in alkyl radicals.

    PubMed

    Ratkiewicz, Artur; Bankiewicz, Barbara; Truong, Thanh N

    2010-09-28

    High pressure limits of thermal rate constants of intramolecular hydrogen migrations, particularly 1,3 to 1,6 H-shift in propyl, butyl, pentyl and hexyl radicals, respectively, were calculated using the canonical variational transition state theory (CVT) with a multi-dimensional small-curvature tunneling (SCT) correction over the temperature range of 300-3000 K. The CCSD(T)/cc-pVDZ//BH&HLYP/cc-pVDZ method was used to provide necessary potential energy surface information. Rate constants for these reactions were used to extrapolate rate constants for reactions of larger alkyls where experimental data are available using the Reaction Class Transition State Theory (RC-TST). Excellent agreement with experimental data confirms the validity of the RC-TST methodology and the accuracy of the calculated kinetic data in this study.

  20. Kinetics of CO{sub 2} desorption from highly concentrated and CO{sub 2}-loaded methyldiethanolamine aqueous solutions in the range 312--383 K

    SciTech Connect

    Cadours, R.; Bouallou, C.; Gaunand, A.; Richon, D.

    1997-12-01

    Absorption by aqueous alkanolamine solutions is the dominant industrial process for acid gases removal, in particular CO{sub 2} and H{sub 2}S, from natural gas. Kinetics of CO{sub 2} desorption from CO{sub 2}-loaded methyldiethanolamine (MDEA) aqueous solutions were measured in the following conditions: 312--383 K, 25--50 wt% MDEA aqueous solutions, CO{sub 2} loadings from 5 to 85%. A thermoregulated constant interfacial area reaction cell was operated by measuring the pressure over the solution. Producing a very slight depression in the cell, the time-dependent equilibrium pressure recovery is accurately recorded during batch desorption. Kinetics are in agreement with a fast reaction regime of desorption according to the film theory. For CO{sub 2} loadings below 0.50 mol of gas/mol of amine, desorption rates are well predicted by using the kinetic constant and orders determined from absorption experiments for the reaction between CO{sub 2} and MDEA. Some discrepancies were pointed out for loadings above 0.50 mol of gas/mol of amine.

  1. Comparison of PAH Biodegradation and Desorption Kinetics During Bioremediation of Aged Petroleum Hydrocarbon Contaminated Soils

    SciTech Connect

    Huesemann, Michael H.; Hausmann, Tom S.; Fortman, Timothy J.

    2000-09-20

    It is commonly assumed that mass-transfer limitations are the cause for slow and incomplete biodegradation of PAHs in aged soils. In order to test this hypothesis, the biodegradation rate and the abiotic release rate were measured and compared for selected PAHs in three different soils. It was found that PAH biodegradation was not mass-transfer limited during slurry bioremediation of an aged loamy soil. By contrast, PAH biodegradation rates were much larger than abiotic release rates in kaolinite clay indicating that sorbed-phase PAHs can apparently be biodegraded directly from mineral surfaces without prior desorption or dissolution into the aqueous phase. A comparison of PAH biodegradation rates and abiotic release rates at termination of the slurry bioremediation treatment revealed that abiotic release rates are much larger than the respective biodegradation rates. In addition, it was found that the number of hydrocarbon degraders decreased by four orders of magnitude during the bioremediation treatment. It can therefore be concluded that the slow and incomplete biodegradation of PAHs is not caused by mass-transfer limitations but rather by microbial factors. Consequently, the residual PAHs that remain after extensive bioremediation treatment are still bioavailable and for that reason could pose a greater risk to environmental receptors than previously thought.

  2. Kinetics of hydrogenation of nitrobenzene to aniline on a copper catalyst

    SciTech Connect

    Petrov, L.A.; Kirkov, N.V.; Shopov, D.M.

    1986-02-01

    The kinetics of the vapor-phase, catalytic hydrogenation of nitrobenzene to aniline on an industrial copper catalyst has been studied in the 503-563/sup 0/K range. A kinetic model of the process is presented which assumes the sequential addition of hydrogen from the gas phase and the absence of retardation by aniline.

  3. Adsorption and desorption of arsenate on sandy sediments from contaminated and uncontaminated saturated zones: Kinetic and equilibrium modeling.

    PubMed

    Hafeznezami, Saeedreza; Zimmer-Faust, Amity G; Dunne, Aislinn; Tran, Tiffany; Yang, Chao; Lam, Jacquelyn R; Reynolds, Matthew D; Davis, James A; Jay, Jennifer A

    2016-08-01

    Application of empirical models to adsorption of contaminants on natural heterogeneous sorbents is often challenging due to the uncertainty associated with fitting experimental data and determining adjustable parameters. Sediment samples from contaminated and uncontaminated portions of a study site in Maine, USA were collected and investigated for adsorption of arsenate [As(V)]. Two kinetic models were used to describe the results of single solute batch adsorption experiments. Piecewise linear regression of data linearized to fit pseudo-first order kinetic model resulted in two distinct rates and a cutoff time point of 14-19 h delineating the biphasic behavior of solute adsorption. During the initial rapid adsorption stage, an average of 60-80% of the total adsorption took place. Pseudo-second order kinetic models provided the best fit to the experimental data (R(2) > 0.99) and were capable of describing the adsorption over the entire range of experiments. Both Langmuir and Freundlich isotherms provided reasonable fits to the adsorption data at equilibrium. Langmuir-derived maximum adsorption capacity (St) of the studied sediments ranged between 29 and 97 mg/kg increasing from contaminated to uncontaminated sites. Solid phase As content of the sediments ranged from 3.8 to 10 mg/kg and the As/Fe ratios were highest in the amorphous phase. High-pH desorption experiments resulted in a greater percentage of solid phase As released into solution from experimentally-loaded sediments than from the unaltered samples suggesting that As(V) adsorption takes place on different reversible and irreversible surface sites.

  4. The dynamics and kinetics of the translational relaxation, adsorption, and desorption during the interaction of gas atoms with a metal surface

    NASA Astrophysics Data System (ADS)

    Markeev, B. M.

    The dynamics and kinetics of translational energy accommodation accompanied by the adsorption and desorption of gas particles are investigated analytically using the 'potential box' approximation. It is shown that the energy and spatial distributions of desorbed particles are largely determined by the dynamics of their interaction with a metal surface, which is explained by the fact that desorption, like adsorption, is an essentially nonequilibrium process. The calculated accommodation coefficients are compared with experimental data on the accommodation of the translational energy of inert gas atoms on the surface of tungsten.

  5. A kinetic folding intermediate probed by native state hydrogen exchange.

    PubMed

    Parker, M J; Marqusee, S

    2001-01-19

    Stopped-flow fluorescence studies on the N-terminal domain of rat CD2 (CD2.d1) have demonstrated that folding from the fully denatured state (U) proceeds via the transient accumulation of an apparent intermediate (I) in a so-called burst phase that precedes the rate-limiting transition leading to the native state (N). A previous pH-dependent equilibrium hydrogen exchange (HX) study identified a subset of amides in CD2.d1 which, under EX2 conditions, exchange from N with free energies greater than or equal to the free energy difference between the N and I states calculated from the stopped-flow data. Under EX1 conditions the rates of HX for these amides tend towards an asymptote that matches the global unfolding rate calculated from the stopped-flow data, suggesting that exchange for these amides requires traversing the N-to-I transition state barrier. Exchange for these amides presumably occurs from exchange-competent forms comprising the kinetic burst phase therefore. To explore this idea further, native state HX (NHX) data have been collected for CD2.d1 under EX2 conditions using denaturant concentrations which span either side of the denaturant concentration where, according to the stopped-flow data, the apparent U and I states are iso-energetic. The data fit to a two-component, sub-global (sg)/global (g) NHX mechanism, yielding Delta G and m value parameters (where the m value is a measure of hydrocarbon solvation). Regression analysis demonstrates that the (m(sg), Delta G(sg)) and (m(g), Delta G(g)) values calculated for this subset of amides correspond with those describing the kinetic burst phase transition. This result confirms the ability of the NHX technique to explore the structural and energetic properties of kinetic folding intermediates. Copyright 2001 Academic Press.

  6. Principles of hydrogen radical mediated peptide/protein fragmentation during matrix-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Asakawa, Daiki

    2016-07-01

    Matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) is a very easy way to obtain large sequence tags and, thereby, reliable identification of peptides and proteins. Recently discovered new matrices have enhanced the MALDI-ISD yield and opened new research avenues. The use of reducing and oxidizing matrices for MALDI-ISD of peptides and proteins favors the production of fragmentation pathways involving "hydrogen-abundant" and "hydrogen-deficient" radical precursors, respectively. Since an oxidizing matrix provides information on peptide/protein sequences complementary to that obtained with a reducing matrix, MALDI-ISD employing both reducing and oxidizing matrices is a potentially useful strategy for de novo peptide sequencing. Moreover, a pseudo-MS(3) method provides sequence information about N- and C-terminus extremities in proteins and allows N- and C-terminal side fragments to be discriminated within the complex MALDI-ISD mass spectrum. The combination of high mass resolution of a Fourier transform-ion cyclotron resonance (FTICR) analyzer and the software suitable for MALDI-ISD facilitates the interpretation of MALDI-ISD mass spectra. A deeper understanding of the MALDI-ISD process is necessary to fully exploit this method. Thus, this review focuses first on the mechanisms underlying MALDI-ISD processes, followed by a discussion of MALDI-ISD applications in the field of proteomics. © 2014 Wiley Periodicals, Inc., Mass Spec Rev 35:535-556, 2016. © 2014 Wiley Periodicals, Inc.

  7. Electron beam exposure mechanisms in hydrogen silsesquioxane investigated by vibrational spectroscopy and in-situ electron beam induced desorption

    SciTech Connect

    Olynick, D.L.; Cord, B.; Schipotinin, A.; Ogletree, D.F.; Schuck, P.J.

    2009-11-13

    Hydrogen Silsesquioxane (HSQ) is used as a high-resolution resist with resolution down below 10nm half-pitch. This material or materials with related functionalities could have widespread impact in nanolithography and nanoscience applications if the exposure mechanism was understood and instabilities controlled. Here we have directly investigated the exposure mechanism using vibrational spectroscopy (both Raman and Fourier transform Infrared) and electron beam desorption spectrocscopy (EBDS). In the non-networked HSQ system, silicon atoms sit at the corners of a cubic structure. Each silicon is bonded to a hydrogen atom and bridges 3 oxygen atoms (formula: HSiO3/2). For the first time, we have shown, via changes in the Si-H2 peak at ~;;2200 cm -1 in the Raman spectra and the release of SiHx products in EBID, that electron-bam exposed materials crosslinks via a redistribution reaction. In addition, we observe the release of significantly more H2 than SiH2 during EBID, which is indicative of additional reaction mechanisms. Additionally, we compare the behavior of HSQ in response to both thermal and electron-beam induced reactions.

  8. Ab-initio kinetics and thermodynamics studies of ammonia-borane for hydrogen storage

    NASA Astrophysics Data System (ADS)

    Miranda, Caetano R.; Ceder, Gerbrand

    2007-03-01

    Ammonia-borane (BH3NH3) is a promising chemical hydrogen storage material given its high gravimetry and volumetric properties. However, the ammonia-borane (AB) thermal hydrogen release is not very efficient, being mainly limited by the kinetics of hydrogenation. Using ab initio calculations, we have investigated the thermodynamics and kinetics of hydrogen release on AB by calculating the free energies of the H2 release reactions for different possible decomposition products. Our results indicate that AB regeneration through the ammonia-borane polymeric and borazine-cyclotriborazane cycles is very unlikely due to the strong exothermic character of the reactions. The kinetics of hydrogen release is further investigated with the recently developed metadynamics method. This method allows us to calculate the multidimensional free energy surface of hydrogen release on AB. Our simulations reveal the atomistic mechanism of hydrogenation and provide the free energies barriers and transition states involved in inter and intramolecule H2 release on AB.

  9. Erbium hydride decomposition kinetics.

    SciTech Connect

    Ferrizz, Robert Matthew

    2006-11-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.

  10. Activated desorption at heterogeneous interfaces and long-time kinetics of hydrocarbon recovery from nanoporous media

    PubMed Central

    Lee, Thomas; Bocquet, Lydéric; Coasne, Benoit

    2016-01-01

    Hydrocarbon recovery from unconventional reservoirs (shale gas) is debated due to its environmental impact and uncertainties on its predictability. But a lack of scientific knowledge impedes the proposal of reliable alternatives. The requirement of hydrofracking, fast recovery decay and ultra-low permeability—inherent to their nanoporosity—are specificities of these reservoirs, which challenge existing frameworks. Here we use molecular simulation and statistical models to show that recovery is hampered by interfacial effects at the wet kerogen surface. Recovery is shown to be thermally activated with an energy barrier modelled from the interface wetting properties. We build a statistical model of the recovery kinetics with a two-regime decline that is consistent with published data: a short time decay, consistent with Darcy description, followed by a fast algebraic decay resulting from increasingly unreachable energy barriers. Replacing water by CO2 or propane eliminates the barriers, therefore raising hopes for clean/efficient recovery. PMID:27327254

  11. Activated desorption at heterogeneous interfaces and long-time kinetics of hydrocarbon recovery from nanoporous media.

    PubMed

    Lee, Thomas; Bocquet, Lydéric; Coasne, Benoit

    2016-06-21

    Hydrocarbon recovery from unconventional reservoirs (shale gas) is debated due to its environmental impact and uncertainties on its predictability. But a lack of scientific knowledge impedes the proposal of reliable alternatives. The requirement of hydrofracking, fast recovery decay and ultra-low permeability-inherent to their nanoporosity-are specificities of these reservoirs, which challenge existing frameworks. Here we use molecular simulation and statistical models to show that recovery is hampered by interfacial effects at the wet kerogen surface. Recovery is shown to be thermally activated with an energy barrier modelled from the interface wetting properties. We build a statistical model of the recovery kinetics with a two-regime decline that is consistent with published data: a short time decay, consistent with Darcy description, followed by a fast algebraic decay resulting from increasingly unreachable energy barriers. Replacing water by CO2 or propane eliminates the barriers, therefore raising hopes for clean/efficient recovery.

  12. Activated desorption at heterogeneous interfaces and long-time kinetics of hydrocarbon recovery from nanoporous media

    NASA Astrophysics Data System (ADS)

    Lee, Thomas; Bocquet, Lydéric; Coasne, Benoit

    2016-06-01

    Hydrocarbon recovery from unconventional reservoirs (shale gas) is debated due to its environmental impact and uncertainties on its predictability. But a lack of scientific knowledge impedes the proposal of reliable alternatives. The requirement of hydrofracking, fast recovery decay and ultra-low permeability--inherent to their nanoporosity--are specificities of these reservoirs, which challenge existing frameworks. Here we use molecular simulation and statistical models to show that recovery is hampered by interfacial effects at the wet kerogen surface. Recovery is shown to be thermally activated with an energy barrier modelled from the interface wetting properties. We build a statistical model of the recovery kinetics with a two-regime decline that is consistent with published data: a short time decay, consistent with Darcy description, followed by a fast algebraic decay resulting from increasingly unreachable energy barriers. Replacing water by CO2 or propane eliminates the barriers, therefore raising hopes for clean/efficient recovery.

  13. A DFT study and micro-kinetic analysis of acetylene selective hydrogenation on Pd-doped Cu(111) surfaces

    NASA Astrophysics Data System (ADS)

    Ma, Ling-Ling; Lv, Cun-Qin; Wang, Gui-Chang

    2017-07-01

    Semi-hydrogenation of acetylene in a hydrogen-rich stream is an industrially important process. Inspired by the recent experiments that Cu(111) surface doped by a small number of Pd atoms can exhibit excellent catalytic performance toward the dissociation of H2 molecule as well as the high selective hydrogenation of acetylene as compared with pure Cu and Pd metal alone at low-temperature, here we performed systematic first-principles calculations to investigate the corresponding reaction mechanism related to the acetylene hydrogenation processes on single atom alloys (SAAs) and monolayer Pd/Cu(111) (i.e.,1.00 ML Pd/Cu(111)) model catalysts in detail, and to explore the possible factors controlling the high selectivity on SAAs. Our results clearly demonstrate that the SAA catalyst has higher selectivity for the ethylene formation than that of 1.00 ML Pd/Cu(111), and lower activity for the acetylene conversion compared with that of 1.00 ML Pd/Cu(111). The relatively high selectivity on SAA is mainly due to the facile desorption of ethylene and moderate activity in the dissociation of molecular H2. The main factor which lowers the selectivity towards the ethylene formation on 1.00 ML Pd/Cu(111) is that this system has a higher capacity to promote the breaking of Csbnd H/Csbnd C bonds, which leads to the formation of carbonaceous deposits and polymers such as benzene, and thus reduces the selectivity for the ethylene formation. Meanwhile, it was found that the desorption energy of ethylene on these two surfaces was smaller than the energy barrier of further hydrogenation, which results in the absence of ethane on these two systems. Micro-kinetic model analysis provides a further valuable insight into the evidence for the key factors controlling the catalytic activity and selectivity towards the selective hydrogenation of acetylene. Our findings may help people to design a highly selective hydrogenation catalyst by controlling the balance between the H2 dissociation and

  14. Trapping state of hydrogen isotopes in carbon and graphite investigated by thermal desorption spectrometry

    SciTech Connect

    Atsumi, H.; Tanabe, T.; Shikama, T.

    2015-03-15

    Thermal desorption spectrometry (TDS) has been investigated to obtain fundamental information of tritium behavior in graphite and carbon materials especially at high temperatures. 29 brands of graphite, HOPG, glassy carbon and CFC materials charged with deuterium gas are tested up to the temperature of 1735 K with a heating rate of 0.1 K/s. TDS spectra have five peaks at 600-700 K, around 900 K, 1200 K, 1300-1450 K and 1600-1650 K. The amounts of released deuterium have been compared with crystallographic parameters derived from XRD analysis. The results can be summarized as follows. First, TDS spectra of deuterium were quite varied among the samples tested, such as existence of peaks, peak temperatures and release amounts of deuterium. Secondly, TDS spectra may consist of five peaks, which are peak 1 (600-700 K), peak 2 (around 900 K), peak 3 (around 1200 K), peak 4 (1300-1450 K) and peak 5 (1600-1650 K). Thirdly, the correlations between the estimated surface area of edge surface and the total amount of released deuterium could be observed for peaks 4 and 5. Fourthly, high energy trapping site (peak 5) may exist even at edge surface or a near surface region, not only for intercalary. And fifth, in order to obtain the lower tritium retention for graphite and CFC materials, the material should be composed of a filler grain with a smaller crystallite size or having the smaller net edge surface in its structure. It is shown that heat treatment does not reduce originally existing trapping sites but trapping sites generated by neutron irradiation for instance can be reduced in some degree.

  15. Kinetics of hydrogen adsorption on MgH{sub 2}/CNT composite

    SciTech Connect

    Rather, Sami ullah Taimoor, Aqeel Ahmad; Muhammad, Ayyaz; Alhamed, Yahia Abobakor; Zaman, Sharif Fakhruz; Ali, Arshid Mahmood

    2016-05-15

    Highlights: • Hydrogen adsorption comparisons of commercial, milled, and MgH{sub 2} composite. • Hydrogen adsorption capacity and kinetics improves tremendously by CNT embedding. • Unsteady state modeling and simulation of adsorption kinetics. - Abstract: Magnesium hydride (MgH{sub 2})–carbon nanotubes (CNT) composite has been prepared by high-energy ball milling method and their experimental and kinetic hydrogen adsorption studies was assessed. Hydrogen adsorption studies were performed by Sievert’s volumetric apparatus and kinetic evaluation was conducted by surface chemistry and Langmuir–Hinshelwood–Hougen–Watson (LHHW) type mode. Powder X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) were performed. Hydrogen adsorption capacity of commercial MgH{sub 2}, milled MgH{sub 2}, and MgH{sub 2}/CNT composite are found to be 0.04, 0.057, and 0.059 g (H{sub 2})/g (MgH{sub 2}) at 673 K and hydrogen pressure of 4.6 MPa. Addition of 5 wt% of CNTs to MgH{sub 2} proved to be very critical to enhance hydrogen adsorption as well as to improve its kinetics. It was observed that hydrogen adsorption is not in quasi-state equilibrium and is modeled using kinetic rate laws.

  16. Effectiveness of passivation techniques on hydrogen desorption in a tritium environment

    NASA Astrophysics Data System (ADS)

    Woodall, Steven Michael

    2009-11-01

    Tritium is a radioactive isotope of hydrogen. It is used as a fuel in fusion reactors, a booster material in nuclear weapons and as a light source in commercial applications. When tritium is used in fusion reactors, and especially when used in the manufacture of nuclear weapons, purity is critical. For U.S. Department of Energy use, tritium is recycled by Savannah River Site in South Carolina and is processed to a minimum purity of 99.5%. For use elsewhere in the country, it must be shipped and stored, while maintaining the highest purity possible. As an isotope of hydrogen it exchanges easily with the most common isotope of hydrogen, protium. Stainless steel bottles are used to transport and store tritium. Protium, present in air, becomes associated in and on the surface of stainless steel during and after the manufacture of the steel. When filled, the tritium within the bottle exchanges with the protium in and on the surface of the stainless steel, slowly contaminating the pure tritium with protium. The stainless steel is therefore passivated to minimize the protium outgrowth of the bottles into the pure tritium. This research is to determine how effective different passivation techniques are in minimizing the contamination of tritium with protium. Additionally, this research will attempt to determine a relationship between surface chemistry of passivated steels and protium contamination of tritium. The conclusions of this research found that passivated bottles by two companies which routinely provide passivated materials to the US Department of Energy provide low levels of protium outgrowth into pure tritium. A bottle passivated with a material to prevent excessive corrosion in a highly corrosive environment, and a clean and polished bottle provided outgrowth rates roughly twice those of the passivated bottles above. Beyond generally high levels of chromium, oxygen, iron and nickel in the passivated bottles, there did not appear to be a strong correlation

  17. Kinetic Controls on the Desorption/Dissolution of Sorbed U(VI) and their Influence on Reactive Transport

    SciTech Connect

    Zachara, John M.; Chongxuan Liu; Qafoku, Nikolla P.; McKinley, James P.; Catalano, Jeffrey G.; Brown, Gordon E., Jr.; Davis, James A.

    2006-04-05

    source to groundwater. (2) Measure desorption/dissolution rates of sorbed U(VI), quantify controlling factors, and develop descriptive kinetic models to provide a scientific basis to forecast U(VI) fluxes to groundwater, future plume dynamics, and long-term contaminant attenuation. (3) Establish reaction networks and determine geochemically/ physically realistic reaction parameters to drive state-of-the-art reactive transport modeling of U in vadose zone pore fluids and groundwater.

  18. Investigation of blistering kinetics in hydrogen implanted aluminium nitride

    NASA Astrophysics Data System (ADS)

    Singh, R.; Scholz, R.; Christiansen, S. H.; Gösele, U.

    2008-04-01

    Epitaxial layers of aluminium nitride (AlN) grown on sapphire by hydride vapour phase epitaxy (HVPE) were implanted with 100 keV hydrogen, H+2, ions with doses in the range of 5 × 1016-2.5 × 1017 cm-2 and subsequently annealed in ambient air at temperatures between 450 and 750 °C in order to determine the kinetics of surface blister formation in AlN. The Arrhenius plot of the blistering time versus temperature shows two different activation energies for the formation of surface blisters: 0.44 eV in the higher temperature regime of 550-750 °C and 1.16 eV in the lower temperature regime of 450-550 °C. The implantation-induced damage was analyzed by cross-sectional transmission electron microscopy, which revealed a band of defects extending from 330 to 550 nm from the surface of AlN. The XTEM image of the implanted and annealed AlN displayed clearly the formation of microcracks that ultimately lead to the formation of surface blisters.

  19. Kinetics of a hydrogen-oxidizing, perchlorate-reducing bacterium.

    PubMed

    Nerenberg, Robert; Kawagoshi, Yasunori; Rittmann, Bruce E

    2006-10-01

    This paper provides the first kinetic parameters for a hydrogen-oxidizing perchlorate-reducing bacterium (PCRB), Dechloromonas sp. PC1. The qmax for perchlorate and chlorate were 3.1 and 6.3 mg/mgDW-day, respectively. The K for perchlorate was 0.14 mg/L, an order of magnitude lower than reported for other PCRB. The yields Y on perchlorate and chlorate were 0.23 and 0.22 mgDW/mg, respectively, and the decay constant b was 0.055/day. The growth-threshold, Smin, for perchlorate was 14 microg/L, suggesting that perchlorate cannot be reduced below this level when perchlorate is the primary electron-acceptor, although it may be possible when oxygen or nitrate is the primary acceptor. Chlorate accumulated at maximum concentrations of 0.6-4.3 mg/L in batch tests with initial perchlorate concentrations ranging from 100 to 600 mg/L. Furthermore, 50 mg/L chlorate inhibited perchlorate reduction with perchlorate at 100 mg/L. This is the first report of chlorate accumulation and inhibition for a pure culture of PCRB. These Chlorate effects are consistent with competitive inhibition between perchlorate and chlorate for the (per)chlorate reductase enzyme.

  20. Kinetics Study of Solid Ammonia Borane Hydrogen Release – Modeling and Experimental Validation for Chemical Hydrogen Storage

    SciTech Connect

    Choi, Yong-Joon; Ronnebro, Ewa; Rassat, Scot D.; Karkamkar, Abhijeet J.; Maupin, Gary D.; Holladay, Jamelyn D.; Simmons, Kevin L.; Brooks, Kriston P.

    2014-02-24

    Ammonia borane (AB), NH3BH3, is a promising material for chemical hydrogen storage with 19.6 wt% gravimetric hydrogen capacity of which 16.2 wt% hydrogen can be utilized below 200°C. We have investigated the kinetics of hydrogen release from AB and from an AB-methyl cellulose (AB/MC) composite at temperatures of 160-300°C using both experiments and modeling. The purpose of our study was to show safe hydrogen release without thermal runaway effects and to validate system model kinetics. AB/MC released hydrogen at ~20°C lower than neat AB and at a rate that is two times faster. Based on the experimental results, the kinetics equations were revised to better represent the growth and nucleation process during decomposition of AB. We explored two different reactor concepts; Auger and fixed bed. The current Auger reactor concept turned out to not be appropriate, however, we demonstrated safe self-propagation of the hydrogen release reaction of solid AB/MC in a fixed bed reactor.

  1. Determination of bacterial and viral transport parameters in a gravel aquifer assuming linear kinetic sorption and desorption

    NASA Astrophysics Data System (ADS)

    Mallén, G.; Maloszewski, P.; Flynn, R.; Rossi, P.; Engel, M.; Seiler, K.-P.

    2005-05-01

    The bacteria Escherichia coli and Pseudomonas putida, and the bacteriophage virus H40/1 are examined both for their transport behaviour relative to inert solute tracers and for their modelability under natural flow conditions in a gravel aquifer. The microbes are attenuated in the following sequence: H40/1≥ P. putida≫ E. coli. The latter is desorbed almost completely within a few days. Breakthrough and recovery curves of the simultaneously injected non-reactive tracers are simulated with the 2D and 1D dispersion equation, in order to ascertain longitudinal dispersivity ( αL) and mean flow time ( T0). Mathematical modelling is difficult due to the aquifer heterogeneity, which results in preferential flow paths between injection and observation wells. Therefore, any attempt of fitting the dispersion model (DM) to the entire inert-tracer breakthrough curve (BTC) fails. Adequate fitting of the model to measured data only succeeds using a DM consisting of a superposition of several BTCs, each representing another set of flow paths. This gives rise to a multimodal, rather than a Gaussian groundwater velocity distribution. Only hydraulic parameters derived from the fastest partial curve, which is fitted to the rising part of the Uranine BTC, are suitable to model microbial breakthroughs. The hydraulic parameters found using 2D and 1D models were nearly identical. Their values were put into an analytical solution of 1D advective-dispersive transport combined with two-site reaction model introduced by Cameron and Klute [Cameron, D.R., Klute, A., 1977. Convective-dispersive solute transport with a combined equilibrium and kinetic adsorption model. Water Resour. Res. 13, 183-189], in order to identify reactive transport parameters (sorption/desorption) and attenuation mechanisms for the microbes migration. This shows that the microbes are almost entirely transported through preferential flow paths, which are represented by the first partial curve. Inert tracers, however

  2. Role of Desorption Kinetics and Porous Medium Heterogeneity in Colloid-Facilitated Transport of Cesium and Strontium: Preliminary Results

    NASA Astrophysics Data System (ADS)

    Dittrich, T. M.; Ryan, J. N.

    2008-12-01

    The presence of mobile colloids (particles between 1 nm and 1 μm in size) in natural soil and groundwater systems has been well established. Colloids generally have a high sorptive capacity resulting from their high surface area to mass ratio, which makes them effective sorbents of low solubility, strongly sorbing contaminants. Mobile colloids that sorb contaminants can increase the apparent solubility and rate of transport of the contaminants when desorption from the colloids is slow relative to the rate of flow. This process is known as colloid-facilitated transport (CFT). The additional transport of contaminants associated with mobile colloids should be accounted for to accurately predict transport rates of strongly-sorbing contaminants in the environment. Some examples of contaminants that have the potential for CFT are hydrophobic pesticides, polycyclic aromatic hydrocarbons (PAHs), actinide cations (e.g., Th, U, Pu, Am), and many metals (e.g, Pb, Cu, Hg). Many low solubility contaminants that have the potential for CFT are also harmful or toxic to humans, underscoring the importance of accurate modeling techniques to protect water sources from contamination. Contaminated Department of Energy (DOE) sites have been particularly valuable research opportunities for studying the transport of radionuclides in the natural environment. The DOE has conducted energy and weapons research and development in thirty-one states and Puerto Rico and has introduced many toxic and radioactive chemicals into surface waters, soils, and groundwater. Field experiments on DOE sites including the Nevada Test Site, the Hanford 200 Area tank farm, Rocky Flats CO, and Oak Ridge TN, have confirmed that metals and radionuclides have moved further than expected due to colloid-facilitated transport. The major goal of this research project is to identify and quantify the effects of sorption kinetics on colloid- facilitated transport in unsaturated porous media. This information will be used

  3. Implementation of New TPD Analysis Techniques in the Evaluation of Second Order Desorption Kinetics of Cyanogen from Cu(001)

    SciTech Connect

    E Ciftlikli; E Lee; J Lallo; S Rangan; S Senanayake; B Hinch

    2011-12-31

    The interactions of cyanide species with a copper (001) surface were studied with temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). Adsorbed cyanide species (CN{sub (a)}) undergo recombinative desorption evolving molecular cyanogen (C{sub 2}N{sub 2}). As the adsorbed CN species charge upon adsorption, mutually repulsive dipolar interactions lead to a marked desorption energy reduction with increasing CN{sub (a)} coverages. Two new TPD analysis approaches were developed, which used only accurately discernible observables and which do not assume constant desorption energies, E{sub d}, and pre-exponential values, v. These two approaches demonstrated a linear variation of E{sub d} with instantaneous coverage. The first approach involved an analysis of the variations of desorption peak asymmetry with initial CN coverages. The second quantitative approach utilized only temperatures and intensities of TPD peaks, together with deduced surface coverages at the peak maxima, also as a function of initial surface coverages. Parameters derived from the latter approach were utilized as initial inputs for a comprehensive curve fit analysis technique. Excellent fits for all experimental desorption curves were produced in simulations. The curve fit analysis confirms that the activation energy of desorption of 170-180 kJ/mol at low coverage decreases by up to 14-15 kJ/mol at CN saturation.

  4. Implementation of New TPD Analysis Techniques in the Evaluation of Second Order Desorption Kinetics of Cyanogen from Cu(001)

    SciTech Connect

    Hinch, B.J.; Senanayake, S.; Ciftlikli, E.Z.; Lee, E.Y.M.; Lallo, J.; Rangan, S.

    2010-12-21

    The interactions of cyanide species with a copper (001) surface were studied with temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). Adsorbed cyanide species (CN{sub (a)}) undergo recombinative desorption evolving molecular cyanogen (C{sub 2}N{sub 2}). As the adsorbed CN species charge upon adsorption, mutually repulsive dipolar interactions lead to a marked desorption energy reduction with increasing CN{sub (a)} coverages. Two new TPD analysis approaches were developed, which used only accurately discernible observables and which do not assume constant desorption energies, E{sub d}, and pre-exponential values, v. These two approaches demonstrated a linear variation of E{sub d} with instantaneous coverage. The first approach involved an analysis of the variations of desorption peak asymmetry with initial CN coverages. The second quantitative approach utilized only temperatures and intensities of TPD peaks, together with deduced surface coverages at the peak maxima, also as a function of initial surface coverages. Parameters derived from the latter approach were utilized as initial inputs for a comprehensive curve fit analysis technique. Excellent fits for all experimental desorption curves were produced in simulations. The curve fit analysis confirms that the activation energy of desorption of 170-180 kJ/mol at low coverage decreases by up to 14-15 kJ/mol at CN saturation.

  5. Kinetics of hydrogenation of acetophenone to methylphenylcarbinol on KGA-43 copper-chromium catalyst

    SciTech Connect

    Ziyatdinov, A.Sh.; Stepanenko, V.V.; Chernykh, I.S.; Leonova, E.B.; Pisarenko, V.N.; Kafarov, V.V.

    1988-08-20

    The purpose of this investigation was to study the kinetics of the hydrogenation of acetophenone on KGA-43 catalyst, to establish a kinetic model for it, and to test the adequacy of the kinetic model for experiment. The kinetic studies of the hydrogenation of acetophenone on the new KGA-43 catalyst were conducted on a laboratory unit. Using the theory of steady-state reactions a kinetic model incorporating 10 unknown parameters was constructed. To determine the point estimates of the kinetic constants they used the method of maximum probability. The results of five repeated experiments were used to calculate the elements of a dispersion-covariation matrix of the reproducibility of the observations.

  6. Effect of Clay Nanoparticle Transport, Desorption Kinetics and Redox Equilibrium on Radionuclide Mobility in Fractured Rock investigated at the Grimsel Test Site (Switzerland)

    NASA Astrophysics Data System (ADS)

    Schaefer, T.; Huber, F. M.; Lagos, M.; Quinto, F.; Heck, S.; Martin, A. J.; Blechschmidt, I.; Lanyon, G. W.; Reiche, T.; Noseck, U.

    2015-12-01

    Transport of contaminants in crystalline environments might occur through dissolved species or attached to colloidal or nanoparticulate phases being mobile in water conducting features of the host rock. In this presentation we will discuss the mobility of clay nanoparticles as detected by laser-induced breakdown detection (LIBD) as a function of fracture surface roughness and groundwater chemistry. The on site observed Tc-99, U-233, Np-237, Pu-242 and Am-243 sorption/desorption kinetics with and without natural or synthetic clay minerals (smectites) are compared to laboratory studies under similar groundwater conditions. The desorption or redox kinetics were monitored over a duration of up to 426 days using natural fracture filling material as a concurrence ligand and monitoring the colloid attachment via detection of Al, Si, Ni and Zn as smectite structural elements. For trivalent actinides smectite desorption rates in the range of 1.2-3.7E-3 per hour could be determined and significantly lower desorption rates for tetravalent actinides were found. This results will be compared with field data of migration experiments performed at the Grimsel Test Site (GTS, Switzerland) using the same radionuclides and clay colloidal phases varying the fracture residence time by flow rate adjustment. Furthermore, the long-term actinide mobility will be addressed by presenting AMS/RIMS measurements of (a) samples collected several months into the tailing of the breakthrough curves not any longer detectable by HR-ICP-MS and (b) background samples of different GTS ground waters showing fallout U-236, whereas fallout Pu could not be detected indicating a much lower mobility under the given conditions.

  7. Modeling of hydrogenation kinetics from triglyceride compositional data.

    PubMed

    Holser, Ronald A; List, Gary R; King, Jerry W; Holliday, Russell L; Neff, William E

    2002-11-20

    A mathematical model was developed to describe the reduction of soybean oil triglycerides during hydrogenation. The model was derived from reaction and transport mechanisms and formulated into a system of first-order irreversible rate expressions that included terms for temperature, hydrogen pressure, and catalyst concentration. The model parameters were estimated from experimental data, and the model was used to simulate the results of hydrogenation performed over the pressure range of 0.069-6.9 MPa. The model could be extended to include geometrical isomers formed during hydrogenation.

  8. FAR-INFRARED SPECTROSCOPY OF CATIONIC POLYCYCLIC AROMATIC HYDROCARBONS: ZERO KINETIC ENERGY PHOTOELECTRON SPECTROSCOPY OF PENTACENE VAPORIZED FROM LASER DESORPTION

    SciTech Connect

    Zhang Jie; Han Fangyuan; Pei Linsen; Kong Wei; Li Aigen

    2010-05-20

    The distinctive set of infrared (IR) emission bands at 3.3, 6.2, 7.7, 8.6, and 11.3 {mu}m are ubiquitously seen in a wide variety of astrophysical environments. They are generally attributed to polycyclic aromatic hydrocarbon (PAH) molecules. However, not a single PAH species has yet been identified in space, as the mid-IR vibrational bands are mostly representative of functional groups and thus do not allow one to fingerprint individual PAH molecules. In contrast, the far-IR (FIR) bands are sensitive to the skeletal characteristics of a molecule, hence they are important for chemical identification of unknown species. With an aim to offer laboratory astrophysical data for the Herschel Space Observatory, Stratospheric Observatory for Infrared Astronomy, and similar future space missions, in this work we report neutral and cation FIR spectroscopy of pentacene (C{sub 22}H{sub 14}), a five-ring PAH molecule. We report three IR active modes of cationic pentacene at 53.3, 84.8, and 266 {mu}m that may be detectable by space missions such as the SAFARI instrument on board SPICA. In the experiment, pentacene is vaporized from a laser desorption source and cooled by a supersonic argon beam. We have obtained results from two-color resonantly enhanced multiphoton ionization and two-color zero kinetic energy photoelectron (ZEKE) spectroscopy. Several skeletal vibrational modes of the first electronically excited state of the neutral species and those of the cation are assigned, with the aid of ab initio and density functional calculations. Although ZEKE is governed by the Franck-Condon principle different from direct IR absorption or emission, vibronic coupling in the long ribbon-like molecule results in the observation of a few IR active modes. Within the experimental resolution of {approx}7 cm{sup -1}, the frequency values from our calculation agree with the experiment for the cation, but differ for the electronically excited intermediate state. Consequently, modeling of the

  9. Calibration of Thermal Desorption System (TDS) Response to Hydrogen for Analysis of Titanium Subhydride and Titanium Hydride

    SciTech Connect

    Mills, Bernice E.

    2013-07-01

    The equipment and method for and results of calibration of the Sandia/CA TDS system for hydrogen quantification is presented. This technique for calibration can be used to quantify the hydrogen content titanium subhydride, titanium hydride, and any other hydrogen-containing material that desorbs its hydrogen in the form of molecular hydrogen below 1450°C.

  10. Complex hydrides for hydrogen storage

    DOEpatents

    Zidan, Ragaiy

    2006-08-22

    A hydrogen storage material and process of forming the material is provided in which complex hydrides are combined under conditions of elevated temperatures and/or elevated temperature and pressure with a titanium metal such as titanium butoxide. The resulting fused product exhibits hydrogen desorption kinetics having a first hydrogen release point which occurs at normal atmospheres and at a temperature between 50.degree. C. and 90.degree. C.

  11. Kinetic Monte Carlo study on the evolution of silicon surface roughness under hydrogen thermal treatment

    NASA Astrophysics Data System (ADS)

    Wang, Gang; Wang, Yu; Wang, Junzhuan; Pan, Lijia; Yu, Linwei; Zheng, Youdou; Shi, Yi

    2017-08-01

    The evolution of a two-dimensional silicon surface under hydrogen thermal treatment is studied by kinetic Monte Carlo simulations, focusing on the dependence of the migration behaviors of surface atoms on both the temperature and hydrogen pressure. We adopt different activation energies to analyze the influence of hydrogen pressure on the evolution of surface morphology at high temperatures. The reduction in surface roughness is divided into two stages, both exhibiting exponential dependence on the equilibrium time. Our results indicate that a high hydrogen pressure is conducive to obtaining optimized surfaces, as a strategy in the applications of three-dimensional devices.

  12. Synthesis of small metallic Mg-based nanoparticles confined in porous carbon materials for hydrogen sorption.

    PubMed

    Zlotea, Claudia; Chevalier-César, Clotaire; Léonel, Eric; Leroy, Eric; Cuevas, Fermin; Dibandjo, Philippe; Vix-Guterl, Cathie; Martens, Thierry; Latroche, Michel

    2011-01-01

    MgH2, Mg-Ni-H and Mg-Fe-H nanoparticles inserted into ordered mesoporous carbon templates have been synthesized by decomposition of organometallic precursors under hydrogen atmosphere and mild temperature conditions. The hydrogen desorption properties of the MgH2 nanoparticles are studied by thermo-desorption spectroscopy. The particle size distribution of MgH2, as determined by TEM, is crucial for understanding the desorption properties. The desorption kinetics are significantly improved by downsizing the particle size below 10 nm. Isothermal absorption/desorption cycling of the MgH2 nanoparticles shows a stable capacity over 13 cycles. The absorption kinetics are unchanged though the desorption kinetics are slower on cycling.

  13. Tailoring Thermodynamics and Kinetics for Hydrogen Storage in Complex Hydrides towards Applications.

    PubMed

    Liu, Yongfeng; Yang, Yaxiong; Gao, Mingxia; Pan, Hongge

    2016-02-01

    Solid-state hydrogen storage using various materials is expected to provide the ultimate solution for safe and efficient on-board storage. Complex hydrides have attracted increasing attention over the past two decades due to their high gravimetric and volumetric hydrogen densities. In this account, we review studies from our lab on tailoring the thermodynamics and kinetics for hydrogen storage in complex hydrides, including metal alanates, borohydrides and amides. By changing the material composition and structure, developing feasible preparation methods, doping high-performance catalysts, optimizing multifunctional additives, creating nanostructures and understanding the interaction mechanisms with hydrogen, the operating temperatures for hydrogen storage in metal amides, alanates and borohydrides are remarkably reduced. This temperature reduction is associated with enhanced reaction kinetics and improved reversibility. The examples discussed in this review are expected to provide new inspiration for the development of complex hydrides with high hydrogen capacity and appropriate thermodynamics and kinetics for hydrogen storage. © 2015 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Atomic-level Pd-Pt alloying and largely enhanced hydrogen-storage capacity in bimetallic nanoparticles reconstructed from core/shell structure by a process of hydrogen absorption/desorption.

    PubMed

    Kobayashi, Hirokazu; Yamauchi, Miho; Kitagawa, Hiroshi; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki

    2010-04-28

    We have achieved the creation of a solid-solution alloy where Pd and Pt are homogeneously mixed at the atomic level, by a process of hydrogen absorption/desorption as a trigger for core (Pd)/shell (Pt) nanoparticles. The structural change from core/shell to solid solution has been confirmed by in situ powder X-ray diffraction, energy dispersive spectra, solid-state (2)H NMR measurement, and hydrogen pressure-composition isotherms. The successfully obtained Pd-Pt solid-solution nanoparticles with a Pt content of 8-21 atom % had a higher hydrogen-storage capacity than Pd nanoparticles. Moreover, the hydrogen-storage capacity of Pd-Pt solid-solution nanoparticles can be tuned by changing the composition of Pd and Pt.

  15. Highly hydrogen-sensitive thermal desorption spectroscopy system for quantitative analysis of low hydrogen concentration (∼1 × 10(16) atoms/cm(3)) in thin-film samples.

    PubMed

    Hanna, Taku; Hiramatsu, Hidenori; Sakaguchi, Isao; Hosono, Hideo

    2017-05-01

    We developed a highly hydrogen-sensitive thermal desorption spectroscopy (HHS-TDS) system to detect and quantitatively analyze low hydrogen concentrations in thin films. The system was connected to an in situ sample-transfer chamber system, manipulators, and an rf magnetron sputtering thin-film deposition chamber under an ultra-high-vacuum (UHV) atmosphere of ∼10(-8) Pa. The following key requirements were proposed in developing the HHS-TDS: (i) a low hydrogen residual partial pressure, (ii) a low hydrogen exhaust velocity, and (iii) minimization of hydrogen thermal desorption except from the bulk region of the thin films. To satisfy these requirements, appropriate materials and components were selected, and the system was constructed to extract the maximum performance from each component. Consequently, ∼2000 times higher sensitivity to hydrogen than that of a commercially available UHV-TDS system was achieved using H(+)-implanted Si samples. Quantitative analysis of an amorphous oxide semiconductor InGaZnO4 thin film (1 cm × 1 cm × 1 μm thickness, hydrogen concentration of 4.5 × 10(17) atoms/cm(3)) was demonstrated using the HHS-TDS system. This concentration level cannot be detected using UHV-TDS or secondary ion mass spectroscopy (SIMS) systems. The hydrogen detection limit of the HHS-TDS system was estimated to be ∼1 × 10(16) atoms/cm(3), which implies ∼2 orders of magnitude higher sensitivity than that of SIMS and resonance nuclear reaction systems (∼10(18) atoms/cm(3)).

  16. Remaining uncertainties in the kinetic mechanism of hydrogen combustion

    SciTech Connect

    Konnov, Alexander A.

    2008-03-15

    An analysis of the performance of an updated hydrogen combustion mechanism is presented. Particular attention was paid to different channels of reaction between H atoms and HO{sub 2} radicals, to pressure dependence of the recombination of HO{sub 2} radicals, and to the anomalous rate constant of reaction between OH and HO{sub 2} radicals. The contemporary choice of the reaction rate constants is presented with the emphasis on their uncertainties. Then the predictions of ignition, oxidation, flame burning velocities, and flame structure of hydrogen-oxygen-inert mixtures are shown. The modeling range covers ignition experiments from 950 to 2700 K and from subatmospheric pressures up to 87 atm; hydrogen oxidation in a flow reactor at temperatures around 900 K from 0.3 up to 15.7 atm; flame burning velocities in hydrogen-oxygen-inert mixtures from 0.35 up to 4 atm; and hydrogen flame structure at 1 and 10 atm. Comparison of the modeling and experiments is discussed in terms of the range of applicability of the present detailed mechanism. The necessity for analysis of the mechanism to have an exhaustive list of reactions is emphasized. (author)

  17. Numerical simulation of the kinetics of dissociation and ionization of molecular hydrogen in the penning discharge plasma with the use of the reduced kinetic model

    NASA Astrophysics Data System (ADS)

    Storozhev, D. A.; E Kuratov, S.

    2017-02-01

    A simplified kinetic scheme for describing the kinetics of ionization and dissociation of hydrogen in the Penning discharge plasma is developed. The calculations of the component composition of the Penning discharge plasma are performed. Numerical simulation results are compared with the results provided by the detailed state-to-state kinetic scheme.

  18. Kinetic limitations of the Mg(2)Si system for reversible hydrogen storage.

    PubMed

    Kelly, Stephen T; Van Atta, Sky L; Vajo, John J; Olson, Gregory L; Clemens, B M

    2009-05-20

    Despite the promising thermodynamics and storage capacities of many destabilized metal hydride hydrogen storage material systems, they are often kinetically limited from achieving practical and reversible behavior. Such is the case with the Mg2Si system. We investigated the kinetic mechanisms responsible for limiting the reversibility of the MgH2+Si system using thin films as a controlled research platform. We observed that the reaction MgH2 + 1/2Mg2Si + H2 is limited by the mass transport of Mg and Si into separate phases. Hydrogen readily diffuses through the Mg2Si material and nucleating MgH2 phase growth does not result in reaction completion. By depositing and characterizing multilayer films of Mg2Si and Mg with varying Mg2Si layer thicknesses, we conclude that the hydrogenation reaction consumes no more than 1 nm of Mg2Si, making this system impractical for reversible hydrogen storage.

  19. Kinetics of Hydrogen Diffusion in LaNi(sub 5-x)Sn(sub x) Alloys

    NASA Technical Reports Server (NTRS)

    Ratnakumar, B. V.; Hightower, A.; Witham, C.; Bowman, R. C.; Fultz, B.

    1996-01-01

    Solid-state diffusion of hydrogen in metal hydride (MH) alloys is recognized as the rate determining step in the discharge of MH alloys in alkaline Ni-MH rechargeable cells. In our pursuit of new ternary solutes in LaNi(sub 5) for extended cycle lifetimes, we have observed noticeable improvement in the cycle life with small substitutions of Sn and Ge for Ni. Furthermore, these substituents also facilitate enhanced charge transfer kinetics for hydriding-dehydriding process. In this paper, we report our studies on the kinetics of hydrogen diffusion in LaNi(sub 5-x) Sn(sub x) alloys by electrochemical pulse techniques, chronoamperometry and chronocoulometry.

  20. The kinetic and dynamic aspects of corrosion fatigue in a gaseous hydrogen environment.

    NASA Technical Reports Server (NTRS)

    Nelson, H. G.; Williams, D. P.; Tetelman, A. S.

    1972-01-01

    The stable, subcritical crack growth stage of fracture under conditions of corrosion fatigue was studied experimentally in order to demonstrate the importance of the kinetic and dynamic aspects of environment-sensitive behavior. The cyclic loading of a titanium alloy in a low-pressure gaseous hydrogen environment is compared to that in a vacuum environment. The influence of the hydrogen environment on the rate of subcritical crack growth is discussed.

  1. Pyrrole Hydrogenation over Rh(111) and Pt(111) Single-Crystal Surfaces and Hydrogenation Promotion Mediated by 1-Methylpyrrole: A Kinetic and Sum-Frequency Generation Vibrational Spectroscopy Study

    SciTech Connect

    Kliewer, Christopher J.; Bieri, Marco; Somorjai, Gabor A.

    2008-03-04

    Sum-frequency generation (SFG) surface vibrational spectroscopy and kinetic measurements using gas chromatography have been used to study the adsorption and hydrogenation of pyrrole over both Pt(111) and Rh(111) single-crystal surfaces at Torr pressures (3 Torr pyrrole, 30 Torr H{sub 2}) to form pyrrolidine and the minor product butylamine. Over Pt(111) at 298 K it was found that pyrrole adsorbs in an upright geometry cleaving the N-H bond to bind through the nitrogen evidenced by SFG data. Over Rh(111) at 298 K pyrrole adsorbs in a tilted geometry relative to the surface through the p-aromatic system. A pyrroline surface reaction intermediate, which was not detected in the gas phase, was seen by SFG during the hydrogenation over both surfaces. Significant enhancement of the reaction rate was achieved over both metal surfaces by adsorbing 1-methylpyrrole before reaction. SFG vibrational spectroscopic results indicate that reaction promotion is achieved by weakening the bonding between the N-containing products and the metal surface because of lateral interactions on the surface between 1-methylpyrrole and the reaction species, reducing the desorption energy of the products. It was found that the ring-opening product butylamine was a reaction poison over both surfaces, but this effect can be minimized by treating the catalyst surfaces with 1-methylpyrrole before reaction. The reaction rate was not enhanced with elevated temperatures, and SFG suggests desorption of pyrrole at elevated temperatures.

  2. Quantum study of Eley-Rideal reaction and collision induced desorption of hydrogen atoms on a graphite surface. II. H-physisorbed case.

    PubMed

    Martinazzo, Rocco; Tantardini, Gian Franco

    2006-03-28

    Following previous investigation of collision induced (CI) processes involving hydrogen atoms chemisorbed on graphite [R. Martinazzo and G. F. Tantardini, J. Chem. Phys. 124, 124702 (2006)], the case in which the target hydrogen atom is initially physisorbed on the surface is considered here. Several adsorbate-substrate initial states of the target H atom in the physisorption well are considered, and CI processes are studied for projectile energies up to 1 eV. Results show that (i) Eley-Rideal cross sections at low collision energies may be larger than those found in the H-chemisorbed case but they rapidly decrease as the collision energy increases; (ii) product hydrogen molecules are vibrationally very excited; (iii) collision induced desorption cross sections rapidly increase, reaching saturation values greater than 10 A2; (iv) trapping of the incident atoms is found to be as efficient as the Eley-Rideal reaction at low energies and remains sizable (3-4 A2) at high energies. The latter adsorbate-induced trapping results mainly in formation of metastable hot hydrogen atoms, i.e., atoms with an excess energy channeled in the motion parallel to the surface. These atoms might contribute in explaining hydrogen formation on graphite.

  3. An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron

    NASA Technical Reports Server (NTRS)

    Shanabarger, Mickey R.

    1993-01-01

    The goal of this program was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of degradation. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. The interaction of hydrogen with the surfaces of alpha-2(Ti3Al) titanium aluminide, gamma(TiAl) titanium aluminide, and beryllium were studied.

  4. Upscaling of Long-Term U(VI) Desorption from Pore Scale Kinetics to Field-Scale Reactive Transport Models

    SciTech Connect

    Steefel, Carl I.; Li Li; Davis, J.A.; Curtis, G.P.; Honeyman, B.D.; Kent, D.B.; Kohler, M.; Rodriguez, D.R.; Johnson, K.J.; Miller, A.

    2006-06-01

    The focus of the project is the development of scientifically defensible approaches for upscaling reactive transport models (RTM) through a detailed understanding of U(VI) desorption across several spatial scales: bench-, intermediate-, and field-scales. The central hypothesis of the project is that the development of this methodology will lead to a scientifically defensible approach for conceptual model development for multicomponent RTM at contaminated DOE sites, leading to predictive transport simulations with reduced uncertainty.

  5. GEOMETRY, HEAT REMOVAL AND KINETICS SCOPING MODELS FOR HYDROGEN STORAGE SYSTEMS

    SciTech Connect

    Hardy, B

    2007-11-16

    It is recognized that detailed models of proposed hydrogen storage systems are essential to gain insight into the complex processes occurring during the charging and discharging processes. Such insight is an invaluable asset for both assessing the viability of a particular system and/or for improving its design. The detailed models, however, require time to develop and run. Clearly, it is much more efficient to begin a modeling effort with a good system design and to progress from that point. To facilitate this approach, it is useful to have simplified models that can quickly estimate optimal loading and discharge kinetics, effective hydrogen capacities, system dimensions and heat removal requirements. Parameters obtained from these models can then be input to the detailed models to obtain an accurate assessment of system performance that includes more complete integration of the physical processes. This report describes three scoping models that assess preliminary system design prior to invoking a more detailed finite element analysis. The three models address the kinetics, the scaling and heat removal parameters of the system, respectively. The kinetics model is used to evaluate the effect of temperature and hydrogen pressure on the loading and discharge kinetics. As part of the kinetics calculations, the model also determines the mass of stored hydrogen per mass of hydride (in a particular reference form). As such, the model can determine the optimal loading and discharge rates for a particular hydride and the maximum achievable loading (over an infinite period of time). The kinetics model developed with the Mathcad{reg_sign} solver, runs in a mater of seconds and can quickly be used to identify the optimal temperature and pressure for either the loading or discharge processes. The geometry scoping model is used to calculate the size of the system, the optimal placement of heat transfer elements, and the gravimetric and volumetric capacities for a particular

  6. 2,4-Dichlorophenol removal in a solid-liquid two phase partitioning bioreactor (TPPB): kinetics of absorption, desorption and biodegradation.

    PubMed

    Tomei, M Concetta; Annesini, M Cristina; Daugulis, Andrew J

    2012-11-15

    The applicability of a sequencing batch two phase partitioning bioreactor (TPPB) to the biodegradation of a highly toxic compound, 2,4-dichlorophenol (DCP) (EC(50)=2.3-40 mgL(-1)) was investigated. A kinetic study of the individual process steps (DCP absorption into the polymer, desorption and biodegradation) was performed and, based on favourable absorption/desorption characteristics (DCP diffusivity of 6.6×10(-8)cm(2)s(-1)), the commercial polymer Tone P787 (Dow Chemical), was utilized as the sequestering phase for TPPB operation. Batch kinetic biodegradation tests were performed in both single- and two-phase modes, and the Haldane equation kinetic parameters were estimated (k=1.3×10(-2) mgDCP mgVSS(-1)h(-1), K(I)=35 mgDCPL(-1) and K(s)=18 mgDCPL(-1)), confirming the highly toxic nature of DCP. Consistent with these findings, operation of the single-phase system showed that for an initial DCP concentration of 130 mg L(-1) the biomass was completely inhibited and DCP was not degraded, while the two-phase system achieved near-complete DCP removal. In sequencing batch mode the TPPB had a removal efficiency of 91% within 500 min for a feed of 320 mg L(-1), which exceeds the highest concentration previously degraded. These results have confirmed the effectiveness of the use of small amounts (5%, v/v) of inexpensive commercial polymers as the partitioning phase in TPPB reactors for the treatment of a highly toxic substrate at influent loads that are prohibitive for conventional single-phase operation, and suggest that similar detoxification of wastewater influents is achievable for other target cytotoxic substrates. Copyright © 2012 Elsevier B.V. All rights reserved.

  7. A Chemical Kinetic Mechanism for the Ignition of Silane/Hydrogen Mixtures

    NASA Technical Reports Server (NTRS)

    Jachimowski, C. J.; Mclain, A. G.

    1983-01-01

    A chemical kinetic reaction mechanism for the oxidation of silane/hydrogen mixtures is presented and discussed. Shock-tube ignition delay time data were used to evaluate and refine the mechanism. Good agreement between experimental results and the results predicted by the mechanism was obtained by adjusting the rate coefficient for the reaction SiH3 + O2 yields SiH2O + OH. The reaction mechanism was used to theoretically investigate the ignition characteristics of silane/hydrogen mixtures. The results revealed that over the entire range of temperature examined (800 K to 1200 K), substantial reduction in ignition delay times is obtained when silane is added to hydrogen.

  8. Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

    USGS Publications Warehouse

    Ni, Y.; Ma, Q.; Ellis, G.S.; Dai, J.; Katz, B.; Zhang, S.; Tang, Y.

    2011-01-01

    Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using ??D values in ethane from several basins in the world are in close agreement with similar predictions based on the ??13C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that ??D values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that ??D values in ethane might be more suitable for modeling than comparable values in methane and propane. ?? 2011 Elsevier Ltd.

  9. Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

    NASA Astrophysics Data System (ADS)

    Ni, Yunyan; Ma, Qisheng; Ellis, Geoffrey S.; Dai, Jinxing; Katz, Barry; Zhang, Shuichang; Tang, Yongchun

    2011-05-01

    Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2 cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using δD values in ethane from several basins in the world are in close agreement with similar predictions based on the δ 13C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that δD values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that δD values in ethane might be more suitable for modeling than comparable values in methane and propane.

  10. Localized surface plasmon resonance sensor for simultaneous kinetic determination of peroxyacetic acid and hydrogen peroxide.

    PubMed

    Tashkhourian, Javad; Hormozi-Nezhad, Mohammad Reza; Khodaveisi, Javad; Dashti, Razieh

    2013-01-31

    A new sensor for simultaneous determination of peroxyacetic acid and hydrogen peroxide using silver nanoparticles (Ag-NPs) as a chromogenic reagent is introduced. The silver nanoparticles have the catalytic ability for the decomposition of peroxyacetic acid and hydrogen peroxide; then the decomposition of them induces the degradation of silver nanoparticles. Hence, a remarkable change in the localized surface plasmon resonance absorbance strength could be observed. Spectra-kinetic approach and artificial neural network was applied for the simultaneous determination of peroxyacetic acid and hydrogen peroxide. Linear calibration graphs were obtained in the concentration range of (8.20×10(-5) to 2.00×10(-3) mol L(-1)) for peroxyacetic acid and (2.00×10(-5) to 4.80×10(-3) mol L(-1)) for hydrogen peroxide. The analytical performance of this sensor has been evaluated for the detection of simultaneous determination of peroxyacetic acid and hydrogen peroxide in real samples.

  11. Corrosion of concrete sewers--the kinetics of hydrogen sulfide oxidation.

    PubMed

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

    2008-05-01

    Hydrogen sulfide absorption and oxidation by corroding concrete surfaces was quantified in a test rig consisting of 6 concrete pipes operated under sewer conditions. The test rig was placed in an underground sewer monitoring station with access to fresh wastewater. Hydrogen sulfide gas was injected into the pipe every 2nd hour to peak concentrations around 1000 ppm. After some months of operation, the hydrogen sulfide became rapidly oxidized by the corroding concrete surfaces. At hydrogen sulfide concentrations of 1000 ppm, oxidation rates as high as 1 mg S m(-2) s(-1) were observed. The oxidation process followed simple nth order kinetics with a process order of 0.45-0.75. Extrapolating the results to gravity sewer systems showed that hydrogen sulfide oxidation by corroding concrete is a fast process compared to the release of hydrogen sulfide from the bulk water, resulting in low gas concentrations compared with equilibrium. Balancing hydrogen sulfide release with hydrogen sulfide oxidation at steady state conditions demonstrated that significant corrosion rates--several millimeters of concrete per year--can potentially occur at hydrogen sulfide gas phase concentrations well below 5-10 ppm. The results obtained in the study advances the knowledge on prediction of sewer concrete corrosion and the extent of odor problems.

  12. Capacitively Coupled Radio Frequency Discharge Plasmas In Hydrogen: Particle Modeling and Negative Ion Kinetics

    SciTech Connect

    Diomede, P.; Longo, S.; Capitelli, M.

    2005-05-16

    We present a 1D(r)2D(v) particle code for capacitively coupled radio frequency discharge plasmas in hydrogen, which includes a rigorous kinetic modeling of ion transport and several solutions to speed up the convergence. In a test case the effect of surface atom recombination and molecule vibrational deactivation on H- concentration is investigated.

  13. Changes in metal availability, desorption kinetics and speciation in contaminated soils during repeated phytoextraction with the Zn/Cd hyperaccumulator Sedum plumbizincicola.

    PubMed

    Li, Zhu; Jia, Mingyun; Wu, Longhua; Christie, Peter; Luo, Yongming

    2016-02-01

    Phytoextraction is one of the most promising technologies for the remediation of metal contaminated soils. Changes in soil metal availability during phytoremediation have direct effects on removal efficiency and can also illustrate the interactive mechanisms between hyperaccumulators and metal contaminated soils. In the present study the changes in metal availability, desorption kinetics and speciation in four metal-contaminated soils during repeated phytoextraction by the zinc/cadmium hyperaccumulator Sedum plumbizincicola (S. plumbizincicola) over three years were investigated by chemical extraction and the DGT-induced fluxes in soils (DIFS) model. The available metal fractions (i.e. metal in the soil solution extracted by CaCl2 and by EDTA) decreased greatly by >84% after phytoextraction in acid soils and the deceases were dramatic at the initial stages of phytoextraction. However, the decreases in metal extractable by CaCl2 and EDTA in calcareous soils were not significant or quite low. Large decreases in metal desorption rate constants evaluated by DIFS were found in calcareous soils. Sequential extraction indicated that the acid-soluble metal fraction was easily removed by S. plumbizincicola from acid soils but not from calcareous soils. Reducible and oxidisable metal fractions showed discernible decreases in acid and calcareous soils, indicating that S. plumbizincicola can mobilize non-labile metal for uptake but the residual metal cannot be removed. The results indicate that phytoextraction significantly decreases metal availability by reducing metal pool sizes and/or desorption rates and that S. plumbizincicola plays an important role in the mobilization of less active metal fractions during repeated phytoextraction. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Kinetics studies of d-glucose hydrogenation over activated charcoal supported platinum catalyst

    NASA Astrophysics Data System (ADS)

    Ahmed, Muthanna J.

    2012-02-01

    The kinetics of the catalytic hydrogenation of d-glucose to produce d-sorbitol was studied in a three-phase laboratory scale reactor. The hydrogenation reactions were performed on activated charcoal supported platinum catalyst in the temperature range 25-65°C and in a constant pressure of 1 atm. The kinetic data were modeled by zero, first and second-order reaction equations. In the operating regimes studied, the results show that the hydrogenation reaction was of a first order with respect to d-glucose concentration. Also the activation energy of the reaction was determined, and found to be 12.33 kJ mole-1. A set of experiment was carried out to test the deactivation of the catalyst, and the results show that the deactivation is slow with the ability of using the catalyst for several times with a small decrease in product yield.

  15. Thermodynamics and kinetics of graphene chemistry: a graphene hydrogenation prototype study.

    PubMed

    Pham, Buu Q; Gordon, Mark S

    2016-12-07

    The thermodynamic and kinetic controls of graphene chemistry are studied computationally using a graphene hydrogenation reaction and polyaromatic hydrocarbons to represent the graphene surface. Hydrogen atoms are concertedly chemisorped onto the surface of graphene models of different shapes (i.e., all-zigzag, all-armchair, zigzag-armchair mixed edges) and sizes (i.e., from 16-42 carbon atoms). The second-order Z-averaged perturbation theory (ZAPT2) method combined with Pople double and triple zeta basis sets are used for all calculations. It is found that both the net enthalpy change and the barrier height of graphene hydrogenation at graphene edges are lower than at their interior surfaces. While the thermodynamic product distribution is mainly determined by the remaining π-islands of functionalized graphenes (Phys. Chem. Chem. Phys., 2013, 15, 3725-3735), the kinetics of the reaction is primarily correlated with the localization of the electrostatic potential of the graphene surface.

  16. Pd Particle Size Effects on Methane Dissociation on MgO-supported Pd Nanoparticles and Desorption Kinetics of Small Alkane Molecules on MgO(100)

    NASA Astrophysics Data System (ADS)

    Tait, Steven L., Jr.; Dohnalek, Zdenek; Kay, Bruce D.; Campbell, Charles T.

    2004-03-01

    Oxide-supported Pd nanoparticle catalysts are active in a variety of reactions involving small alkanes, including low-temperature methane combustion. Temperature programmed desorption (TPD) was used to study the adsorption of small alkane molecules, C_nH_2n+2 (n=1-10), on the MgO(100) surface at low temperatures (24 K). Hydrocarbon molecules are deposited on the surface by a highly collimated molecular beam with a well-defined kinetic energy. The sample is heated at a controlled rate and desorption products are observed by QMS. Adsorption energy increases linearly with alkane chain length with a small y-intercept. Dissociative adsorption probability of methane on MgO-supported Pd particles (<5 nm dia.) is measured by titration of C fragments with molecular oxygen beam. Dissociation probability is observed to increase with decreasing Pd particle size. PNNL is a multiprogram National Laboratory operated for the U.S. Department of Energy by Battelle Memorial Institute under contract DE-AC06-76RLO 1830. SLT supported by a UW/PNNL Joint Institute for Nanotechnology fellowship.

  17. Lowering the desorption temperature of Mg(BH4)2 through doping

    NASA Astrophysics Data System (ADS)

    Harrison, D.; Thonhauser, T.

    2014-03-01

    Magnesium borohydride Mg(BH4)2 is a very promising hydrogen storage material due to its high gravimetric (14.9 mass%) and volumetric density. However, it is limited for practical storage applications by its high hydrogen desorption temperature of 270°C. Arguments have been made for both high thermodynamic stability and slow kinetics to be responsible for this high desorption temperature. In our study we show that doping of Mg(BH4)2 can address the thermodynamic stability issue and predictably lower its desorption enthalpy. We use ab initio calculations at the DFT level (utilizing vdW-DF) and calculate the change in desorption enthalpy from ground state energy and phonon contributions for several possible hydrogen release reactions. Note that van der Waals interactions are crucial to correctly describe the ground state of this complex hydride. We find that, depending on the reaction, the undoped phase has a desorption enthalpy of 50-75 kJ/mol H2 and doping can lower this number by approximately 5 kJ/mol per 10% doping at 300 K, making the desired range of 40 kJ/mol easily accessible. We argue that this lowering of desorption enthalpy will correspond to a lowering of the desorption temperature. Supported by NSF DMR-1145968.

  18. Stereoselectivity of the hydrogen-atom transfer in benzophenone-tyrosine dyads: an intramolecular kinetic solvent effect.

    PubMed

    Hörner, Gerald; Hug, Gordon L; Lewandowska, Anna; Kazmierczak, Franciszek; Marciniak, Bronislaw

    2009-01-01

    To be or not to be solvated is the decisive parameter that controls the photoinduced hydrogen-atom transfer in diastereomeric ketone/phenol dyads. A kinetic solvent effect that refers to hydrogen bonding between the phenol and the solvent is suggested to be the main source of the stereoselective discrimination in the hydrogen transfer (see figure).

  19. Kinetics of toluene sorption and desorption in Ca- and Cu-montmorillonites investigated with Fourier transform infrared spectroscopy under two different levels of humidity.

    PubMed

    Shih, Yang-Hsin; Wu, Shian-Chee

    2004-09-01

    Clays in soils or groundwater aquifer materials play roles in the sorption of organic pollutants. The intrinsic sorption kinetics of toluene in dry and humid clay films was investigated by tracking the change of infrared absorbance. Under the humid condition, similar toluene-sorbed intensities were found in Ca- and Cu-montmorillonites. However, a higher intensity of sorbed toluene was found in the Cu-form than in the Ca-form under the dry condition, which indicates a stronger interaction occurring in dry Cu-montmorillonite. The general time scale of sorption of toluene on clays is around 100 s. In both forms of montmorillonite, some portion of toluene was desorbed at an extremely slow rate under the dry condition. Some newly identified peaks were persistent against desorption from montmorillonites, suggesting the existence of irreversibly sorbed species and the possibility of toluene transformation occurring in clay systems.

  20. The kinetics of catalytic hydrogenation of pyrene-implications for direct coal liquefaction processing

    SciTech Connect

    Stephens, H.P.; Chapman, R.N.

    1983-01-01

    Although recycling heavy solvents has recently re-emerged as a key to cutting the cost of direct coal liquefaction, little data for the hydrogenation of heavy solvent donors have been reported. This study addresses the kinetic and thermodynamic aspects of catalytic hydrogenation of pyrene, a donor solvent precursor thought to play an important role in coal liquefaction processes that use heavy recycle solvents. In the presence of a catalyst, pyrene (Py) is hydrogenated to di- (H/sub 2/Py), tetra- (H/sub 4/Py), hexa- (H/sub 6/Py), deca- (H/sub 10/Py) and perhydro- (H/sub 16/Py) species via a complex mechanism involving a network of reversible parallel and series reactions. Though several studies have dealt with aspects of pyrene hydrogenation, including hydrocracking reactions, reaction product distributions and thermodynamic properties, the kinetics of hydrogenation have not been previously reported. Ultimate application of kinetic and thermodynamic data to direct coal liquefaction must take into consideration the conditions imposed by the particular process used. However, two generalizations may be made regarding hydrogen supplied by the dihydropyrene component of donor solvents: (1) Increasing hydrogen partial pressure increases both the rate at which H/sub 2/Py is formed and the equilibrium concentration of H/sub 2/Py. Therefore, pyrene rehydrogenation should be done at as high a pressure as is cost effective. Although an increase in temperature favors the rate of attainment of equilibrium between Py and H/sub 2/Py, the position of the equilibrium is shifted toward pyrene. Temperature must therefore be adjusted to achieve an optimum trade-off between rate of formation and maximum possible concentration of H/sub 2/Py.

  1. Non-isothermal reduction kinetics of titanomagnetite by hydrogen

    NASA Astrophysics Data System (ADS)

    Dang, Jie; Zhang, Guo-hua; Hu, Xiao-jun; Chou, Kuo-chih

    2013-12-01

    Reduction of titanomagnetite (TTM) powders by H2-Ar gas mixtures was investigated under a non-isothermal condition by using a thermogravimetric analysis system. It was found that non-isothermal reduction of TTM proceeded via a dual-reaction mechanism. The first reaction was reduction of TTM to wüstite and ilmenite, whereas the second one was reduction of wüstite and ilmenite to iron and titanium dioxide. By using a new model for the dual reactions, which was in an analytical form and incorporated different variables, such as time, temperature, particle size, and hydrogen partial pressure, rate-controlling steps for the dual reactions were obtained with the apparent activation energies calculated to be 90-98 and 115-132 kJ/mol for the first and second reactions, respectively.

  2. Kinetics of the reaction of nitric oxide with hydrogen

    NASA Technical Reports Server (NTRS)

    Flower, W. L.; Hanson, R. K.; Kruger, C. H.

    1974-01-01

    Mixtures of NO and H2 diluted in argon or krypton were heated by incident shock waves, and the infrared emission from the fundamental vibration-rotation band of NO at 5.3 microns was used to monitor the time-varying NO concentration. The reaction kinetics were studied in the temperature range 2400-4500 K using a shock-tube technique. The decomposition of nitric oxide behind the shock was found to be modeled well by a fifteen-reaction system. A principle result of the study was the determination of the rate constant for the reaction H + NO yields N + OH, which may be the rate-limiting step for NO removal in some combustion systems. Experimental values of k sub 1 were obtained for each test through comparisons of measured and numerically predicted NO profiles.

  3. Texture in a ternary Nd 16.2Fe 78.2B 5.6 powder using a modified hydrogenation-disproportionation-desorption-recombination process

    NASA Astrophysics Data System (ADS)

    Gutfleisch, O.; Gebel, B.; Mattern, N.

    2000-02-01

    A modified hydrogenation-disproportionation desorption-recombination (HDDR) process consisting of (i) solid disproportionation and (ii) slow recombination under partial hydrogen pressure has been applied to a Nd 16.2Fe 78.2B 5.6 alloy. Scanning electron microscopy shows that an initially fine rod-like structure of NdH 2± x and Fe observed after 15 min of hydrogenation at 900°C is transformed into a granular morphology with prolonged annealing. Simultaneously, finely dispersed tetragonal Fe 3B particles of 10-50 nm diameter exist. XRD studies show that this metastable Fe 3B phase is transformed to Fe 2B and Fe on further annealing. Short solid-disproportionation times result in a higher degree of anisotropy after recombination, whereas long annealing times and conventional processing lead to isotropic material. It is concluded that the formation of the intermediate tetragonal Fe 3B phase after solid disproportionation is pivotal for the inducement of texture in HDDR processed ternary NdFeB-type alloys.

  4. Ultraviolet/matrix-assisted laser desorption/ionization mass spectrometric characterization of 2,5-dihydroxybenzoic acid-induced reductive hydrogenation of oligonucleotides on cytosine residues.

    PubMed

    Koomen, J M; Russell, D H

    2000-08-01

    The changes in the ion signals in the isotope cluster, mass resolution, signal-to-noise ratio and mass accuracy for matrix-assisted laser desorption/ionization (MALDI) of DNA oligonucleotides (dGGATC, dCAGCt, and dAACCGTT) and their fragment ions were evaluated, and these data were compared with those obtained using 3-hydroxypicolinic acid. Mass spectra obtained by using 2,5-dihydroxybenzoic acid (2,5-DHB) appear to have differences from the theoretical isotopic clusters, which arise by reductive hydrogenation producing a second peak at the M + 2 isotope of the native oligonucleotide. Based on the patterns of the isotopic envelope observed in the in-source decay fragments, we propose that cytosine is the site of reduction. We do not find evidence of reduction of oligonucleotides, viz. dTGGGGTT, that do not contain cytosine; however, 2'-deoxycytidine and 2'-deoxycytidine-5'-monophosphate undergo reductive hydrogenation. Several experiments were carried out in an effort to determine whether the reductive hydrogenation occurs during sample preparation or as a result of laser irradiation. The results of these experiments suggest that it occurs during sample preparation. The relative intensities of ion signals corresponding to the reduced base can be altered by using different matrix additives (aminonaphthalenes) or a different substrate (copper). Also, the oxidized form of 2,5-DHB is trapped by reaction with the side chain of cysteine in glutathione, providing evidence that the reaction occurs in solution as the matrix crystallizes.

  5. Kinetics of Hydrogen Oxidation Downstream of Lean Propane and Hydrogen Flames

    NASA Technical Reports Server (NTRS)

    Fine, Burton

    1961-01-01

    The decay of hydrogen was measured downstream of lean, flat, premixed hydrogen and propane-air flames seated on cooled porous burners. Experimental variables included temperature, pressure, initial equivalence ratio and diluent. Sampling of burned gas was done through uncooled quartz orifice probes, and the analysis was based on gas chromatography. An approximate treatment of the data in which diffusion was neglected led to the following rate expression for the zone downstream of hydrogen flames d[H (sub 2)] divided by (d times t) equals 1.7 times 10 (sup 10) [H (sub 2)] (sup 3) divided by (sub 2) [O (sub 2)]e (sup (-8100 divided by RT)) moles per liters per second. On the basis of a rate expression of this form, the specific rate constant for the reaction downstream of hydrogen flames was about three times as great as that determined downstream of propane flames. This result was explained on the basis of the existence of a steady state between hydrogen and carbon monoxide in the burned gas downstream of propane flames.

  6. Washout kinetics of inhaled hydrogen cyanide in breath.

    PubMed

    Stamyr, Kristin; Nord, Pierre; Johanson, Gunnar

    2008-06-10

    Hydrogen cyanide (HCN) intoxication causes or contributes significantly to many of the fatalities among fire victims. To enable fast treatment of HCN poisoning, a more rapid diagnostic method than currently available is required. One possibility would be measurement in exhaled air. However, as HCN is highly water soluble, it may be absorbed during inhalation and reabsorbed during exhalation. If this, so-called, washin-washout effect is substantial it may interfere with the diagnosis, as a major part of breath HCN may originate from the respiratory tract, due to recent exposure, and not from systemic exposure. The aim of this study was to estimate the importance of the washin-washout effect of HCN. The time-course of cyanide in exhaled air was measured with an electrochemical detector in 10 volunteers during and after a 1 min x 10 ppm exposure to HCN. The experiment revealed an average half-life of 16s (range 10-24s) in breath. Extrapolating the results to higher exposures suggests that the contribution from washin-washout from the airways will be negligible even at fatal exposures. The results support the use of breath HCN as a potential indicator of systemic intoxication.

  7. Analytical chemical kinetic investigation of the effects of oxygen, hydrogen, and hydroxyl radicals on hydrogen-air combustion

    NASA Technical Reports Server (NTRS)

    Carson, G. T., Jr.

    1974-01-01

    Quantitative values were computed which show the effects of the presence of small amounts of oxygen, hydrogen, and hydroxyl radicals on the finite-rate chemical kinetics of premixed hydrogen-air mixtures undergoing isobaric autoignition and combustion. The free radicals were considered to be initially present in hydrogen-air mixtures at equivalence ratios of 0.2, 0.6, 1.0, and 1.2. Initial mixture temperatures were 1100 K, 1200 K, and 1500 K, and pressures were 0.5, 1.0, 2.0, and 4.0 atm. Of the radicals investigated, atomic oxygen was found to be the most effective for reducing induction time, defined as the time to 5 percent of the total combustion temperature rise. The reaction time, the time between 5 percent and 95 percent of the temperature rise, is not decreased by the presence of free radicals in the initial hydrogen-air mixture. Fuel additives which yield free radicals might be used to effect a compact supersonic combustor design for efficient operation in an otherwise reaction-limited combustion regime.

  8. Kinetic solvent effects on hydrogen abstraction reactions from carbon by the cumyloxyl radical. The role of hydrogen bonding.

    PubMed

    Bietti, Massimo; Salamone, Michela

    2010-08-20

    A kinetic study of the H-atom abstraction reactions from 1,4-cyclohexadiene and triethylamine by the cumyloxyl radical has been carried out in different solvents. Negligible effects are observed with 1,4-cyclohexadiene, whereas with triethylamine a significant decrease in rate constant (k(H)) is observed on going from benzene to MeOH. A good correlation between log k(H) and the solvent hydrogen bond donor parameter alpha is observed, indicative of an H-bonding interaction between the amine lone pair and the solvent.

  9. Process development for hydrogen production with Chlamydomonas reinhardtii based on growth and product formation kinetics.

    PubMed

    Lehr, Florian; Morweiser, Michael; Rosello Sastre, Rosa; Kruse, Olaf; Posten, Clemens

    2012-11-30

    Certain strains of microalgae are long known to produce hydrogen under anaerobic conditions. In Chlamydomonas reinhardtii the oxygen-sensitive hydrogenase enzyme recombines electrons from the chloroplast electron transport chain with protons to form molecular hydrogen directly inside the chloroplast. A sustained hydrogen production can be obtained under low sulfur conditions in C. reinhardtii, reducing the net oxygen evolution by reducing the photosystem II activity and thereby overcoming the inhibition of the hydrogenases. The development of specially adapted hydrogen production strains led to higher yields and optimized biological process preconditions. So far sustainable hydrogen production required a complete exchange of the growth medium to establish sulfur-deprived conditions after biomass growth. In this work we demonstrate the transition from the biomass growth phase to the hydrogen production phase in a single batch culture only by exact dosage of sulfur. This eliminates the elaborate and energy intensive solid-liquid separation step and establishes a process strategy to proceed further versus large scale production. This strategy has been applied to determine light dependent biomass growth and hydrogen production kinetics to assess the potential of H₂ production with C. reinhardtii as a basis for scale up and further process optimization.

  10. Stereoselective synthesis of norephedrine and norpseudoephedrine by using asymmetric transfer hydrogenation accompanied by dynamic kinetic resolution.

    PubMed

    Lee, Hyeon-Kyu; Kang, Soyeong; Choi, Eun Bok

    2012-06-15

    Each of the enantiomers of both norephedrine and norpseudoephedrine were stereoselectively prepared from the common, prochiral cyclic sulfamidate imine of racemic 1-hydroxy-1-phenyl-propan-2-one by employing asymmetric transfer hydrogenation (ATH) catalyzed by the well-defined chiral Rh-complexes, (S,S)- or (R,R)-Cp*RhCl(TsDPEN), and HCO(2)H/Et(3)N as the hydrogen source. The ATH processes are carried out under mild conditions (rt, 15 min) and are accompanied by dynamic kinetic resolution.

  11. Understanding kinetic solvent effects on hydrogen abstraction reactions from carbon by the cumyloxyl radical.

    PubMed

    Bietti, Massimo; Martella, Roberto; Salamone, Michela

    2011-11-18

    A kinetic study of the hydrogen abstraction reactions from tetrahydrofuran (THF) and cyclohexane (CHX) by the cumyloxyl radical was carried out in different solvents. With THF, a 4.5-fold decrease in rate constant (k(H)) was observed on going from isooctane to 2,2,2-trifluoroethanol. An opposite behavior was observed with CHX, where k(H) increased by a factor 4 on going from isooctane to 2,2,2-trifluoroethanol. The important role of substrate structure and of the solvent hydrogen bond donor ability is discussed.

  12. Kinetics of vapor-phase hydrogenation of furfural on a copper-chromium catalyst

    SciTech Connect

    Borts, M.S.; Gil'chenok, N.D.; Gurevich, G.S.; Ignat'ev, V.M.

    1986-08-01

    This paper studies the principal kinetic relationships of hydrogenation of furfural to furfuryl alcohol, which must be known for development of the industrial process. Prelininary experiments showed that at linear velocities of the vapor-gas stream (calculated for the free cross section of the reactor) above 0.26 matsec and with an average catalyst particle size less than 0.30 mm neither external nor internal diffusio resistance has any effect. In all the subsequent experiments a 0.20-0.25-mm catalyst fraction was used at a linear vapor-gas velocity of 0.50 m/sec, when the reaction proceeded with kinetic control.

  13. Kinetics and models of hydrogenation of phenylhydroxylamine and azobenzene on nickel catalysts in aqueous 2-propanol solutions

    NASA Astrophysics Data System (ADS)

    Romanenko, Yu. E.; Merkin, A. A.; Komarov, A. A.; Lefedova, O. V.

    2014-08-01

    The kinetics of the hydrogenation of intermediates in the reduction of nitrobenzene in aqueous 2-propanol with acetic acid and sodium hydroxide additions on nickel catalysts was studied. A kinetic description of liquid-phase hydrogenation of azobenzene and phenylhydroxylamine was suggested. A kinetic model was developed. The dependences that characterize the variation of the amounts of the starting compound, reaction product, and absorbed hydrogen during the reaction were calculated. The calculated values were shown to be in satisfactory agreement with the experimental values under different reaction conditions.

  14. Adsorption isotherms, kinetics, thermodynamics and desorption studies of 2,4,6-trichlorophenol on oil palm empty fruit bunch-based activated carbon.

    PubMed

    Tan, I A W; Ahmad, A L; Hameed, B H

    2009-05-30

    The adsorption characteristics of 2,4,6-trichlorophenol (TCP) on activated carbon prepared from oil palm empty fruit bunch (EFB) were evaluated. The effects of TCP initial concentration, agitation time, solution pH and temperature on TCP adsorption were investigated. TCP adsorption uptake was found to increase with increase in initial concentration, agitation time and solution temperature whereas adsorption of TCP was more favourable at acidic pH. The adsorption equilibrium data were best represented by the Freundlich and Redlich-Peterson isotherms. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. The mechanism of the adsorption process was determined from the intraparticle diffusion model. Boyd plot revealed that the adsorption of TCP on the activated carbon was mainly governed by particle diffusion. Thermodynamic parameters such as standard enthalpy (DeltaH degrees ), standard entropy (DeltaS degrees ), standard free energy (DeltaG degrees ) and activation energy were determined. The regeneration efficiency of the spent activated carbon was high, with TCP desorption of 99.6%.

  15. Density Functional Theory Based Kinetic Monte Carlo Approach for Understanding Atomistic Mechanisms for Reversible Hydrogen Storage in Metal Hydrides: Application to Alane Formation on Ti Doped Al Surfaces

    NASA Astrophysics Data System (ADS)

    Karim, A.; Muckerman, J.; Sutter, P.; Muller, E.

    2008-03-01

    We describe a density functional kinetic Monte Carlo approach enabling us to study and simulate the steady-state situation of dissociative adsorption of hydrogen along with diffusion and reaction of Al and H atoms leading towards the formation of alane species on Ti-doped Al surfaces. In the first step, density functional theory is used in conjunction with the nudged elastic band/drag method to obtain the energetics of the relevant atomistic processes of Al and H diffusion and their reactions on Al surfaces with different concentration of dopant Ti atoms. Subsequently, the kinetic Monte Carlo method is employed, which accounts for the spatial distribution, fluctuations, and evolution of chemical species at Ti-doped Al surfaces under steady-state conditions. This DFT-based KMC approach provides an insight into the kinetics of alanes at technologically relevant pressure and temperature conditions. Our computed production rates of AlH3 on Al surfaces are in agreement with experimental data. We also obtained temperature programmed desorption spectra of different alane species, which is agreeing well with experiments.

  16. Oxygen atom kinetics in silane-hydrogen-nitrous oxide mixtures behind reflected shock waves

    NASA Astrophysics Data System (ADS)

    Javoy, S.; Mével, R.; Dupré, G.

    2010-11-01

    Resonance Absorption Spectroscopy has been used to study the O-atom dynamics behind reflected shock waves in highly argon diluted silane-hydrogen-nitrous oxide mixtures in the temperature range 1606-2528 K and at total pressures from 234 to 584 kPa. The absorptions at 130.5 nm of N 2O, SiH 4 and Si have been taken into account to compare simulated and experimental absorption profiles. A detailed kinetic model has been also used to interpret the results and reaction pathway and sensitivity analyses have been performed to underline important elementary reactions. A comparison with the O-atom kinetic in silane-nitrous oxide and hydrogen-nitrous oxide mixtures is also proposed.

  17. Hydrogen-bond driven loop-closure kinetics in unfolded polypeptide chains

    SciTech Connect

    Daidone, Isabella; Neuweiler, H; Doose, S; Sauer, M; Smith, Jeremy C

    2010-12-01

    Characterization of the length dependence of end-to-end loop-closure kinetics in unfolded polypeptide chains provides an understanding of early steps in protein folding. Here, loop-closure in poly-glycine-serine peptides is investigated by combining single-molecule fluorescence spectroscopy with molecular dynamics simulation. For chains containing more than 10 peptide bonds loop-closing rate constants on the 20-100 nanosecond time range exhibit a power-law length dependence. However, this scaling breaks down for shorter peptides, which exhibit slower kinetics arising from a perturbation induced by the dye reporter system used in the experimental setup. The loop-closure kinetics in the longer peptides is found to be determined by the formation of intra-peptide hydrogen bonds and transient beta-sheet structure, that accelerate the search for contacts among residues distant in sequence relative to the case of a polypeptide chain in which hydrogen bonds cannot form. Hydrogen-bond-driven polypeptide-chain collapse in unfolded peptides under physiological conditions found here is not only consistent with hierarchical models of protein folding, that highlights the importance of secondary structure formation early in the folding process, but is also shown to speed up the search for productive folding events.

  18. In situ hydrogen consumption kinetics as an indicator of subsurface microbial activity

    USGS Publications Warehouse

    Harris, S.H.; Smith, R.L.; Suflita, J.M.

    2007-01-01

    There are few methods available for broadly assessing microbial community metabolism directly within a groundwater environment. In this study, hydrogen consumption rates were estimated from in situ injection/withdrawal tests conducted in two geochemically varying, contaminated aquifers as an approach towards developing such a method. The hydrogen consumption first-order rates varied from 0.002 nM h-1 for an uncontaminated, aerobic site to 2.5 nM h-1 for a contaminated site where sulfate reduction was a predominant process. The method could accommodate the over three orders of magnitude range in rates that existed between subsurface sites. In a denitrifying zone, the hydrogen consumption rate (0.02 nM h-1) was immediately abolished in the presence of air or an antibiotic mixture, suggesting that such measurements may also be sensitive to the effects of environmental perturbations on field microbial activities. Comparable laboratory determinations with sediment slurries exhibited hydrogen consumption kinetics that differed substantially from the field estimates. Because anaerobic degradation of organic matter relies on the rapid consumption of hydrogen and subsequent maintenance at low levels, such in situ measures of hydrogen turnover can serve as a key indicator of the functioning of microbial food webs and may be more reliable than laboratory determinations. ?? 2007 Federation of European Microbiological Societies.

  19. In situ oxidation remediation technologies: kinetic of hydrogen peroxide decomposition on soil organic matter.

    PubMed

    Romero, Arturo; Santos, Aurora; Vicente, Fernando; Rodriguez, Sergio; Lafuente, A Lopez

    2009-10-30

    Rates of hydrogen peroxide decomposition were investigated in soils slurries. The interaction soil-hydrogen peroxide was studied using a slurry system at 20 degrees C and pH 7. To determine the role of soil organic matter (SOM) in the decomposition of hydrogen peroxide, several experiments were carried out with two soils with different SOM content (S1=15.1%, S2=10%). The influence of the oxidant dosage ([H2O2](o) from 10 to 30 g L(-1) and soil weight to liquid phase volume ratio=500 g L(-1)) was investigated using the two calcareous loamy sand soil samples. The results showed a rate dependency on both SOM and hydrogen peroxide concentration being the H2O2 decomposition rate over soil surface described by a second-order kinetic expression r(H2O2) = -dn(H2O2) / W(SOM) dt = kC(H2O2) C(SOM). Thermogravimetric analysis (TGA) was used to evaluate the effect caused by the application of this oxidant on the SOM content. It was found a slightly increase of SOM content after treatment with hydrogen peroxide, probably due to the incorporation of oxygen from the oxidant (hydrogen peroxide).

  20. Effect of electrolytical hydrogenation on the thermal stability and crystallization kinetics of METGLASS MBF-50

    NASA Astrophysics Data System (ADS)

    Górecki, Cz; Górecki, T.

    2007-08-01

    The effect of electrolytical hydrogenation on both the surface and volume crystallization kinetics and thermal stability of amorphous alloy METGLASS MBF-50 has been investigated. The surface crystallization has been investigated by the exoelectron emission (EEE) technique, whereas the volume crystallization has been followed by differential thermal analysis (DTA). It has been found that both the surface and volume crystallization of investigated material occur in two stages. The surface crystallization occurs at temperature lower and with activation energy distinctly smaller than the volume crystallization. Hydrogenation of the investigated metallic glass enhances its thermal stability by increasing the activation energies for both the surface and volume crystallization. The results of DTA measurements indicate that hydrogenation causes an increase in the enthalpy of both stages of volume crystallization.

  1. Anisotropic hydrogen diffusion in α-Zr and Zircaloy predicted by accelerated kinetic Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Zhang, Yongfeng; Jiang, Chao; Bai, Xianming

    2017-01-01

    This report presents an accelerated kinetic Monte Carlo (KMC) method to compute the diffusivity of hydrogen in hcp metals and alloys, considering both thermally activated hopping and quantum tunneling. The acceleration is achieved by replacing regular KMC jumps in trapping energy basins formed by neighboring tetrahedral interstitial sites, with analytical solutions for basin exiting time and probability. Parameterized by density functional theory (DFT) calculations, the accelerated KMC method is shown to be capable of efficiently calculating hydrogen diffusivity in α-Zr and Zircaloy, without altering the kinetics of long-range diffusion. Above room temperature, hydrogen diffusion in α-Zr and Zircaloy is dominated by thermal hopping, with negligible contribution from quantum tunneling. The diffusivity predicted by this DFT + KMC approach agrees well with that from previous independent experiments and theories, without using any data fitting. The diffusivity along is found to be slightly higher than that along , with the anisotropy saturated at about 1.20 at high temperatures, resolving contradictory results in previous experiments. Demonstrated using hydrogen diffusion in α-Zr, the same method can be extended for on-lattice diffusion in hcp metals, or systems with similar trapping basins.

  2. Anisotropic hydrogen diffusion in α-Zr and Zircaloy predicted by accelerated kinetic Monte Carlo simulations

    PubMed Central

    Zhang, Yongfeng; Jiang, Chao; Bai, Xianming

    2017-01-01

    This report presents an accelerated kinetic Monte Carlo (KMC) method to compute the diffusivity of hydrogen in hcp metals and alloys, considering both thermally activated hopping and quantum tunneling. The acceleration is achieved by replacing regular KMC jumps in trapping energy basins formed by neighboring tetrahedral interstitial sites, with analytical solutions for basin exiting time and probability. Parameterized by density functional theory (DFT) calculations, the accelerated KMC method is shown to be capable of efficiently calculating hydrogen diffusivity in α-Zr and Zircaloy, without altering the kinetics of long-range diffusion. Above room temperature, hydrogen diffusion in α-Zr and Zircaloy is dominated by thermal hopping, with negligible contribution from quantum tunneling. The diffusivity predicted by this DFT + KMC approach agrees well with that from previous independent experiments and theories, without using any data fitting. The diffusivity along is found to be slightly higher than that along , with the anisotropy saturated at about 1.20 at high temperatures, resolving contradictory results in previous experiments. Demonstrated using hydrogen diffusion in α-Zr, the same method can be extended for on-lattice diffusion in hcp metals, or systems with similar trapping basins. PMID:28106154

  3. Anisotropic hydrogen diffusion in α-Zr and Zircaloy predicted by accelerated kinetic Monte Carlo simulations

    DOE PAGES

    Zhang, Yongfeng; Jiang, Chao; Bai, Xianming

    2017-01-20

    Here, this report presents an accelerated kinetic Monte Carlo (KMC) method to compute the diffusivity of hydrogen in hcp metals and alloys, considering both thermally activated hopping and quantum tunneling. The acceleration is achieved by replacing regular KMC jumps in trapping energy basins formed by neighboring tetrahedral interstitial sites, with analytical solutions for basin exiting time and probability. Parameterized by density functional theory (DFT) calculations, the accelerated KMC method is shown to be capable of efficiently calculating hydrogen diffusivity in α-Zr and Zircaloy, without altering the kinetics of long-range diffusion. Above room temperature, hydrogen diffusion in α-Zr and Zircaloy ismore » dominated by thermal hopping, with negligible contribution from quantum tunneling. The diffusivity predicted by this DFT + KMC approach agrees well with that from previous independent experiments and theories, without using any data fitting. The diffusivity along < c > is found to be slightly higher than that along < a >, with the anisotropy saturated at about 1.20 at high temperatures, resolving contradictory results in previous experiments. Demonstrated using hydrogen diffusion in α-Zr, the same method can be extended for on-lattice diffusion in hcp metals, or systems with similar trapping basins.« less

  4. Anisotropic hydrogen diffusion in α-Zr and Zircaloy predicted by accelerated kinetic Monte Carlo simulations.

    PubMed

    Zhang, Yongfeng; Jiang, Chao; Bai, Xianming

    2017-01-20

    This report presents an accelerated kinetic Monte Carlo (KMC) method to compute the diffusivity of hydrogen in hcp metals and alloys, considering both thermally activated hopping and quantum tunneling. The acceleration is achieved by replacing regular KMC jumps in trapping energy basins formed by neighboring tetrahedral interstitial sites, with analytical solutions for basin exiting time and probability. Parameterized by density functional theory (DFT) calculations, the accelerated KMC method is shown to be capable of efficiently calculating hydrogen diffusivity in α-Zr and Zircaloy, without altering the kinetics of long-range diffusion. Above room temperature, hydrogen diffusion in α-Zr and Zircaloy is dominated by thermal hopping, with negligible contribution from quantum tunneling. The diffusivity predicted by this DFT + KMC approach agrees well with that from previous independent experiments and theories, without using any data fitting. The diffusivity along is found to be slightly higher than that along , with the anisotropy saturated at about 1.20 at high temperatures, resolving contradictory results in previous experiments. Demonstrated using hydrogen diffusion in α-Zr, the same method can be extended for on-lattice diffusion in hcp metals, or systems with similar trapping basins.

  5. Kinetic limitations of the Mg2Si system for reversible hydrogen storage

    NASA Astrophysics Data System (ADS)

    Kelly, Stephen T.; Van Atta, Sky L.; Vajo, John J.; Olson, Gregory L.; Clemens, B. M.

    2009-05-01

    Despite the promising thermodynamics and storage capacities of many destabilized metal hydride hydrogen storage material systems, they are often kinetically limited from achieving practical and reversible behavior. Such is the case with the Mg2Si system. We investigated the kinetic mechanisms responsible for limiting the reversibility of the MgH2+Si system using thin films as a controlled research platform. We observed that the reaction \\mathrm {MgH}_2+\\frac {1}{2}\\mathrm {Si} \\Leftrightarrow \\frac {1}{2}\\mathrm {Mg}_2\\mathrm {Si}+\\mathrm {H}_2 is limited by the mass transport of Mg and Si into separate phases. Hydrogen readily diffuses through the Mg2Si material and nucleating MgH2 phase growth does not result in reaction completion. By depositing and characterizing multilayer films of Mg2Si and Mg with varying Mg2Si layer thicknesses, we conclude that the hydrogenation reaction consumes no more than 1 nm of Mg2Si, making this system impractical for reversible hydrogen storage.

  6. Reduced kinetic mechanism of ignition for nonpremixed hydrogen/air in a supersonic mixing layer

    SciTech Connect

    Ju, Y.; Niioka, T. . Inst. of Fluid Science)

    1994-11-01

    Transient ignition processes in a two-dimensional spatially evolving supersonic mixing layer consisting of a parallel nonpremixed airstream and a hydrogen stream both with temperatures higher than 1,000 K were investigated numerically by using the full chemistry and its reduced chemistry. A phenomenon different from that examined in previous studies, in which ignition of hydrogen/oxygen mixtures was considered, was found in the nonpremixed case examined here. It was shown that the concentration of O was greater than that of OH before ignition, but became smaller with the development of ignition process. Fourteen important reactions for ignition were obtained and verified using sensitivity analyses of ignition delay time and radical concentrations. Several different four-step and three-step reduced kinetic mechanisms were then deduced by introducing the steady-state approximation to different species. Comparison of these reduced kinetic mechanisms with the full chemistry showed that the steady-state approximation of O used in previous studies caused serious errors in the prediction of ignition delay time in supersonic flow, in which nonpremixed character is predominant and the transport phenomenon is important. Ignition locations predicted with the proper four-step and three-step reduced kinetic mechanisms were within 5% and 20% of those predicted with the full chemistry. Finally, these two reduced mechanisms were used to evaluate the effect of viscous dissipation on ignition in the supersonic shear layer. Good agreements between the results of the present reduced kinetic mechanisms and those of the full chemistry were obtained.

  7. The Role of Desorption Kinetics on the Colloid-Facilitated Transport of Cesium and Strontium in a Partially-Saturated Quartz Sand Column

    NASA Astrophysics Data System (ADS)

    Dittrich, T. M.; Ryan, J. N.; Saiers, J. E.

    2010-12-01

    Colloid-facilitated transport (CFT) is a mechanism for enhanced transport of contaminants under certain environmental conditions. In order for CFT to be significant, three conditions must be met: (1) colloids must be present at a significant concentration, 2) the contaminant must associate with and remain associated with the colloids, and 3) colloids must be transported faster than the contaminant on its own. Colloids are often present in significant concentrations; therefore, CFT strongly depends on slow desorption kinetics and colloid mobility. The goal of this research was to identify and quantify the effects of desorption kinetics on the transport of cesium and strontium through a quartz sand column at different degrees of saturation (moisture contents). Breakthrough experiments were conducted using a rainfall simulator suspended over a column (12.7 cm diameter, 33.5 cm depth) packed with clean, sieved quartz sand (d50 = 360 µm). The effluent was collected with a fraction collector. Cesium and strontium were used as model contaminants because they are common contaminants found on Department of Energy sites in the US and because they have contrasting sorption kinetics with illite, which was used as the model colloid. The column was instrumented with three tensiometers and three moisture sensors to ensure uniform flow under partially-saturated conditions. Relative saturations of 0.33, 0.80, and 1.0 were established in the column. For aqueous breakthrough experiments, solutions at pH 7.3 containing cesium or strontium at a concentration of 7.5 x 10-6 M were applied to the top of the column until breakthrough (C/C0 > 0.5) was achieved. Following breakthrough, the solution was switched to a cesium- or strontium-free pH 7.3 solution for about 40 pore volumes. These experiments were repeated with the addition of illite colloids at a concentration of 100 mg L-1 in equilibrium with the cesium of strontium solution. Cesium and strontium breakthrough was monitored by

  8. Influence of adsorption or desorption and surface diffusion on the formation kinetics of open half-monolayer coverage

    NASA Astrophysics Data System (ADS)

    Feldman, E. P.; Stefanovich, L. I.; Terekhova, Yu. V.

    2014-06-01

    The formation kinetics of open half-monolayer films on solid substrates is studied by the deposition of particles from a gaseous (vapor) phase to a cold substrate (room temperature) provided the lateral interaction between the particles of adsorbed layer (adlayer) is attractive. A detailed analysis of two limiting cases is presented: when the half-monolayer film formation rate is limited by the adsorption of particles from the gas phase and when the formation of the half-monolayer film surface is determined by the rate of surface diffusion of the adsorbed particles. The asymptotic analysis of the coverage dispersion evolution and the characteristic spatial scale of coverage inhomogeneities at the early and late stages of relaxation of a submonolayer film after quenching under the spinodal is carried out. It is found that separation of the adlayer occurs, so inhomogeneities of submonolayer films at the later stages of the process tend to equilibrium values of coverage in any case. However, asymptotic and numerical analysis shows that in the second case for some relationship between the kinetic and thermodynamic parameters of the adlayer an intermediate asymptotic relaxation process can be observed. It testifies to a kinetic slowdown of the separation process at the spinodal values of coverages. This fact manifests as the appearance of the intermediate plateau in the evolution curves for the coverage dispersion and nonmonotonic change of the characteristic spatial scale of coverage inhomogeneities. Moreover, at the early stages of the coverage evolution, the incubation period is revealed in the development of its inhomogeneities. It is shown that at the later stages of the separation of the half-monolayer film, the characteristic spatial scale of coverage inhomogeneities increases with time according to the law τ1/2 and the width of the transition region between enriched and depleted regions of adlayer decreases as 1/τ1/2.

  9. Isothermal-desorption-rate measurements in the vicinity of the Curie temperature for H2 chemisorbed on nickel films

    NASA Technical Reports Server (NTRS)

    Shanabarger, M. R.

    1979-01-01

    Measurements of the isothermal desorption rate of H2 chemisorbed onto polycrystalline nickel films made for temperatures spanning the Curie temperature of the nickel film are presented. Desorption kinetics were followed by measuring the decay of the change in resistance of the nickel film brought about by hydrogen chemisorption after gas-phase H2 had been rapidly evacuated. The desorption rate is found to undergo an anomalous decrease in the vicinity of the Curie temperature, accompanied by an increase in the desorption activation energy and the equilibrium constant for the chemisorbed hydrogen. The results are interpreted in terms of anomalous variations in rate constants for the formation of the precursor molecular adsorbed state and the chemisorbed atomic state due to the phase transition in the nickel. The changes in rate constants are also considered to be in qualitative agreement with theoretical predictions based on a spin coupling between the adatom and the magnetic substrate.

  10. Kinetic measurement and prediction of the hydrogen outgassing from the polycrystalline LiH/LiOH system

    SciTech Connect

    Dinh, L N; Grant, D M; Schildbach, M A; Smith, R A; Leckey, J H; Siekhaus, W J; Balazs, B; McLean II, W

    2005-03-09

    In this report, we present the use of temperature programmed reaction/decomposition (TPR) in the isoconversion mode to measure outgassing kinetics and to make kinetic prediction concerning hydrogen release from the polycrystalline LiH/LiOH system in the absence of any external H{sub 2}O source.

  11. Exploring adsorption and desorption characteristics of molecular hydrogen on neutral and charged Mg nanoclusters: A first principles study

    NASA Astrophysics Data System (ADS)

    Banerjee, Paramita; Chandrakumar, K. R. S.; Das, G. P.

    2016-05-01

    To surmount the limitations of bulk MgH2 for the purpose of hydrogen storage, we report here, a detailed first principles density functional theory (DFT) based study on the structure and stability of neutral (Mgm) and positively charged (Mgm+) Mg nanoclusters of different sizes (m = 2, 4, 8 and 12) and their interaction with molecular hydrogen (H2). Our results demonstrate that H2 is weakly bound to the Mg nanoclusters through van der Waals interactions. Incorporation of Grimme's dispersion correction (D3) in the DFT based exchange-correlation functionals leads to improved accuracy of H2 interaction energy (IE) values that fall within an energy window (between physisorption and chemisorption) desirable for hydrogen storage. Energy decomposition analysis reveals the significance of polarization energy for these Mg-H2 binding. Ab-initio molecular dynamics simulation shows that complete dehydrogenation from these Mg nanoclusters occur at ∼100 °C which is a significant improvement over bulk MgH2 (∼300 °C).

  12. Modeling of the Kinetics of Supercritical Fluid Extraction of Lipids from Microalgae with Emphasis on Extract Desorption

    PubMed Central

    Sovová, Helena; Nobre, Beatriz P.; Palavra, António

    2016-01-01

    Microalgae contain valuable biologically active lipophilic substances such as omega-3 fatty acids and carotenoids. In contrast to the recovery of vegetable oils from seeds, where the extraction with supercritical CO2 is used as a mild and selective method, economically viable application of this method on similarly soluble oils from microalgae requires, in most cases, much higher pressure. This paper presents and verifies hypothesis that this difference is caused by high adsorption capacity of microalgae. Under the pressures usually applied in supercritical fluid extraction from plants, microalgae bind a large fraction of the extracted oil, while under extremely high CO2 pressures their adsorption capacity diminishes and the extraction rate depends on oil solubility in supercritical CO2. A mathematical model for the extraction from microalgae was derived and applied to literature data on the extraction kinetics in order to determine model parameters. PMID:28773546

  13. Modeling of the Kinetics of Supercritical Fluid Extraction of Lipids from Microalgae with Emphasis on Extract Desorption.

    PubMed

    Sovová, Helena; Nobre, Beatriz P; Palavra, António

    2016-05-27

    Microalgae contain valuable biologically active lipophilic substances such as omega-3 fatty acids and carotenoids. In contrast to the recovery of vegetable oils from seeds, where the extraction with supercritical CO₂ is used as a mild and selective method, economically viable application of this method on similarly soluble oils from microalgae requires, in most cases, much higher pressure. This paper presents and verifies hypothesis that this difference is caused by high adsorption capacity of microalgae. Under the pressures usually applied in supercritical fluid extraction from plants, microalgae bind a large fraction of the extracted oil, while under extremely high CO₂ pressures their adsorption capacity diminishes and the extraction rate depends on oil solubility in supercritical CO₂. A mathematical model for the extraction from microalgae was derived and applied to literature data on the extraction kinetics in order to determine model parameters.

  14. Surface Hydrogen and Subsurface Hydrogen: Their Roles in Bulk Absorption and Surface Reaction

    NASA Astrophysics Data System (ADS)

    Fukutani, Katsuyuki

    Hydrogen adsorbed on metal surfaces possibly penetrates into “subsurface” sites, which might further diffuse into bulk. When temperature is raised, on the other hand, such absorbed hydrogen diffuses back to the surface via the subsurface site eventually desorbing from the surface. The kinetics of these absorption and desorption are ideally expressed by the potential energy surfaces of hydrogen near the surfaces. This article describes how the potential of hydrogen is described, and how the surface and subsurface sites influence the kinetics of absorption and desorption for Pd and Ni as examples. As well as these phenomena, the subsurface sites could serve to promote particular hydrogenation reactions occurring at surfaces. The mechanism of subsurface chemistry is discussed.

  15. Fundamental Kinetics of Supercritical Coal Liquefaction: Effect of Catalysts and Hydrogen-Donor Solvents

    SciTech Connect

    McCoy, Ben J; Madras, Girodhar; Smith, J M; Kodera, Yoichi

    1997-04-16

    This is the quarterly report on our recent progress toward the overall objective to understand the supercritical fluid extraction of hydrocarbons from coal. Our strategy is to simulate coal as a high molecular-weight polymeric material by studying the degradation of polymers under various conditions. The hypothesis we are testing is that degradation of such macromolecules is applicable to the decomposition (depolymerization) of the coal network. Polymer degradation and coal liquefaction are influenced strongly by the solvent in the reaction. This motivated our investigation of the effect of hydrogen donor solvents on polymer degradation. In particular, we obtained new experimental data to show how a hydrogen donor, 6-hydroxy tetralin, influences the degradation rate of polystyrene. We also developed a detailed radical mechanism for hydrogen donation based on the Rice-Herzfeld chain reaction concept with the elementary steps of initiation, depropagation, hydrogen abstraction, and termination. Expressions for the degradation rate parameters were obtained by applying continuous distribution kinetics to the MWD of the reacting polymer. The theory explains the different influences of the hydrogen donor solvent on the degradation rate coefficients for different polymers. Though developed for the degradation of polymers, the mechanism and the theory are potentially applicable for chain scission and addition reactions among distributions of paraffins, olefins, and radicals of all chain lengths. The concepts can, in principle, be extended to examine the effect of hydrogen donors on coal liquefaction and on the complex mixture of liquefaction compounds. Based on this work, a research paper titled "Effect of Hydrogen Donors on Polymer Degradation", has been submitted for publication. Our research paper entitled, "Molecular weight effect on the dynamics of polystyrene degradation", has been accepted for publication by the journal, Industrial and Engineering Chemistry Research.

  16. Optimization, equilibrium, kinetic, thermodynamic and desorption studies on the sorption of Cu(II) from an aqueous solution using marine green algae: Halimeda gracilis.

    PubMed

    Jayakumar, R; Rajasimman, M; Karthikeyan, C

    2015-11-01

    The aptitude of marine green algae Helimeda gracilis for sorption of Cu(II) ions from an aqueous solution was studied in batch experiments. The effect of relevant parameters such as function of pH, sorbent dosage, agitation speed and contact time was evaluated by using Response surface methodology (RSM). A maximum percentage removal of Cu (II) by Halimeda gracilis occurs at pH-4.49, sorbent dosage-1.98g/L, agitation speed-119.43rpm and contact time-60.21min. Further, the sorbent was characterized by using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning electron microscope (SEM) analysis. Experimental data were analyzed in terms of pseudo-first order, pseudo-second order, intraparticle diffusion, power function and elovich kinetic models. The results showed that the sorption process of Cu(II) ions followed well pseudo-second order kinetics. The sorption data of Cu(II) ions at 308.15K are fitted to Langmuir, Freundlich, Dubinin-Radushkevich (D-R), Temkin, Sips and Toth isotherms. Sorption of Cu(II) onto marine green algae Helimeda gracilis followed the Langmuir and Toth isotherm models (R(2)=0.998 and R(2)=0.999) with the maximum sorption capacity of 38.46 and 38.07mg/g. The calculated thermodynamic parameters such as ΔG°, ΔH° and ΔS° showed that the sorption of Cu(II) ions onto Helimeda gracilis biomass was feasible, spontaneous and endothermic. Desorption study shows that the sorbent could be regenerated using 0.2M HCl solution, with up to 89% recovery. Copyright © 2015 Elsevier Inc. All rights reserved.

  17. Clarified sludge (basic oxygen furnace sludge)--an adsorbent for removal of Pb(II) from aqueous solutions--kinetics, thermodynamics and desorption studies.

    PubMed

    Naiya, Tarun Kumar; Bhattacharya, Ashim Kumar; Das, Sudip Kumar

    2009-10-15

    The basic oxygen furnace waste generated in steel plant has been used as a low cost adsorbent for the removal of Pb(II) from aqueous solution. The effect of pH, adsorbent dosage, initial metal ion concentration, contact time and temperature on adsorption process was studied in batch experiments. Results of the equilibrium experiments showed that the solution pH was the key factor affecting the adsorption characteristics. Optimum pH for the adsorption was found to be 5 with corresponding adsorbent dosage level of 5 g/L. The equilibrium was achieved within 1h of contact time. Kinetics data were best described by pseudo second order model. The effective particle diffusion coefficient of Pb(II) is the order of 10(-10)m(2)/s. The maximum uptake was 92.5mg/g. The adsorption data can be well fitted by Freundlich isotherm. The result of the equilibrium studies showed that the solution pH was the key factor affecting the adsorption. External mass transfer analysis was also carried out for the adsorption process. The thermodynamic studies indicated that the adsorption is spontaneous and endothermic. The sorption energy (10.1745 kJ/mol) calculated from Dubinin-Radushkevich isotherm indicated that the adsorption process is chemical in nature. Desorption studies were carried out using dilute mineral acids to elucidate the mechanism of adsorption. Application studies were carried out considering the economic viewpoint of wastewater treatment plant operations.

  18. Adsorption/desorption of Cd(II), Cu(II) and Pb(II) using chemically modified orange peel: Equilibrium and kinetic studies

    NASA Astrophysics Data System (ADS)

    Lasheen, Mohamed R.; Ammar, Nabila S.; Ibrahim, Hanan S.

    2012-02-01

    Waste materials from industries such as food processing may act as cost effective and efficient biosorbents to remove toxic contaminants from wastewater. This study aimed to establish an optimized condition and closed loop application of processed orange peel for metals removal. A comparative study of the adsorption capacity of the chemically modified orange peel was performed against environmentally problematic metal ions, namely, Cd 2+, Cu 2+ and Pb 2+, from aqueous solutions. Chemically modified orange peel (MOP) showed a significantly higher metal uptake capacity compared to original orange peel (OP). Fourier Transform Infrared (FTIR) Spectra of peel showed that the carboxylic group peak shifted from 1637 to 1644 cm -1 after Pb (II) ions binding, indicated the involvement of carboxyl groups in Pb(II) ions binding. The metals uptake by MOP was rapid and the equilibrium time was 30 min at constant temperature and pH. Sorption kinetics followed a second-order model. The mechanism of metal sorption by MOP gave good fits for Freundlich and Langmuir models. Desorption of metals and regeneration of the biosorbent was attained simultaneously by acid elution. Even after four cycles of adsorption-elution, the adsorption capacity was regained completely and adsorption efficiency of metal was maintained at around 90%.

  19. Capacitively coupled hydrogen plasmas sustained by tailored voltage waveforms: vibrational kinetics and negative ions control

    NASA Astrophysics Data System (ADS)

    Diomede, P.; Bruneau, B.; Longo, S.; Johnson, E.; Booth, J.-P.

    2017-07-01

    A comprehensive hybrid model of a hydrogen capacitively coupled plasma, including a detailed description of the molecular vibrational kinetics, has been applied to the study of the effect of tailored voltage waveforms (TVWs) on the production kinetics and transport of negative ions in these discharges. Two kinds of TVWs are considered, valleys-to-peaks and saw-tooth, with amplitude and slope asymmetry respectively. By tailoring the voltage waveform only, it is possible to exert substantial control over the peak density and position of negative ions inside the discharge volume. This control is particularly effective for saw-tooth waveforms. Insight into the mechanisms allowing this control is provided by an analysis of the model results. This reveals the roles of the vibrational distribution function and of the electron energy distribution and their correlations, as well as changes in the negative ion transport in the electric field when using different TVWs. Considering the chemical reactivity of H- ions, the possibility of a purely electrical control of the negative ion cloud in a reactor operating with a feedstock gas diluted by hydrogen may find interesting applications. This is the first study of vibrational kinetics in the context of TVWs in molecular gases.

  20. Dynamic model of hydrogen peroxide diffusion kinetics into the pulp cavity.

    PubMed

    Kwon, So Ran; Li, Yiming; Oyoyo, Udochukwu; Aprecio, Raydolfo M

    2012-07-01

    To measure the time course hydrogen peroxide penetration into the pulp cavity and evaluate short-term tooth color changes after bleaching. Twenty extracted human canines were sectioned, pulp tissue removed and the cavity enlarged. Teeth were painted with nail varnish to leave a 6-mm diameter circle on the buccal surface. Baseline color was measured spectrophotometrically. Teeth were randomized into a control group (n = 10) treated with 30 µl of glycerin base and a bleaching group (n = 10) exposed to 30 µl of 40% hydrogen peroxide for 1 hour. A linear low density polyethylene wrap was placed to prevent evaporation of the material. Acetate buffer was placed into the cavity and replenished every 10 minutes and placed into plastic tubes. Hydrogen peroxide amount was estimated spectrophotometrically using leukocrystal violet and horseradish peroxidase. Specimen color was remeasured immediately after bleaching, 1 hour, 1 day 1, 2 and 6 weeks postbleaching. Color change was measured per Commission Internationale de l'Eclairage methodology. Mann-Whitney procedure was used to assess baseline color measurements and total hydrogen peroxide penetration amount. Friedman's test was used to assess within group differences for color change and hydrogen peroxide penetration. There was significantly greater hydrogen peroxide penetration in the bleaching group (p < 0.05). Hydrogen peroxide penetration levels were constant throughout the 1-hour evaluation period in the bleaching group. The groups showed no difference at baseline with respect to any of L*a*b color measurements (p > 0.05). The postbleaching color measurement showed an increase of change in overall color (ΔE) and lightness (ΔL) up to 1 week followed by a gradual stabilization up to 6 weeks. This dynamic model provided information about the time course diffusion kinetics into the pulp cavity, demonstrating constant penetration of hydrogen peroxide into the pulp cavity during a 1-hour bleaching session. A prolonged

  1. Dehydrogenation kinetics, reversibility, and reaction mechanisms of reversible hydrogen storage material based on nanoconfined MgH2-NaAlH4

    NASA Astrophysics Data System (ADS)

    Plerdsranoy, Praphatsorn; Meethom, Sukanya; Utke, Rapee

    2015-12-01

    Studies of dehydrogenation kinetics, reversibility, and reaction mechanisms during de/rehydrogenation of nanoconfined MgH2-NaAlH4 into carbon aerogel scaffold (CAS) for reversible hydrogen storage material are for the first time proposed. Two different MgH2:NaAlH4 molar ratios (1:1 and 2:1) of hydride composite are melt infiltrated into CAS under 1:1 (CAS:hydride composite) weight ratio. Successful nanoconfinement is confirmed by N2 adsorption-desorption. Multiple-step dehydrogenation of milled samples is reduced to two-step reaction due to nanoconfinement. Peak temperatures corresponding to main dehydrogenation of nanoconfined samples significantly reduce as compared with those of milled samples, i.e., ∆T=up to 50 and 34 °C for nanoconfined sample with 1:1 and 2:1 (MgH2:NaAlH4) molar ratios, respectively. Hydrogen content released (the 1st cycle) and reproduced (the 2nd, 3rd, and 4th cycles) of nanoconfined samples enhance up to 80% and 68% with respect to theoretical hydrogen storage capacity, respectively, while those of milled samples are 71% and 38%, respectively. Remarkable hydrogen content reproduced after nanoconfinement is due to the fact that metallic Al obtained after dehydrogenation (T=300 °C under vacuum) of nanoconfined samples prefer to react with MgH2 and produces Al12Mg17, favorable for reversibility of MgH2-NaAlH4 system, whereas that of milled samples stays in the form of unreacted Al under the same temperature and pressure condition.

  2. Improvement in low-temperature and instantaneous high-rate output performance of Al-free AB5-type hydrogen storage alloy for negative electrode in Ni/MH battery: Effect of thermodynamic and kinetic regulation via partial Mn substituting

    NASA Astrophysics Data System (ADS)

    Zhou, Wanhai; Zhu, Ding; Tang, Zhengyao; Wu, Chaoling; Huang, Liwu; Ma, Zhewen; Chen, Yungui

    2017-03-01

    A series of Al-free Mn-modified AB5-type hydrogen storage alloys have been designed and the effects of thermodynamic stability and electrochemical kinetics on electrochemical performance via Mn substituting have been investigated. Compared with high-Al alloys, the Al-free alloys in this study have better low-temperature performance and instantaneous high-rate output because of the higher surface catalytic ability. After partial substitution of Ni by Mn, both the hydrogen desorption capacity and plateau pressure decrease, and correspondingly results in an improved thermodynamic stability which is adverse to low-temperature delivery. Additionally, with the improvement of charge acceptance ability and anti-corrosion property via Mn substitution, the room-temperature discharge capacity and cycling stability increase slightly. However, Mn adversely affects the electrochemical kinetics and deteriorates both the surface catalytic ability and the bulk hydrogen diffusion ability, leading to the drop of low-temperature dischargeability, high-rate dischargeability and peak power (Ppeak). Based on the thermodynamic and kinetic regulation and overall electrochemical properties, the optimal composition is obtained when x = 0.2, the discharge capacity is 243.6 mAh g-1 at -40 °C with 60 mA g-1, and the Ppeak attains to 969.6 W kg-1 at -40 °C.

  3. Isotopic effect on the non-isothermal dehydrogenation kinetics of lithium alanates

    NASA Astrophysics Data System (ADS)

    Kumar, Sanjay; Tiwari, Gyanendra Prasad; Krishnamurthy, Nagaiyar; Kojima, Yoshitsugu

    2017-08-01

    The isotopic effect on the dehydrogenation kinetics of lithium alanate has been studied. The desorption of hydrogen/deuterium of LiAlH4/LiAlD4 occurs in two steps below 300 °C. The deuterium desorption temperature of LiAlD4 was found to be marginally higher for both the steps as compared to hydrogen desorption of LiAlH4. The apparent activation energy of hydrogen/deuterium desorption was evaluated and found to be in the order of EaLiAlH4 >EaLiAlD4 . The higher desorption temperature of LiAlD4 has been explained on the basis the zero point energy per unit H/D atom of the alanates. The results indicate the normal isotopic effect of lithium alanate, which could be extended for the tritium.

  4. Hydrogen in the upper mantle: Diffusion and effects on olivine transformation kinetics

    NASA Astrophysics Data System (ADS)

    Du Frane, Wyatt Louis

    Olivine is the most abundant mineral in Earth's upper mantle and can host significant amounts of hydrogen within its crystal structure. The presence of hydrogen affects many of olivine's physical properties such as electrical conductivity, viscosity, sound speed, transformation kinetics, phase equilibrium, and generally speaking the physics governing the interior of the earth. Understanding how hydrogen affects olivine is integral to understanding the Earth's interior. In this work olivine was experimentally hydrated and reacted at high pressure and temperature, to simulate upper mantle conditions. The physical properties measured in this work are used to understand seismic and magnetotelluric observations of the Earth. In the first project the effects of hydrogen on olivine transformation kinetics were examined. Growth rates for olivine's high pressure polymorphs, wadsleyite and ringwoodite, to determine if olivine can persist metastably inside cold subducting slabs in the mantle transition zone. Hydrogen significantly enhances the growth rates of olivine into ringwoodite. For olivine containing ˜75 (or higher) ppmw H2O At 18 GPa and 900°C the growth rate for ringwoodite rims is 1.0x10-9 m/s with activation enthalpy of 235 +/- 30 kJ/mol, which is too high for persistence of metastable olivine into the transition zone. Confirmation of the existence of metastable olivine by seismologists would constrain H2O contents at such locations to be < 75 ppmw H2O. In the second project deuterium-hydrogen interdiffusion coefficients were measured to help understand electrical conductivity, point defect populations, chemical transport, and defect dominated properties in olivine. For the fastest H-diffusing [100] orientation DD-H, [100] = 10(-5.04 +/- 1.43)*e(-137 +/- 31 kJ/mol)/(RT) m²/s at 2 GPa and 750--900°C. Comparison of DD-H to chemical diffusion coefficients allows us to calculate diffusivity of intrinsic defects. Olivine electrical conductivity is calculated from DD

  5. Novel Molecular Spectroscopic Multimethod Approach for Monitoring Water Absorption/Desorption Kinetics of CAD/CAM Poly(Methyl Methacrylate) Prosthodontics.

    PubMed

    Wiedemair, Verena; Mayr, Sophia; Wimmer, Daniel S; Köck, Eva Maria; Penner, Simon; Kerstan, Andreas; Steinmassl, Patricia-Anca; Dumfahrt, Herbert; Huck, Christian W

    2016-12-12

    Water absorbed to poly(methyl methacrylate) (PMMA)-based CAD/CAM (computer-assisted design/computer-assisted manufacturing) prosthodontics can alter their properties including hardness and stability. In the present contribution, water absorption and desorption kinetics under defined experimental conditions were monitored employing several supplementary and advanced Fourier transform infrared (FT-IR) spectroscopic techniques in combination with multivariate analysis (MVA). In this synergistic vibrational spectroscopic multimethod approach, first a novel near-infrared (NIR) diffuse fiber optic probe reflection spectroscopic method was established for time-resolved analysis of water uptake within seven days under controlled conditions. Near-infrared water absorbance spectra in a wavenumber range between 5288-5100 cm(-1) (combination band) and 5424-5352 cm(-1) (second overtone) were used establishing corresponding calibration and validation models to quantify the amount of water in the milligram range. Therefore, 14 well-defined samples exposed to prior optimized experimental conditions were taken into consideration. The average daily water uptake conducting reference analysis was calculated as 22 mg/day for one week. Additionally, in this study for the first time NIR two-dimensional correlation spectroscopy (2D-COS) was conducted to monitor and interpret the spectral dynamics of water absorption on the prosthodontics in a wavenumber range of 5100-5300 cm(-1) For sensitive time-resolved recording of water desorption, a recently developed high-temperature, high-pressure FT-IR reaction cell with water-free ultra-dry in situ and operando operation was applied. The reaction cell, as well as the sample holder, was fully made of quartz glass, with no hot metal or ceramic parts in the vicinity of the high temperature zone. Applying a temperature gradient in the range of 25-150 ℃, mid-infrared (MIR) 2D-COS was successfully conducted to get insights into the dynamic

  6. Theoretical mechanisms and kinetics of the hydrogen abstraction reaction of acetone by chlorine radical

    NASA Astrophysics Data System (ADS)

    Tiu, Gerald C.; Tao, Fu-Ming

    2006-09-01

    Reaction mechanisms and kinetics of the hydrogen abstraction of acetone by chlorine radical are studied by theoretical calculations. Density functional theory and ab initio methods are used to explore the reaction pathways. The hydrogen abstraction is found to be highly favored over the addition pathway, and the latter is insignificant in atmospheric conditions. Classical transition state theory with Eckart tunneling corrections is employed to obtain rate constants of the reaction from 210 K to 360 K. The reaction is characterized by a small barrier, and rate constants approximated by the expression k( T) = 6.44 × 10 -12 e (-672/ T) cm 3 molecule -1 s -1, which is in reasonable agreement with experiment.

  7. Computation of Kinetics for the Hydrogen/Oxygen System Using the Thermodynamic Method

    NASA Technical Reports Server (NTRS)

    Marek, C. John

    1996-01-01

    A new method for predicting chemical rate constants using thermodynamics has been applied to the hydrogen/oxygen system. This method is based on using the gradient of the Gibbs free energy and a single proportionality constant D to determine the kinetic rate constants. Using this method the rate constants for any gas phase reaction can be computed from thermodynamic properties. A modified reaction set for the H/O system is determined. A11 of the third body efficiencies M are taken to be unity. Good agreement was obtained between the thermodynamic method and the experimental shock tube data. In addition, the hydrogen bromide experimental data presented in previous work is recomputed with M's of unity.

  8. Decomposition Kinetics of Hydrogen Peroxide: Novel Lab Experiments Employing Computer Technology

    NASA Astrophysics Data System (ADS)

    Abramovitch, Dorota A.; Cunningham, Latrice K.; Litwer, Mitchell R.

    2003-07-01

    The quantitative catalytic decomposition of hydrogen peroxide has been used in many general chemistry experiments. The typical procedure involves measuring the volume of oxygen generated in the reaction under constant pressure using a displacement method and calculating the necessary data. A pressure sensor interfaced with a computer using LabWorks II software allowed us to modify this reaction and to measure the change in pressure, at constant volume. Since the software allows the collection and display of real-time data and the ability to import the data to Excel, we re-examined the kinetics of this reaction. Using different concentrations of hydrogen peroxide and catalase enzyme and graphing initial concentrations versus initial rates, we determined the rate and the order of the decomposition.

  9. Hydrogen exchange kinetics of proteins in denaturants: a generalized two-process model.

    PubMed

    Qian, H; Chan, S I

    1999-02-19

    The recent progress in measurements on the amide hydrogen exchange (HX) in proteins under varying denaturing conditions, both at equilibrium and in transient relaxation, necessitates the development of a unifying theory which quantitatively relates the HX rates to the conformational energetics of the proteins. We present here a comprehensive kinetic model for the site-specific HX of proteins under varying solvent denaturing conditions based on the two-state protein folding model. The generalized two-process model considers both conformational fluctuations and residual protections, respectively, within the folded and unfolded states of a protein, as well as a global kinetic folding-unfolding transition between the two states. The global transition can be either rapid or slow, depending on the solvent condition for the protein. This novel model is applicable to the traditional equilibrium HX measurements in both EX2 and EX1 regimes, and also the recently introduced transient pulse-labeling HX experiments. A set of simple analytical equations is provided for quantitative interpretation of experimental data. The model emphasizes the use of full time-course of bi-exponential HX kinetics, rather than fitting time-course data to single rate constants, to obtain quantitative information about fluctuating conformers within the folded and unfolded states of proteins. This HX kinetic model naturally unfolds into a simple two-state and two-stage kinetic interpretation for protein folding. It suggests that the various observed intermediates of a protein can be interpreted as dominant isomers of either the folded or the unfolded state under different solvent conditions. This simple, minimalist's view of protein folding is consistent with various recent experimental observations on folding kinetics by HX.

  10. Insight to the Thermal Decomposition and Hydrogen Desorption Behaviors of NaNH2-NaBH4 Hydrogen Storage Composite.

    PubMed

    Pei, Ziwei; Bai, Ying; Wang, Yue; Wu, Feng; Wu, Chuan

    2017-09-20

    The lightweight compound material NaNH2-NaBH4 is regarded as a promising hydrogen storage composite due to the high hydrogen density. Mechanical ball milling was employed to synthesize the composite NaNH2-NaBH4 (2/1 molar ratio), and the samples were investigated utilizing thermogravimetric-differential thermal analysis-mass spectroscopy (TG-DTA-MS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) analyses. The full-spectrum test (range of the ratio of mass to charge: 0-200) shows that the released gaseous species contain H2, NH3, B2H6, and N2 in the heating process from room temperature to 400 °C, and possibly the impurity gas B6H12 also exists. The TG/DTA analyses show that the composite NaNH2-NaBH4 (2/1 molar ratio) is conductive to generate hydrogen so that the dehydrogenation process can be finished before 400 °C. Moreover, the thermal decomposition process from 200 to 400 °C involves two-step dehydrogenation reactions: (1) Na3(NH2)2BH4 hydride decomposes into Na3BN2 and H2 (200-350 °C); (2) remaining Na3(NH2)2BH4 reacts with NaBH4 and Na3BN2, generating Na, BN, NH3, N2, and H2 (350-400 °C). The better mechanism understanding of the thermal decomposition pathway lays a foundation for tailoring the hydrogen storage performance of the composite complex hydrides system.

  11. Microscopic observation of kinetic molecular sieving of hydrogen isotopes in a nanoporous material.

    PubMed

    Nguyen, T X; Jobic, H; Bhatia, S K

    2010-08-20

    We report quasielastic neutron scattering studies of H2-D2 diffusion in a carbon molecular sieve, demonstrating remarkable quantum effects, with the heavier isotope diffusing faster below 100 K, confirming our recent predictions. Our transition state theory and molecular dynamics calculations show that while it is critical for this effect to have narrow windows of size comparable to the de Broglie wavelength, high flux requires that the energy barrier be reduced through small cages. Such materials will enable novel processes for kinetic molecular sieving of hydrogen isotopes.

  12. Microscopic Observation of Kinetic Molecular Sieving of Hydrogen Isotopes in a Nanoporous Material

    NASA Astrophysics Data System (ADS)

    Nguyen, T. X.; Jobic, H.; Bhatia, S. K.

    2010-08-01

    We report quasielastic neutron scattering studies of H2-D2 diffusion in a carbon molecular sieve, demonstrating remarkable quantum effects, with the heavier isotope diffusing faster below 100 K, confirming our recent predictions. Our transition state theory and molecular dynamics calculations show that while it is critical for this effect to have narrow windows of size comparable to the de Broglie wavelength, high flux requires that the energy barrier be reduced through small cages. Such materials will enable novel processes for kinetic molecular sieving of hydrogen isotopes.

  13. Microscopic Observation of Kinetic Molecular Sieving of Hydrogen Isotopes in a Nanoporous Material

    SciTech Connect

    Nguyen, T. X.; Bhatia, S. K.; Jobic, H.

    2010-08-20

    We report quasielastic neutron scattering studies of H{sub 2}-D{sub 2} diffusion in a carbon molecular sieve, demonstrating remarkable quantum effects, with the heavier isotope diffusing faster below 100 K, confirming our recent predictions. Our transition state theory and molecular dynamics calculations show that while it is critical for this effect to have narrow windows of size comparable to the de Broglie wavelength, high flux requires that the energy barrier be reduced through small cages. Such materials will enable novel processes for kinetic molecular sieving of hydrogen isotopes.

  14. Localized Hydration in Lyophilized Myoglobin by Hydrogen-Deuterium Exchange Mass Spectrometry. 2. Exchange Kinetics

    PubMed Central

    Sophocleous, Andreas M.; Topp, Elizabeth M.

    2012-01-01

    Solid-state hydrogen deuterium exchange with mass spectrometric analysis (ssHDX) is a promising method for characterizing proteins in amorphous solids. Though analysis of HDX kinetics is informative and well-established in solution, application of these methods to solid samples is complicated by possible heterogeneities in the solid. The studies reported here provide a detailed analysis of the kinetics of hydration and ssHDX for equine myoglobin (Mb) in solid matrices containing sucrose or mannitol. Water sorption was rapid relative to ssHDX, indicating that ssHDX kinetics was not limited by bulk water transport. Deuterium uptake in solids was well-characterized by a bi-exponential model; values for regression parameters provided insight into differences between the two solid matrices. Analysis of the widths of peptide mass envelopes revealed that in solution, an apparent EX2 mechanism prevails, consistent with native conformation of the protein. In contrast, in mannitol-containing samples, a smaller non-native subpopulation exchanges by an EX1-like mechanism. Together, the results indicate that the analysis of ssHDX kinetic data and the widths of peptide mass envelopes are useful in screening solid formulations of protein drugs for the presence of non-native species that cannot be detected by amide I FTIR. PMID:22352990

  15. An Experimental and Chemical Kinetics Study of the Combustion of Syngas and High Hydrogen Content Fuels

    SciTech Connect

    Santoro, Robers; Dryer, Frederick; Ju, Yiguang

    2013-09-30

    An integrated and collaborative effort involving experiments and complementary chemical kinetic modeling investigated the effects of significant concentrations of water and CO2 and minor contaminant species (methane [CH4], ethane [C2H6], NOX, etc.) on the ignition and combustion of HHC fuels. The research effort specifically addressed broadening the experimental data base for ignition delay, burning rate, and oxidation kinetics at high pressures, and further refinement of chemical kinetic models so as to develop compositional specifications related to the above major and minor species. The foundation for the chemical kinetic modeling was the well validated mechanism for hydrogen and carbon monoxide developed over the last 25 years by Professor Frederick Dryer and his co-workers at Princeton University. This research furthered advance the understanding needed to develop practical guidelines for realistic composition limits and operating characteristics for HHC fuels. A suite of experiments was utilized that that involved a high-pressure laminar flow reactor, a pressure-release type high-pressure combustion chamber and a high-pressure turbulent flow reactor.

  16. Hydrogen desorption properties of MgH2-TiCr1.2Fe0.6 nanocomposite prepared by high-energy mechanical alloying

    NASA Astrophysics Data System (ADS)

    Mahmoudi, Nafiseh; Kaflou, A.; Simchi, A.

    2011-05-01

    In the present work, high-energy mechanical alloying (MA) was employed to synthesize a nanostructured magnesium-based composite for hydrogen storage. The preparation of the composite material with composition of MgH2-5 at% (TiCr1.2Fe0.6) was performed by co-milling of commercial available MgH2 powder with the body-centered cubic (bcc) alloy either in the form of Ti-Cr-Fe powder mixture with the proper mass fraction (sample A) or prealloyed TiCr1.2Fe0.6 powder (sample B). The prealloyed powder with an average crystallite size of 14 nm and particle size of 384 nm was prepared by the mechanical alloying process. It is shown that the addition of the Ti-based bcc alloy to magnesium hydride yields a finer particle size and grain structure after mechanical alloying. As a result, the desorption temperature of mechanically activated MgH2 for 4 h decreased from 327 °C to 262 °C for sample A and 241 °C for sample B. A high dehydrogenation capacity (∼5 wt%) at 300 °C is also obtained. The effect of the Ti-based alloy on improvement of the dehydrogenation is discussed.

  17. Hydrogen-bonded porous coordination polymers: structural transformation, sorption properties, and particle size from kinetic studies.

    PubMed

    Uemura, Kazuhiro; Saito, Kazuya; Kitagawa, Susumu; Kita, Hidetoshi

    2006-12-20

    Three new coordination polymers, [CoCl2(4-pmna)2]n (1), {[Co(NCS)2(4-pmna)2].2Me2CO}n (2 superset 2Me2CO), and {[Co(4-pmna)2(H2O)2](NO3)2.2CH3OH}n (3 superset 2H2O.2MeOH) (4-pmna = N-(pyridin-4-ylmethyl)nicotinamide), have been synthesized and characterized using single-crystal X-ray diffraction. The cobalt(II) atoms are bridged by 4-pmna ligands in all three compounds to form double-stranded one-dimensional "repeated rhomboid-type" chains with rectangular-shaped cavities. In 1, each chain slips and obstructs the neighboring cavities so that there are no guest-incorporated pores. Both 2 superset 2Me2CO and 3 superset 2H2O.2MeOH do not have such a staggered arrangement and have pores that can be filled with a guest molecule. Compound 3 superset 2H2O.2MeOH traps guest molecules with multiple hydrogen bonds and shows a reversible structural rearrangement during adsorption and desorption. The new crystalline compound, 3, is stabilized by forming hydrogen bonds with the amide moieties of the 4-pmna ligands and was characterized using infrared spectroscopy. The clathration enthalpy of the reaction 3 + 2H2O(l) + 2MeOH(l) <==> 3 superset 2H2O.2MeOH (approximately 35 kJ/mol) was estimated from differential scanning calorimetry data by considering the vaporization enthalpies of H2O and MeOH. The desorption process of 3 superset 2H2O.2MeOH --> 3 follows a single zero-order reaction mechanism under isothermal conditions. The activation energy of ca. 100 kJ/mol was obtained by plotting the logarithm of the reaction time for the same reacted fraction versus the reciprocal of the temperature. Moreover, the distribution of the one-dimensional channels in 3 superset 2H2O.2MeOH was estimated using the observation that the reaction rate is directly proportional to the total sectional area.

  18. Kinetic and Thermodynamic Investigation of Hydrogen Release from Ethane 1,2-di-amineborane

    SciTech Connect

    Neiner, Doinita; Karkamkar, Abhijeet J.; Bowden, Mark; Choi, Young Joon; Luedtke, Avery T.; Holladay, Jamelyn D.; Fisher, Allison M.; Szymczak, Nathaniel; Autrey, Thomas

    2011-07-18

    The thermodynamics and kinetics of hydrogen (H2) release from ethane 1,2-di-amineborane (EDAB, BH3NH2CH2CH2NH2BH3) were measured using Calvet and differential scanning calorimetry (DSC), pressure-composition isotherms, and volumetric gas-burette experiments. The results presented here indicate that EDAB releases ~ 9 wt.% H2 at temperatures ranging from 100 °C to 200 °C in two moderately exothermic steps, approximately -10±1 kJ/mol H2 and -3.8±1 kJ/mol H2. Isothermal kinetic analysis shows that EDAB is more stable than ammonia borane (AB) at temperatures lower than 100°C; however, the rates of hydrogen release are faster for EDAB than for AB at temperatures higher than 120°C. In addition, no volatile impurities in the H2 released by EDAB were detected by mass spectrometry upon heating with 1°C/min to 200°C in a calorimeter.

  19. Kinetic study of the reactions between chloramine disinfectants and hydrogen peroxide: temperature dependence and reaction mechanism.

    PubMed

    McKay, Garrett; Sjelin, Brittney; Chagnon, Matthew; Ishida, Kenneth P; Mezyk, Stephen P

    2013-09-01

    The temperature-dependent kinetics for the reaction between hydrogen peroxide and chloramine water disinfectants (NH2Cl, NHCl2, and NCl3) have been determined using stopped flow-UV/Vis spectrophotometry. Rate constants for the mono- and dichloramine-peroxide reaction were on the order of 10(-2)M(-1)s(-1) and 10(-5)M(-1)s(-1), respectively. The reaction of trichloramine with peroxide was negligibly slow compared to its thermal and photolytically-induced decomposition. Arrhenius expressions of ln(kH2O2-NH2Cl)=(17.3±1.5)-(51500±3700)/RT and ln(kH2O2-NHCl2)=(18.2±1.9)-(75800±5100)/RT were obtained for the mono- and dichloramine peroxide reaction over the temperature ranges 11.4-37.9 and 35.0-55.0°C, respectively. Both monochloramine and hydrogen peroxide were first-order in the rate-limiting kinetic step and concomitant measurements made using a chloride ion selective electrode showed that the chloride was produced quantitatively. These data will aid water utilities in predicting chloramine concentrations (and thus disinfection potential) throughout the water distribution system.

  20. A kinetic model for quantitative evaluation of the effect of hydrogen and osmolarity on hydrogen production by Caldicellulosiruptor saccharolyticus

    PubMed Central

    2011-01-01

    Background Caldicellulosiruptor saccharolyticus has attracted increased interest as an industrial hydrogen (H2) producer. The aim of the present study was to develop a kinetic growth model for this extreme thermophile. The model is based on Monod kinetics supplemented with the inhibitory effects of H2 and osmotic pressure, as well as the liquid-to-gas mass transfer of H2. Results Mathematical expressions were developed to enable the simulation of microbial growth, substrate consumption and product formation. The model parameters were determined by fitting them to experimental data. The derived model corresponded well with experimental data from batch fermentations in which the stripping rates and substrate concentrations were varied. The model was used to simulate the inhibition of growth by H2 and solute concentrations, giving a critical dissolved H2 concentration of 2.2 mmol/L and an osmolarity of 0.27 to 29 mol/L. The inhibition by H2, being a function of the dissolved H2 concentration, was demonstrated to be mainly dependent on H2 productivity and mass transfer rate. The latter can be improved by increasing the stripping rate, thereby allowing higher H2 productivity. The experimentally determined degree of oversaturation of dissolved H2 was 12 to 34 times the equilibrium concentration and was comparable to the values given by the model. Conclusions The derived model is the first mechanistically based model for fermentative H2 production and provides useful information to improve the understanding of the growth behavior of C. saccharolyticus. The model can be used to determine optimal operating conditions for H2 production regarding the substrate concentration and the stripping rate. PMID:21914204

  1. The impact of soil organic matter and soil sterilisation on the bioaccessibility of 14C-azoxystrobin determined by desorption kinetics.

    PubMed

    Clegg, Helen; Riding, Matthew J; Oliver, Robin; Jones, Kevin C; Semple, Kirk T

    2014-08-15

    As soils represent a major sink for most pesticides, factors influencing pesticide degradation are essential in identifying their potential environmental risk. Desorption of (14)C-azoxystrobin was investigated over time in two soils under sterile and non-sterile conditions using exhaustive (solvent) and non-exhaustive (aqueous) methods. Desorption data were fitted to a two-compartment model, differentiating between fast and slow desorbing fractions. With increased ageing, rapid desorption (Frap) (bioaccessibility) decreased with corresponding increases in slowly desorbing fractions (F(slow)). The rapid desorption rate constant (k(fast)) was not affected by ageing, sterility or extraction solvent. The non-exhaustive extractions had similar desorption profiles; whereas exhaustive extractions in aged soils had the highest F(rap). In non-sterile soil, F(rap) was lower resulting in higher F(slow), while desorption rates remained unaffected. Organic matter (OM) reduces F(rap); but not desorption rates. Microorganisms and OM enhanced ageing effects, reducing the fraction of fast desorbing chemicals and potentially the bioaccessibility of pesticides in soil. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Efficient hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics

    NASA Astrophysics Data System (ADS)

    Zhang, Jian; Wang, Tao; Liu, Pan; Liao, Zhongquan; Liu, Shaohua; Zhuang, Xiaodong; Chen, Mingwei; Zschech, Ehrenfried; Feng, Xinliang

    2017-05-01

    Various platinum-free electrocatalysts have been explored for hydrogen evolution reaction in acidic solutions. However, in economical water-alkali electrolysers, sluggish water dissociation kinetics (Volmer step) on platinum-free electrocatalysts results in poor hydrogen-production activities. Here we report a MoNi4 electrocatalyst supported by MoO2 cuboids on nickel foam (MoNi4/MoO2@Ni), which is constructed by controlling the outward diffusion of nickel atoms on annealing precursor NiMoO4 cuboids on nickel foam. Experimental and theoretical results confirm that a rapid Tafel-step-decided hydrogen evolution proceeds on MoNi4 electrocatalyst. As a result, the MoNi4 electrocatalyst exhibits zero onset overpotential, an overpotential of 15 mV at 10 mA cm-2 and a low Tafel slope of 30 mV per decade in 1 M potassium hydroxide electrolyte, which are comparable to the results for platinum and superior to those for state-of-the-art platinum-free electrocatalysts. Benefiting from its scalable preparation and stability, the MoNi4 electrocatalyst is promising for practical water-alkali electrolysers.

  3. Kinetics of suprathermal hydrogen atom reactions with saturated hydrides in planetary and satellite atmospheres

    NASA Astrophysics Data System (ADS)

    Morton, Richard J.; Kaiser, Ralf I.

    2003-05-01

    The kinetics of saturated hydrides methane (CH 4), silane (SiH 4), germane (GeH 4), ammonia (NH 3), phosphine (PH 3), arsane (AsH 3), water (H 2O), and hydrogen sulfide (H 2S) in the low-temperature atmospheres of Jupiter, Saturn, Uranus, Neptune, Pluto, Titan, and Triton reacting with suprathermal hydrogen atoms were investigated computationally to extract suprathermal rate constants k( E) via an inverse Laplace transformation from experimentally available thermal rate constants k( T). Our data reveal that all suprathermal rate constants range up to 10 -10 cm3 s-1, whereas the thermal counterparts are as low as 8×10 -73 cm3 s-1. These data demonstrate explicitly a significantly enhanced reactivity of photolytically generated suprathermal hydrogen atoms in the low-temperature planetary and satellite atmospheres and suggest that this hitherto unaccounted reaction class should be included by the planetary modeling community into future photochemical networks of atmospheres of outer solar system planets and their moons.

  4. Hydrogen Attack kinetics of 2.25 Cr-1 Mo steel weld metals

    NASA Astrophysics Data System (ADS)

    Parthasarathy, T. A.; Lopez, H. F.; Shewmon, P. G.

    1985-06-01

    The kinetics of Hydrogen Attack (HA) of the base metals and the weld metals of two Q&T 2.25 Cr-1 Mo steel weldments made by different techniques (SMAW and SAW) were studied in the temperature range 460 to 590°C (860 to 1094 °F) and 10 to 23 MPa of hydrogen. A sensitive dilatometer used to measure the rate of HA showed that the weld metals suffered HA at significantly higher rates than the base metals. The SMAW weld metal was inferior to the SAW weld metal and swelled nearly an order of magnitude faster than the base metal. This behavior is due to a significantly higher bubble density, and a resulting higher contribution of power law creep of the matrix. The SAW behavior was intermediate between those of the base metals and the SMAW. For the same hydrogen pressure the operating limit of the SMAW weld would be roughly 100°C lower than that of the base metals, and that of the SAW roughly 50°C lower.

  5. Kinetic and thermodynamic studies on the disulfide-bond reducing potential of hydrogen sulfide.

    PubMed

    Vasas, Anita; Dóka, Éva; Fábián, István; Nagy, Péter

    2015-04-30

    The significance of persulfide species in hydrogen sulfide biology is increasingly recognized. However, the molecular mechanisms of their formation remain largely elusive. The obvious pathway of the reduction of biologically abundant disulfide moieties by sulfide was challenged on both thermodynamic and kinetic grounds. Using DTNB (5,5'-dithiobis-(2-nitrobenzoic acid), also known as Ellman's reagent) as a model disulfide we conducted a comprehensive kinetic study for its reaction with sulfide. The bimolecular reaction is relatively fast with a second-order rate constant of 889 ± 12 M(-1)s(-1) at pH = 7.4. pH dependence of the rate law revealed that the reaction proceeds via the bisulfide anion species with an initial nucleophilic thiol-disulfide exchange reaction to give 5-thio-2-nitrobenzoic acid (TNB) and TNB-persulfide with a pH independent second-order rate constant of 1090 ± 12 M(-1)s(-1). However, kinetic studies and stoichiometric analyses in a wide range of reactant ratios together with kinetic simulations revealed that it is a multistep process that proceeds via kinetically driven, practically irreversible reactions along the disulfide → persulfide → inorganic polysulfides axis. The kinetic model postulated here, which is fully consistent with the experimental data, suggests that the TNB-persulfide is further reduced by sulfide with a second-order rate constant in the range of 5 × 10(3) - 5 × 10(4) M(-1)s(-1) at pH 7.4 and eventually yields inorganic polysulfides and TNB. The reactions of cystine and GSSG with sulfide were found to be significantly slower and to occur via more complicated reaction schemes. (1)H NMR studies suggest that these reactions also generate Cys-persulfide and inorganic polysulfide species, but in contrast with DTNB, in consecutive equilibrium processes that are sensitive to changes in the reactant and product ratios. Collectively, our results demonstrate that the reaction of disulfides with sulfide is a highly system

  6. Effects of radiation on NO kinetics in turbulent hydrogen/air diffusion flames

    SciTech Connect

    Sivathanu, Y.R.; Gore, J.P.; Laurendeau, N.M.

    1997-07-01

    The authors describe a coupled radiation and NO kinetics calculation of turbulent hydrogen/air diffusion flame properties. Transport equations for mass, momentum, mixture fraction, enthalpy (sensible + chemical) including gas band radiation, and NO mass fraction are solved. NO kinetics is described by a one step thermal production mechanism. The local temperature is obtained by solving the enthalpy equation taking radiation loss from H{sub 2}O into consideration. Radiation/turbulence and chemical kinetics/turbulence interactions are treated using a clipped Gaussian probability density function (PDF) for the mixture fraction, and a delta PDF for the enthalpy. The source terms in the enthalpy and mass fraction of NO equations are treated using assumed PDF integration over the mixture fraction space. The results of the simulation are compared with existing measurements of the Emission Indices of NO (EINO) in turbulent H{sub 2}/air diffusion flames. The major conclusion of the paper is that coupled turbulence/radiation interactions should be taken into account while computing the EINO.

  7. An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron

    NASA Technical Reports Server (NTRS)

    Shanabarger, Mickey R.

    1991-01-01

    The goal was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of the degradation process. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. Modern advanced aerospace applications often require the use of structural materials in high pressure hydrogen environments at temperatures which range from low cryogenic temperatures to very high temperatures (1300 K and greater). Materials proposed for these applications, such as the titanium aluminides, beta-titanium alloys, nickel- and cobalt-based superalloys, molybdenum-rhenium alloys, beryllium, and various beryllides, need to possess a high degree of immunity from hydrogen induced degradation of mechanical properties. In the present program, the interaction of hydrogen with the surfaces of alpha-2 (Ti3Al) titanium aluminide, gamma (TiAl) titanium aluminide, and beryllium were studied. The interaction of low pressure hydrogen with gamma titanium aluminide and beryllium was found to be relatively weak, in the sense that adsorption leads to a low surface concentration of dissociated hydrogen, i.e., the chemisorption process is reversible at room temperature (300 K) for gamma titanium aluminide and the sticking coefficient for chemisorption is extremely small for beryllium. Hydrogen was found to interact readily with alpha-2 titanium aluminide to form a stable surface hydride at 300 K. These results correlate well with other recent studies which show that the mechanical properties for alpha-2 titanium aluminide are readily degraded in

  8. Hydrogen Sorption Kinetics on Bare and Platinum-Modified Palladium Nanofilms, Grown by Electrochemical Atomic Layer Deposition (E-ALD)

    SciTech Connect

    Jagannathan, Kaushik; Benson, David M.; Robinson, David B.; Stickney, John L.

    2016-01-01

    Nanofilms of Pd were grown using an electrochemical form of atomic layer deposition (E-ALD) on 100 nm evaporated Au films on glass. Multiple cycles of surface-limited redox replacement (SLRR) were used to grow deposits. Each SLRR involved the underpotential deposition (UPD) of a Cu atomic layer, followed by open circuit replacement via redox exchange with tetrachloropalladate, forming a Pd atomic layer: one E-ALD deposition cycle. That cycle was repeated in order to grow deposits of a desired thickness. 5 cycles of Pd deposition were performed on the Au on glass substrates, resulting in the formation of 2.5 monolayers of Pd. Those Pd films were then modified with varying coverages of Pt, also formed using SLRR. The amount of Pt was controlled by changing the potential for Cu UPD, and by increasing the number of Pt deposition cycles. Hydrogen absorption was studied using coulometry and cyclic voltammetry in 0.1 M H2SO4 as a function of Pt coverage. The presence of even a small fraction of a Pt monolayer dramatically increased the rate of hydrogen desorption. However, this did not reduce the films’ hydrogen storage capacity. The increase in desorption rate in the presence of Pt was over an order of magnitude.

  9. Hydrogen Sorption Kinetics on Bare and Platinum-Modified Palladium Nanofilms, Grown by Electrochemical Atomic Layer Deposition (E-ALD)

    DOE PAGES

    Jagannathan, Kaushik; Benson, David M.; Robinson, David B.; ...

    2016-01-01

    Nanofilms of Pd were grown using an electrochemical form of atomic layer deposition (E-ALD) on 100 nm evaporated Au films on glass. Multiple cycles of surface-limited redox replacement (SLRR) were used to grow deposits. Each SLRR involved the underpotential deposition (UPD) of a Cu atomic layer, followed by open circuit replacement via redox exchange with tetrachloropalladate, forming a Pd atomic layer: one E-ALD deposition cycle. That cycle was repeated in order to grow deposits of a desired thickness. 5 cycles of Pd deposition were performed on the Au on glass substrates, resulting in the formation of 2.5 monolayers of Pd.more » Those Pd films were then modified with varying coverages of Pt, also formed using SLRR. The amount of Pt was controlled by changing the potential for Cu UPD, and by increasing the number of Pt deposition cycles. Hydrogen absorption was studied using coulometry and cyclic voltammetry in 0.1 M H2SO4 as a function of Pt coverage. The presence of even a small fraction of a Pt monolayer dramatically increased the rate of hydrogen desorption. However, this did not reduce the films’ hydrogen storage capacity. The increase in desorption rate in the presence of Pt was over an order of magnitude.« less

  10. Modeling of hydrogen production methods: Single particle model and kinetics assessment

    SciTech Connect

    Miller, R.S.; Bellan, J.

    1996-10-01

    The investigation carried out by the Jet Propulsion Laboratory (JPL) is devoted to the modeling of biomass pyrolysis reactors producing an oil vapor (tar) which is a precursor to hydrogen. This is an informal collaboration with NREL whereby JPL uses the experimentally-generated NREL data both as initial and boundary conditions for the calculations, and as a benchmark for model validation. The goal of this investigation is to find drivers of biomass fast-pyrolysis in the low temperature regime. The rationale is that experimental observations produce sparse discrete conditions for model validation, and that numerical simulations produced with a validated model are an economic way to find control parameters and an optimal operation regime, thereby circumventing costly changes in hardware and tests. During this first year of the investigation, a detailed mathematical model has been formulated for the temporal and spatial accurate modeling of solid-fluid reactions in biomass particles. These are porous particles for which volumetric reaction rate data is known a priori and both the porosity and the permeability of the particle are large enough to allow for continuous gas phase flow. The methodology has been applied to the pyrolysis of spherically symmetric biomass particles by considering previously published kinetics schemes for both cellulose and wood. The results show that models which neglect the thermal and species boundary layers exterior to the particle will generally over predict both the pyrolysis rates and experimentally obtainable tar yields. An evaluation of the simulation results through comparisons with experimental data indicates that while the cellulose kinetics is reasonably accurate, the wood pyrolysis kinetics is not accurate; particularly at high reactor temperatures. Current effort in collaboration with NREL is aimed at finding accurate wood kinetics.

  11. An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron. Annual status report, 1 January-31 December 1993

    SciTech Connect

    Shanabarger, M.R.

    1993-01-01

    The goal of this program was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of degradation. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. The interaction of hydrogen with the surfaces of alpha-2(Ti3Al) titanium aluminide, gamma(TiAl) titanium aluminide, and beryllium were studied.

  12. Gallium desorption kinetics on (0001) GaN surface during the growth of GaN by molecular-beam epitaxy

    SciTech Connect

    He, L.; Moon, Y.T.; Xie, J.; Munoz, M.; Johnstone, D.; Morkoc, H.

    2006-02-13

    Gallium (Ga) surface desorption behavior was investigated using reflection high-energy electron diffraction during the GaN growth. It was found that the desorption of Ga atoms from the (0001) GaN surfaces under different III-V ratio dependents on the coverage of adsorbed atoms. Doing so led to desorption energies of 2.76 eV for Ga droplets, 1.24-1.89 eV for Ga under Ga-rich growth conditions, and 0.82 eV - 0.94 eV for Ga under stoichiometric growth conditions. Moreover, the variation of the GaN surface morphology under different III-V ratios on porous templates supports the conclusion that Ga desorption energy depends on the coverage, and the III/V ratio dominates the growth mode.

  13. Comparison of the growth kinetics of In{sub 2}O{sub 3} and Ga{sub 2}O{sub 3} and their suboxide desorption during plasma-assisted molecular beam epitaxy

    SciTech Connect

    Vogt, Patrick Bierwagen, Oliver

    2016-08-08

    We present a comprehensive study of the In{sub 2}O{sub 3} growth kinetics during plasma-assisted molecular beam epitaxy and compare it to that of the related oxide Ga{sub 2}O{sub 3} [P. Vogt and O. Bierwagen, Appl. Phys. Lett. 108, 072101 (2016)]. The growth rate and desorbing fluxes were measured during growth in-situ by a laser reflectometry set-up and line-of-sight quadrupole mass spectrometer, respectively. We extracted the In incorporation as a function of the provided In flux, different growth temperatures T{sub G}, and In-to-O flux ratios r. The data are discussed in terms of the competing formation of In{sub 2}O{sub 3} and desorption of the suboxide In{sub 2}O and O. The same three growth regimes as in the case of Ga{sub 2}O{sub 3} can be distinguished: (i) In-transport limited, O-rich (ii) In{sub 2}O-desorption limited, O-rich, and (iii) O-transport limited, In-rich. In regime (iii), In droplets are formed on the growth surface at low T{sub G}. The growth kinetics follows qualitatively that of Ga{sub 2}O{sub 3} in agreement with their common oxide and suboxide stoichiometry. The quantitative differences are mainly rationalized by the difference in In{sub 2}O and Ga{sub 2}O desorption rates and vapor pressures. For the In{sub 2}O, Ga{sub 2}O, and O desorption, we extracted the activation energies and frequency factors by means of Arrhenius-plots.

  14. Stability of hydrogenation states of graphene and conditions for hydrogen spillover

    NASA Astrophysics Data System (ADS)

    Han, Sang Soo; Jung, Hyun; Jung, Dong Hyun; Choi, Seung-Hoon; Park, Noejung

    2012-04-01

    The hydrogen spillover mechanism has been discussed in the field of hydrogen storage and is believed to have particular advantage over the storage as metal or chemical hydrides. We investigate conditions for practicality realizing the hydrogen spillover mechanism onto carbon surfaces, using first-principles methods. Our results show that contrary to common belief, types of hydrogenation configurations of graphene (the aggregated all-paired configurations) can satisfy the thermodynamic requirement for room-temperature hydrogen storage. However, the peculiarity of the paired adsorption modes gives rise to a large kinetic barrier against hydrogen migration and desorption. It means that an extremely high pressure is required to induce the migration-derived hydrogenation. However, if mobile catalytic particles are present inside the graphitic interstitials, hydrogen migration channels can open and the spillover phenomena can be realized. We suggest a molecular model for such a mobile catalyst which can exchange hydrogen atoms with the wall of graphene.

  15. Hybrid electrodynamics and kinetics simulation for electromagnetic wave propagation in weakly ionized hydrogen plasmas.

    PubMed

    Chen, Qiang; Chen, Bin

    2012-10-01

    In this paper, a hybrid electrodynamics and kinetics numerical model based on the finite-difference time-domain method and lattice Boltzmann method is presented for electromagnetic wave propagation in weakly ionized hydrogen plasmas. In this framework, the multicomponent Bhatnagar-Gross-Krook collision model considering both elastic and Coulomb collisions and the multicomponent force model based on the Guo model are introduced, which supply a hyperfine description on the interaction between electromagnetic wave and weakly ionized plasma. Cubic spline interpolation and mean filtering technique are separately introduced to solve the multiscalar problem and enhance the physical quantities, which are polluted by numerical noise. Several simulations have been implemented to validate our model. The numerical results are consistent with a simplified analytical model, which demonstrates that this model can obtain satisfying numerical solutions successfully.

  16. Dual Studies on a Hydrogen-Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect.

    PubMed

    Giles, Richard; Kim, Iris; Chao, Weyjuin Eric; Moore, Jennifer; Jung, Kyung Woon

    2014-08-12

    An efficient laboratory experiment has been developed for undergraduate students to conduct hydrogen-deuterium (H-D) exchange of resorcinol by electrophilic aromatic substitution using D2O and a catalytic amount of H2SO4. The resulting labeled product is characterized by (1)H NMR. Students also visualize a significant kinetic isotope effect (kH/kD ≈ 3 to 4) by adding iodine tincture to solutions of unlabeled resorcinol and the H-D exchange product. This method is highly adaptable to fit a target audience and has been successfully implemented in a pedagogical capacity with second-year introductory organic chemistry students as part of their laboratory curriculum. It was also adapted for students at the advanced high school level.

  17. Kinetics of 1,5-hydrogen migration in alkyl radical reaction class.

    PubMed

    Ratkiewicz, Artur; Bankiewicz, Barbara

    2012-01-12

    Kinetics of the 1,5-intramolecular hydrogen migration in the alkyl radicals reaction class has been studied using the reaction class transition state theory combined with the linear energy relationship (LER) and the barrier height grouping (BHG) approach. The high pressure limits of the rate constants for the reference reaction of 1-pentyl → 1-pentyl, calculated by the Canonical Variational Transition State Theory (CVT) with the Small Curvature Tunneling (SCT), are taken from the literature. Direct comparison with available experimental data indicates that the RC-TST/LER, where only reaction energy is needed, can predict rate constants for any reaction in this reaction class with excellent accuracy. Specifically for this reaction class, the RC-TST/LER method has less than 65% systematic errors in the predicted rate constants when compared to explicit rate calculations.

  18. Polymer-induced surface modifications of Pd-based thin films leading to improved kinetics in hydrogen sensing and energy storage applications.

    PubMed

    Ngene, Peter; Westerwaal, Ruud J; Sachdeva, Sumit; Haije, Wim; de Smet, Louis C P M; Dam, Bernard

    2014-11-03

    The catalytic properties of Pd alloy thin films are enhanced by a thin sputtered PTFE coating, resulting in profound improvements in hydrogen adsorption and desorption in Pd-based and Pd-catalyzed hydrogen sensors and hydrogen storage materials. The remarkably enhanced catalytic performance is attributed to chemical modifications of the catalyst surface by the sputtered PTFE leading to a possible change in the binding strength of the intermediate species involved in the hydrogen sorption process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Absorption-Desorption Compressor for Spaceborne/Airborne Cryogenic Refrigerators.

    DTIC Science & Technology

    Refrigerant compressors, *Refrigeration systems), Spaceborne, Airborne, Cryogenics, Gases, Absorption, Desorption, Hydrogen, Hydrides, Lanthanum compounds, Nickel alloys, Joule Thomson effect , Heat transfer

  20. Theoretical study of the thermodynamics and kinetics of hydrogen abstractions from hydrocarbons.

    PubMed

    Vandeputte, Aäron G; Sabbe, Maarten K; Reyniers, Marie-Françoise; Van Speybroeck, Veronique; Waroquier, Michel; Marin, Guy B

    2007-11-22

    Thermochemical and kinetic data were calculated at four cost-effective levels of theory for a set consisting of five hydrogen abstraction reactions between hydrocarbons for which experimental data are available. The selection of a reliable, yet cost-effective method to study this type of reactions for a broad range of applications was done on the basis of comparison with experimental data or with results obtained from computationally demanding high level of theory calculations. For this benchmark study two composite methods (CBS-QB3 and G3B3) and two density functional theory (DFT) methods, MPW1PW91/6-311G(2d,d,p) and BMK/6-311G(2d,d,p), were selected. All four methods succeeded well in describing the thermochemical properties of the five studied hydrogen abstraction reactions. High-level Weizmann-1 (W1) calculations indicated that CBS-QB3 succeeds in predicting the most accurate reaction barrier for the hydrogen abstraction of methane by methyl but tends to underestimate the reaction barriers for reactions where spin contamination is observed in the transition state. Experimental rate coefficients were most accurately predicted with CBS-QB3. Therefore, CBS-QB3 was selected to investigate the influence of both the 1D hindered internal rotor treatment about the forming bond (1D-HR) and tunneling on the rate coefficients for a set of 21 hydrogen abstraction reactions. Three zero curvature tunneling (ZCT) methods were evaluated (Wigner, Skodje & Truhlar, Eckart). As the computationally more demanding centrifugal dominant small curvature semiclassical (CD-SCS) tunneling method did not yield significantly better agreement with experiment compared to the ZCT methods, CD-SCS tunneling contributions were only assessed for the hydrogen abstractions by methyl from methane and ethane. The best agreement with experimental rate coefficients was found when Eckart tunneling and 1D-HR corrections were applied. A mean deviation of a factor 6 on the rate coefficients is found for

  1. On the mean kinetic energy of the proton in strong hydrogen bonded systems

    SciTech Connect

    Finkelstein, Y.; Moreh, R.; Shang, S. L.; Wang, Y.; Liu, Z. K.; Shchur, Ya.

    2016-02-07

    The mean atomic kinetic energies of the proton, Ke(H), and of the deuteron, Ke(D), were calculated in moderate and strongly hydrogen bonded (HB) systems, such as the ferro-electric crystals of the KDP type (XH{sub 2}PO{sub 4}, X = K, Cs, Rb, Tl), the DKDP (XD{sub 2}PO{sub 4}, X = K, Cs, Rb) type, and the X{sub 3}H(SO{sub 4}){sub 2} superprotonic conductors (X = K, Rb). All calculations utilized the simulated partial phonon density of states, deduced from density functional theory based first-principle calculations and from empirical lattice dynamics simulations in which the Coulomb, short range, covalent, and van der Waals interactions were accounted for. The presently calculated Ke(H) values for the two systems were found to be in excellent agreement with published values obtained by deep inelastic neutron scattering measurements carried out using the VESUVIO instrument of the Rutherford Laboratory, UK. The Ke(H) values of the M{sub 3}H(SO{sub 4}){sub 2} compounds, in which the hydrogen bonds are centro-symmetric, are much lower than those of the KDP type crystals, in direct consistency with the oxygen-oxygen distance R{sub OO}, being a measure of the HB strength.

  2. Inhibition of tafel kinetics for electrolytic hydrogen evolution on isolated micron scale electrocatalysts on semiconductor interfaces

    DOE PAGES

    Coridan, Robert H.; Schichtl, Zebulon G.; Sun, Tao; ...

    2016-08-30

    Semiconductor-liquid junctions are ubiquitous in photoelectrochemical approaches for solar-to-fuels energy conversion. Electrocatalysts are added to the interface to improve catalytic efficiency, but they can also impair the photovoltage-generating energetics of the electrode without appropriate microscopic organization of catalytically active area on the surface. This balance is more complicated when gas products are evolved, like hydrogen on water splitting electrodes. Discrete catalysts can be blocked by the gas liquid-solid boundary of a bubble stuck to the surface. Here, we study the kinetics of hydrogen evolution on semiconductor electrodes fabricated with an isolated, micronscale platinum electrocatalyst pad. Movies of in operando bubblemore » evolution were recorded with synchrotron-based high-speed x-ray phase-contrast imaging in a compatible electrochemical cell. The self-limited growth of a bubble residing on the isolated electrocatalyst was measured by tracking the evolution of the gas-liquid boundary through the sequence of images in the movie. As a result, the effect of pad size on the catalytic currents and the issues with reactant transport can be inferred from these dynamics.« less

  3. Inhibition of tafel kinetics for electrolytic hydrogen evolution on isolated micron scale electrocatalysts on semiconductor interfaces

    SciTech Connect

    Coridan, Robert H.; Schichtl, Zebulon G.; Sun, Tao; Fezzaa, Kamel

    2016-08-30

    Semiconductor-liquid junctions are ubiquitous in photoelectrochemical approaches for solar-to-fuels energy conversion. Electrocatalysts are added to the interface to improve catalytic efficiency, but they can also impair the photovoltage-generating energetics of the electrode without appropriate microscopic organization of catalytically active area on the surface. This balance is more complicated when gas products are evolved, like hydrogen on water splitting electrodes. Discrete catalysts can be blocked by the gas liquid-solid boundary of a bubble stuck to the surface. Here, we study the kinetics of hydrogen evolution on semiconductor electrodes fabricated with an isolated, micronscale platinum electrocatalyst pad. Movies of in operando bubble evolution were recorded with synchrotron-based high-speed x-ray phase-contrast imaging in a compatible electrochemical cell. The self-limited growth of a bubble residing on the isolated electrocatalyst was measured by tracking the evolution of the gas-liquid boundary through the sequence of images in the movie. As a result, the effect of pad size on the catalytic currents and the issues with reactant transport can be inferred from these dynamics.

  4. Fundamental Kinetics of Supercritical Coal Liquefaction: Effect of Catalysts and Hydrogen-Donor Solvents.

    SciTech Connect

    McCoy, B.J.; Smith, J.M.

    1997-07-21

    Most research on polymer degradation is for single polymers, even though the thermal decomposition of polymer mixtures is of interest both practically and theoretically. Polymer degradation rates depend on the mixture type, and adding a polymer can increase, decrease, or leave unchanged the degradation rate of the first polymer. We show how distribution-kinetics theory, based on molecular-weight distributions (MWDs), provides expressions for degradation rates of binary polymer mixtures. The approach accounts for initiation, termination, hydrogen abstraction, and radical chain scission in the governing equations for MWDS. Molecular-weight moments yield expressions for molar and mass concentrations and rate coefficients for combinations of random and chain-end scission. Experimental data show the concentration effect of poly((x-methyl styrene)) (PAMS) on the degradation of polystyrene dissolved in mineral oil at 275 {degrees}C in a batch reactor. Samples analyzed by gel permeation chromatography yielded the time evolution of the MD. The results indicated that, owing to the interaction of mixed radicals with polymer by hydrogen abstraction, polystyrene degradation rate decreases with increasing PAMS concentration.

  5. Simulating the Heliosphere with Kinetic Hydrogen and Dynamic MHD Source Terms

    SciTech Connect

    Heerikhuisen, Jacob; Pogorelov, Nikolai; Zank, Gary

    2013-04-01

    The interaction between the ionized plasma of the solar wind (SW) emanating from the sun and the partially ionized plasma of the local interstellar medium (LISM) creates the heliosphere. The heliospheric interface is characterized by the tangential discontinuity known as the heliopause that separates the SW and LISM plasmas, and a termination shock on the SW side along with a possible bow shock on the LISM side. Neutral Hydrogen of interstellar origin plays a critical role in shaping the heliospheric interface, since it freely traverses the heliopause. Charge-exchange between H-atoms and plasma protons couples the ions and neutrals, but the mean free paths are large, resulting in non-equilibrated energetic ion and neutral components. In our model, source terms for the MHD equations are generated using a kinetic approach for hydrogen, and the key computational challenge is to resolve these sources with sufficient statistics. For steady-state simulations, statistics can accumulate over arbitrarily long time intervals. In this paper we discuss an approach for improving the statistics in time-dependent calculations, and present results from simulations of the heliosphere where the SW conditions at the inner boundary of the computation vary according to an idealized solar cycle.

  6. Simulating the Heliosphere with Kinetic Hydrogen and Dynamic MHD Source Terms

    DOE PAGES

    Heerikhuisen, Jacob; Pogorelov, Nikolai; Zank, Gary

    2013-04-01

    The interaction between the ionized plasma of the solar wind (SW) emanating from the sun and the partially ionized plasma of the local interstellar medium (LISM) creates the heliosphere. The heliospheric interface is characterized by the tangential discontinuity known as the heliopause that separates the SW and LISM plasmas, and a termination shock on the SW side along with a possible bow shock on the LISM side. Neutral Hydrogen of interstellar origin plays a critical role in shaping the heliospheric interface, since it freely traverses the heliopause. Charge-exchange between H-atoms and plasma protons couples the ions and neutrals, but themore » mean free paths are large, resulting in non-equilibrated energetic ion and neutral components. In our model, source terms for the MHD equations are generated using a kinetic approach for hydrogen, and the key computational challenge is to resolve these sources with sufficient statistics. For steady-state simulations, statistics can accumulate over arbitrarily long time intervals. In this paper we discuss an approach for improving the statistics in time-dependent calculations, and present results from simulations of the heliosphere where the SW conditions at the inner boundary of the computation vary according to an idealized solar cycle.« less

  7. Capacitively coupled radio-frequency hydrogen discharges: The role of kinetics

    SciTech Connect

    Marques, L.; Jolly, J.; Alves, L. L.

    2007-09-15

    This paper presents a systematic characterization of capacitively coupled radio-frequency hydrogen discharges, produced within a parallel plate cylindrical setup at different rf applied voltages (V{sub rf}=50-600 V), frequencies (f=13.56-40.68 MHz), and pressures (p=0.2-1 torr). A two-dimensional, time-dependent fluid model for charged particle transport is self-consistently solved coupled to a homogeneous kinetic model for hydrogen, including vibrationally excited molecular species and electronically excited atomic species. Numerical simulations are compared with experimental measurements of various plasma parameters. A good quantitative agreement is found between simulations and experiment for the coupled electrical power and the plasma potential. The model underestimates the values of the electron density, the self-bias potential, and the H(n=1) atom density with respect to measurements, but agrees with experiment when predicting that all these parameters increase with either V{sub rf}, f, or p. The dissociation degree is about 10{sup -3} for the work conditions considered. Simulations adopt a wall recombination probability for H atoms that was experimentally measured, thus accounting for surface modification with discharge operating conditions. Results show the key role played by the atomic wall recombination mechanism in plasma description.

  8. On the mean kinetic energy of the proton in strong hydrogen bonded systems

    NASA Astrophysics Data System (ADS)

    Finkelstein, Y.; Moreh, R.; Shang, S. L.; Shchur, Ya.; Wang, Y.; Liu, Z. K.

    2016-02-01

    The mean atomic kinetic energies of the proton, Ke(H), and of the deuteron, Ke(D), were calculated in moderate and strongly hydrogen bonded (HB) systems, such as the ferro-electric crystals of the KDP type (XH2PO4, X = K, Cs, Rb, Tl), the DKDP (XD2PO4, X = K, Cs, Rb) type, and the X3H(SO4)2 superprotonic conductors (X = K, Rb). All calculations utilized the simulated partial phonon density of states, deduced from density functional theory based first-principle calculations and from empirical lattice dynamics simulations in which the Coulomb, short range, covalent, and van der Waals interactions were accounted for. The presently calculated Ke(H) values for the two systems were found to be in excellent agreement with published values obtained by deep inelastic neutron scattering measurements carried out using the VESUVIO instrument of the Rutherford Laboratory, UK. The Ke(H) values of the M3H(SO4)2 compounds, in which the hydrogen bonds are centro-symmetric, are much lower than those of the KDP type crystals, in direct consistency with the oxygen-oxygen distance ROO, being a measure of the HB strength.

  9. Coal desulfurization in oxidative acid media using hydrogen peroxide and ozone: a kinetic and statistical approach

    SciTech Connect

    F.R. Carrillo-Pedroza; A. Davalos Sanchez; M. Soria-Aguilar; E.T. Pecina Trevino

    2009-07-15

    The removal of pyritic sulfur from a Mexican sub-bituminous coal in nitric, sulfuric, and hydrochloric acid solutions was investigated. The effect of the type and concentration of acid, in the presence of hydrogen peroxide and ozone as oxidants, in a temperature range of 20-60{sup o}C, was studied. The relevant factors in pyrite dissolution were determined by means of the statistical analysis of variance and optimized by the response surface method. Kinetic models were also evaluated, showing that the dissolution of pyritic sulfur follows the kinetic model of the shrinking core model, with diffusion through the solid product of the reaction as the controlling stage. The results of statistical analysis indicate that the use of ozone as an oxidant improves the pyrite dissolution because, at 0.25 M HNO{sub 3} or H{sub 2}SO{sub 4} at 20{sup o}C and 0.33 g/h O{sub 3}, the obtained dissolution is similar to that of 1 M H{sub 2}O{sub 2} and 1 M HNO{sub 3} or H{sub 2}SO{sub 4} at 40{sup o}C. 42 refs., 9 figs., 3 tabs.

  10. Compensation effect in the hydrogenation/dehydrogenation kinetics of metal hydrides.

    PubMed

    Andreasen, Anders; Vegge, Tejs; Pedersen, Allan S

    2005-03-03

    The possible existence of a compensation effect, i.e. concurrent changes in activation energy and prefactor, is investigated for the hydrogenation and dehydrogenation kinetics of metal hydrides, by analyzing a series of reported kinetic studies on Mg and LaNi(5) based hydrides. For these systems, we find a clear linear relation between apparent prefactors and apparent activation energies, as obtained from an Arrhenius analysis, indicating the existence of a compensation effect. Large changes in apparent activation energies in the case of Mg based hydrides are rationalized in terms of a dependency of observed apparent activation energy on the degree of surface oxidation, i.e., a physical effect. On the other hand, we find the large concurrent changes in apparent prefactors to be a direct result of the Arrhenius analysis. Thus, we find the observed compensation effect to be an artifact of the data analysis rather than a physical phenomenon. In the case of LaNi(5) based hydrides, observed scatter in reported apparent activation energies is less pronounced supporting the general experience that LaNi(5) is less sensitive toward surface contamination.

  11. Chemical kinetic analysis of hydrogen-air ignition and reaction times

    NASA Technical Reports Server (NTRS)

    Rogers, R. C.; Schexnayder, C. J., Jr.

    1981-01-01

    An anaytical study of hydrogen air kinetics was performed. Calculations were made over a range of pressure from 0.2 to 4.0 atm, temperatures from 850 to 2000 K, and mixture equivalence ratios from 0.2 to 2.0. The finite rate chemistry model included 60 reactions in 20 species of the H2-O2-N2 system. The calculations also included an assessment of how small amounts of the chemicals H2O, NOx, H2O2, and O3 in the initial mixture affect ignition and reaction times, and how the variation of the third body efficiency of H2O relative of N2 in certain key reactions may affect reaction time. The results indicate that for mixture equivalence ratios between 0.5 and 1.7, ignition times are nearly constant; however, the presence of H2O and NO can have significant effects on ignition times, depending on the mixture temperature. Reaction time is dominantly influenced by pressure but is nearly independent of initial temperature, equivalence ratio, and the addition of chemicals. Effects of kinetics on reaction at supersonic combustor conditions are discussed.

  12. Kinetic modeling of E-to-H mode transition in inductively coupled hydrogen plasmas

    SciTech Connect

    Nishida, K. Mochizuki, S.; Hatayama, A.; Mattei, S.; Lettry, J.

    2016-06-21

    Radio Frequency (RF) Inductively Coupled Plasmas (ICPs) are widely known for their two discharge modes, i.e., H-mode and E-mode, where the dynamics of the plasmas are completely different from each other. We have performed a kinetic simulation of a hydrogen plasma discharge in order to clarify the discharge mechanism and the E-to-H transition of the RF ICPs. The numerical simulation results, such as the time variations of spatial distribution of electron density and the power dissipated in the plasma, show the characteristic changes of the plasma dynamics due to E-to-H mode transition. Especially, the drastic change during the mode transition has been observed in the time evolution of the electron energy distribution function (EEDF). The EEDF deviates from a Maxwellian distribution before/after the transition and the deviation is more significant in the E-mode phase. These results indicate the importance of kinetic modeling for the physical understanding of E-to-H transition.

  13. Hydrogen Donor-Acceptor Fluctuations from Kinetic Isotope Effects: A Phenomenological Model

    PubMed Central

    Roston, Daniel; Cheatum, Christopher M.; Kohen, Amnon

    2012-01-01

    Kinetic isotope effects (KIEs) and their temperature dependence can probe the structural and dynamic nature of enzyme-catalyzed proton or hydride transfers. The molecular interpretation of their temperature dependence requires expensive and specialized QM/MM calculations to provide a quantitative molecular understanding. Currently available phenomenological models use a non-adiabatic assumption that is not appropriate for most hydride and proton-transfer reactions, while others require more parameters than the experimental data justify. Here we propose a phenomenological interpretation of KIEs based on a simple method to quantitatively link the size and temperature dependence of KIEs to a conformational distribution of the catalyzed reaction. The present model assumes adiabatic hydrogen tunneling, and by fitting experimental KIE data, the model yields a population distribution for fluctuations of the distance between donor and acceptor atoms. Fits to data from a variety of proton and hydride transfers catalyzed by enzymes and their mutants, as well as non-enzymatic reactions, reveal that steeply temperature-dependent KIEs indicate the presence of at least two distinct conformational populations, each with different kinetic behaviors. We present the results of these calculations for several published cases and discuss how the predictions of the calculations might be experimentally tested. The current analysis does not replace molecular quantum mechanics/molecular mechanics (QM/MM) investigations, but it provides a fast and accessible way to quantitatively interpret KIEs in the context of a Marcus-like model. PMID:22857146

  14. Kinetic Analysis of Competitive Electrocatalytic Pathways: New Insights into Hydrogen Production with Nickel Electrocatalysts

    SciTech Connect

    Wiedner, Eric S.; Brown, Houston J.; Helm, Monte L.

    2016-01-20

    The hydrogen production electrocatalyst Ni(PPh2NPh2)22+ (1) is capable of traversing multiple electrocatalytic pathways. When using dimethylformamidium, DMF(H)+, the mechanism of formation of H2 catalyzed by 1 changes from an ECEC to an EECC mechanism as the potential approaches the Ni(I/0) couple. Two recent electrochemical methods, current-potential analysis and foot-of-the-wave analysis (FOWA), were performed on 1 to measure the detailed chemical kinetics of the competing ECEC and EECC pathways. A sensitivity analysis was performed on the electrochemical methods using digital simulations to gain a better understanding of their strengths and limitations. Notably, chemical rate constants were significantly underestimated when not accounting for electron transfer kinetics, even when electron transfer was fast enough to afford a reversible non-catalytic wave. The EECC pathway of 1 was found to be faster than the ECEC pathway under all conditions studied. Using buffered DMF: DMF(H)+ mixtures led to an increase in the catalytic rate constant (kobs) of the EECC pathway, but kobs for the ECEC pathway did not change when using buffered acid. Further kinetic analysis of the ECEC path revealed that added base increases the rate of isomerization of the exo-protonated Ni(0) isomers to the catalytically active endo-isomers, but decreases the net rate of protonation of Ni(I). FOWA on 1 did not provide accurate rate constants due to incomplete reduction of the exo-protonated Ni(I) intermediate at the foot of the wave, but FOWA could be used to estimate the reduction potential of this previously undetected intermediate. This research 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. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  15. Real-Time Studies of Gallium Adsorption and Desorption Kinetics by Grazing-Incidence Small-Angle X-ray Scattering and X-ray Fluorescence

    SciTech Connect

    Wang, Y.; Ozcan, A; Ludwig, K; Bhattacharyya, A

    2008-01-01

    Gallium adsorption and desorption on c-plane sapphire has been studied by real-time grazing incidence small-angle x-ray scattering and x-ray fluorescence as a function of substrate temperature (680-740 C) and Ga flux. The x-ray techniques monitor the surface morphology evolution and amount of Ga on the surface. During deposition, nanodroplets of liquid Ga are observed to form on the surface and coarsen. The growth of droplet size during continuous deposition follows dynamical scaling, in agreement with expectations from theory and simulations which include deposition-induced droplet coalescence. However, observation of continued droplet distance scale coarsening during desorption points to the necessity of including further physical processes in the modeling. The desorption rate at different substrate temperatures gives the activation energy of Ga desorption as 2.7 eV, comparable to measured activation energies for desorption from Ga droplets on other substrates and to the Ga heat of vaporization.

  16. Kinetics of microbial bromate reduction in a hydrogen-oxidizing, denitrifying biofilm reactor.

    PubMed

    Downing, Leon S; Nerenberg, Robert

    2007-10-15

    Bromate (BrO(3)(-)) is an oxidized contaminant produced from bromide (Br(-)) during ozonation and advanced oxidation of drinking water. Previous research shows that denitrifying bioreactors can reduce bromate to innocuous bromide. We studied a hydrogen-based, denitrifying membrane-biofilm reactor (MBfR) for bromate reduction, and report the first kinetics for a hydrogen-based bromate reduction process. A mixed-culture MBfR reduced up to 1,500 microg/L bromate to below 10 microg/L with a 50-min hydraulic residence time. Kinetics were determined using short-term tests on a completely mixed MBfR at steady state with an influent of 5 mg N/L nitrate plus 100 microg/L bromate. Short-term tests examined the impact of pH, nitrite, nitrate, and bromate on bromate reduction rates in the MBfR. Kinetic parameters for the process were estimated based on the short-term bromate tests. The q(max) for bromate reduction was 0.12 mg BrO(3)(-) x mg(x)(-1) x day(-1), and the K was 1.2 mg BrO(3)(-)/L. This q(max) is 2-3 times higher than reported for heterotrophic enrichments, and the K is the first reported in the literature. Nitrite and nitrate partially inhibited bromate reduction, with nitrite exerting a stronger inhibitory effect. Bromate was self-inhibitory at concentrations above 15 mg/L, but up to 50 mg/L of bromate had no inhibitory effect on denitrification. The optimum pH was approximately 7. We also examined the performance of an MBfR containing pure culture of the denitrifying bacterium Ralstonia eutropha. Under conditions similar to the mixed-culture tests, no bromate reduction was detected, showing that not all denitrifying bacteria are active in bromate reduction. Our results suggest the presence of specialized, dissimilatory bromate-reducing bacteria in the mixed-culture MBfR. Copyright 2007 Wiley Periodicals, Inc.

  17. Mechanisms and Kinetics of Boron Removal from Silicon by Humidified Hydrogen

    NASA Astrophysics Data System (ADS)

    Safarian, Jafar; Tang, Kai; Olsen, Jan Erik; Andersson, Stefan; Tranell, Gabriella; Hildal, Kjetil

    2016-04-01

    The removal of boron from silicon by top blowing of humidified hydrogen has been studied in the present work through experimental work, thermodynamic calculations, computational fluid dynamic modeling, and quantum chemistry calculations. The effect of process parameters; temperature, lance diameter, lance distance from the melt surface, gas flow rate, and crucible material on the kinetics of boron removal were studied. It has been shown that the rate of boron removal is decreased with increasing temperature due to the competitive reactions between silicon and oxygen as well as boron and oxygen, which can be confirmed with the increases of p SiO/ p HBO in the system. The rate of boron removal is increased with increasing the gas flow rate due mainly to the better supply and transport of the gas over the melt surface, as confirmed by the CFD modeling. Moreover, the rate of boron removal in alumina crucible is the highest followed by that in quartz and graphite crucibles, respectively. Faster B removal in quartz crucible than that in graphite crucible can be attributed to more oxygen dissolves in silicon melts. The fastest boron removal in alumina crucible is attributed to the additional boron gasification through aluminum borate (AlBO2) formation on the melt surface. Thermodynamic properties of the AlBO2 species have thus been revised by quantum chemistry calculations, which were more accurate to describe the formation of gaseous AlBO2 than those in the JANAF Thermochemical Tables. The main chemical reactions for boron gasification from silicon melts are proposed as In graphite, quartz and alumina crucible:quad \\underline{{B}} + \\underline{{H}} + \\underline{{O}} = {{ HBO}}( {{g}} ) {{In alumina crucible}}:\\underline{{Al}} + \\underline{{B}} + \\underline{{O}} = {{ AlBO}}2 ( {{g}} ) Based on the obtained results, it has been proposed that boron removal from silicon melt by humidified hydrogen is controlled both by the chemical reaction for boron gasification and

  18. Kinetics of uranium(VI) reduction by hydrogen sulfide in anoxic aqueous systems.

    PubMed

    Hua, Bin; Xu, Huifang; Terry, Jeff; Deng, Baolin

    2006-08-01

    Aqueous U(VI) reduction by hydrogen sulfide was investigated by batch experiments and speciation modeling; product analysis by transmission electron microscopy (TEM) was also performed. The molar ratio of U(VI) reduced to sulfide consumed, and the TEM result suggested that the reaction stoichiometry could be best represented by UO2(2+) + HS- = UO2+ S* + H+. At pH 6.89 and total carbonate concentration ([CO32-]T) of 4.0 mM, the reaction took place according to the following kinetics: -d[U(VI)]/dt = 0.0103[U(VI)][S2-]T0.54 where [U(VI)] is the concentration of hexavalent uranium, and [S2-]T is the total concentration of sulfide. The kinetics of U(VI) reduction was found to be largely controlled by [CO32-]T (examined from 0.0 to 30.0 mM) and pH (examined from 6.37 to 9.06). The reduction was almost completely inhibited with the following [CO32-]T and pH combinations: [(> or = 15.0 mM, pH 6.89); (> or = 4.0 mM, pH 8.01); and (> or = 2.0 mM, pH 9.06)]. By comparing the experimental results with the calculated speciation of U(VI), it was found that there was a strong correlation between the measured initial reaction rates and the calculated total concentrations of uranium-hydroxyl species; we, therefore, concluded that uranium-hydroxyl species were the ones being reduced by sulfide, not the dominant U-carbonate species present in many carbonate-containing systems.

  19. Hydrogen production in anaerobic reactors during shock loads--influence of formate production and H2 kinetics.

    PubMed

    Voolapalli, R K; Stuckey, D C

    2001-05-01

    In this article the role of hydrogen as a process monitoring tool in methanogenic systems was studied by considering the influence of several key system parameters. Hydrogen production was found to be influenced mainly by the inocula's source pH, and varied only slightly with external pH and HCO3- levels. When an inoculum adapted to above neutral conditions (pH > 7) was shocked, reducing equivalents were selectively channelled through formate, while high hydrogen production was noticed with acidically (pH < 6.5) adapted inocula. The results also revealed that the production of hydrogen or formate during shock loads was not strongly associated with microbial morphology (granules or flocs) as high electron fluxes were possible through either during acidogenesis. Shock load experiments in continuous reactors revealed that neither hydrogen nor formate accumulated to any significant degree, nevertheless digester recovery took a long time due to the slow kinetics of volatile fatty acid degradation. Selective formate production under neutral pH environments, coupled with high hydrogenotrophic activity, was found to be responsible for the dampened hydrogen response during the early phases of gradually shocked systems (step change). Based on these results it appears that the role of hydrogen as a process monitoring tool has been overemphasised in the literature.

  20. An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron

    NASA Technical Reports Server (NTRS)

    Shanabarger, Mickey R.

    1994-01-01

    The goal of this program has been to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. During the present program, the interaction of hydrogen with the surfaces of alpha-2 (Ti3Al) titanium aluminide, gamma (TiAl) titanium aluminide, and beryllium were studied. The interaction of low pressure hydrogen with gamma titanium aluminide and beryllium was found to be relatively weak. Weak in the sense that adsorption leads to a low surface concentration of dissociated hydrogen, i.e., the chemisorption process is reversible at room temperature (300 K) for gamma titanium aluminide and the sticking coefficient for chemisorption is extremely small for beryllium. Hydrogen was found to interact readily with alpha-2 titanium aluminide to form a stable surface hydride at 300 K. These results correlate well with other recent studies which show that the mechanical properties for alpha-2 titanium aluminide are readily degraded in hydrogen while gamma titanium aluminide exhibits less degradation and beryllium essentially no degradation. The interaction of oxygen with the surface of several of these materials was studied. More recently, preliminary hydrogen permeation studies were completed for three high temperature alloys, Incoloy 909, Mo-47.5Re (wt. %), and this past year, Haynes 188.

  1. Influence of Hydrogen Bonding on the Kinetic Stability of Vapor Deposited Glasses of Triazine Derivatives

    DOE Data Explorer

    Laventure, Audrey [Departement de chimie, Universite de Montreal, C.P. 6128, Succ. Centre-Ville, Montreal, Quebec H3C 3J7, Canada] (ORCID:0000000208670231); Gujral, Ankit [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States] (ORCID:0000000250652694); Lebel, Olivier [Department of Chemistry and Chemical Engineering, Royal Military College of Canada, Kingston, Ontario K7K 7B4] (ORCID:0000000217376843); Ediger, Mark [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States] (ORCID:0000000347158473); Pellerin, Christian [Departement de chimie, Universite de Montreal, C.P. 6128, Succ. Centre-Ville, Montreal, Quebec H3C 3J7, Canada] (ORCID:0000000161441318)

    2017-02-01

    It has recently been established that physical vapor deposition (PVD) can produce organic glasses with enhanced kinetic stability, high density, and anisotropic packing, with the substrate temperature during deposition (Tsubstrate) as the key control parameter. The influence of hydrogen bonding on the formation of PVD glasses has not been fully explored. Herein, we use a high-throughput preparation method to vapor-deposit three triazine derivatives over a wide range of Tsubstrate, from 0.69 to 1.08Tg, where Tg is the glass transition temperature. These model systems are structural analogues containing a functional group with different H-bonding capability at the 2-position of a triazine ring: (1) 2-methylamino-4,6-bis(3,5-dimethyl-phenylamino)-1,3,5-triazine (NHMe) (H-bond donor), (2) 2-methoxy-4,6-bis(3,5-dimethyl-phenylamino)-1,3,5-triazine (OMe) (H-bond acceptor), and (3) 2-ethyl-4,6-bis(3,5-dimethyl-phenylamino)-1,3,5-triazine (Et) (none). Using spectroscopic ellipsometry, we find that the Et and OMe compounds form PVD glasses with relatively high kinetic stability, with the transformation time (scaled by the α-relaxation time) on the order of 103, comparable to other highly stable glasses formed by PVD. In contrast, PVD glasses of NHMe are only slightly more stable than the corresponding liquid-cooled glass. Using IR spectroscopy, we find that both the supercooled liquid and the PVD glasses of the NHMe derivative show a higher average number of bonded NH per molecule than that in the other two compounds. These results suggest that H-bonds hinder the formation of stable glasses, perhaps by limiting the surface mobility. Interestingly, despite this difference in kinetic stability, all three compounds show properties typically observed in highly stable glasses prepared by PVD, including a higher density and anisotropic molecular packing (as characterized by IR and wide-angle X-ray scattering).

  2. Influence of Hydrogen Bonding on the Kinetic Stability of Vapor-Deposited Glasses of Triazine Derivatives.

    PubMed

    Laventure, Audrey; Gujral, Ankit; Lebel, Olivier; Pellerin, Christian; Ediger, M D

    2017-03-16

    It has recently been established that physical vapor deposition (PVD) can produce organic glasses with enhanced kinetic stability, high density, and anisotropic packing, with the substrate temperature during deposition (Tsubstrate) as the key control parameter. The influence of hydrogen bonding on the formation of PVD glasses has not been fully explored. Herein, we use a high-throughput preparation method to vapor-deposit three triazine derivatives over a wide range of Tsubstrate, from 0.69 to 1.08Tg, where Tg is the glass transition temperature. These model systems are structural analogues containing a functional group with different H-bonding capability at the 2-position of a triazine ring: (1) 2-methylamino-4,6-bis(3,5-dimethyl-phenylamino)-1,3,5-triazine (NHMe) (H-bond donor), (2) 2-methoxy-4,6-bis(3,5-dimethyl-phenylamino)-1,3,5-triazine (OMe) (H-bond acceptor), and (3) 2-ethyl-4,6-bis(3,5-dimethyl-phenylamino)-1,3,5-triazine (Et) (none). Using spectroscopic ellipsometry, we find that the Et and OMe compounds form PVD glasses with relatively high kinetic stability, with the transformation time (scaled by the α-relaxation time) on the order of 10(3), comparable to other highly stable glasses formed by PVD. In contrast, PVD glasses of NHMe are only slightly more stable than the corresponding liquid-cooled glass. Using IR spectroscopy, we find that both the supercooled liquid and the PVD glasses of the NHMe derivative show a higher average number of bonded NH per molecule than that in the other two compounds. These results suggest that H-bonds hinder the formation of stable glasses, perhaps by limiting the surface mobility. Interestingly, despite this difference in kinetic stability, all three compounds show properties typically observed in highly stable glasses prepared by PVD, including a higher density and anisotropic molecular packing (as characterized by IR and wide-angle X-ray scattering).

  3. Kinetic-energy release of fragments from electron-impact dissociation of the molecular hydrogen ion and its isotopologues

    NASA Astrophysics Data System (ADS)

    Scarlett, Liam H.; Zammit, Mark C.; Fursa, Dmitry V.; Bray, Igor

    2017-08-01

    We calculate the kinetic-energy release distributions of fragments produced for electron-impact dissociation of the vibrationally excited molecular hydrogen ion H2 + and its isotopologues D2 + and T2 +. Here we apply the adiabatic-nuclei convergent close-coupling method and compare results with several different methods, including the δ approximation. Results are presented for a number of dissociative excitation transitions and dissociative ionization as a function of the initial vibrational state of the molecule. We confirm that the square root approximation is a good approximation for the adiabatic-nuclei kinetic-energy release cross sections of H2 +. Agreement with experiment, where available, is good.

  4. Kinetics of hydrogen isotope exchange in β-phase Pd-H-D

    DOE PAGES

    Luo, Weifang; Cowgill, Donald F.

    2015-07-22

    Hydrogen isotope gas exchange within palladium powders is examined using a batch-type reactor coupled to a residual gas analyzer (RGA). Furthermore, the exchange rates in both directions (H2 + PdD and D2 + PdH) are measured in the temperature range 178–323 K for the samples with different particle sizes. The results show this batch-type exchange is closely approximated as a first-order kinetic process with a rate directly proportional to the surface area of the powder particles. An exchange rate constant of 1.40 ± 0.24 μmol H2/atm cm2 s is found for H2 + PdD at 298 K, 1.4 times highermore » than that for D2 + PdH, with an activation energy of 25.0 ± 3.2 kJ/mol H for both exchange directions. Finally, a comparison of exchange measurement techniques shows these coefficients, and the fundamental exchange probabilities are in good agreement with those obtained by NMR and flow techniques.« less

  5. Kinetics of hydrogen isotope exchange in β-phase Pd-H-D

    SciTech Connect

    Luo, Weifang; Cowgill, Donald F.

    2015-07-22

    Hydrogen isotope gas exchange within palladium powders is examined using a batch-type reactor coupled to a residual gas analyzer (RGA). Furthermore, the exchange rates in both directions (H2 + PdD and D2 + PdH) are measured in the temperature range 178–323 K for the samples with different particle sizes. The results show this batch-type exchange is closely approximated as a first-order kinetic process with a rate directly proportional to the surface area of the powder particles. An exchange rate constant of 1.40 ± 0.24 μmol H2/atm cm2 s is found for H2 + PdD at 298 K, 1.4 times higher than that for D2 + PdH, with an activation energy of 25.0 ± 3.2 kJ/mol H for both exchange directions. Finally, a comparison of exchange measurement techniques shows these coefficients, and the fundamental exchange probabilities are in good agreement with those obtained by NMR and flow techniques.

  6. Investigation of the kinetics of reduction of nickel tungstate by hydrogen

    SciTech Connect

    Sridhar, S. . Dept. of Materials Science and Engineering); Du Sichen; Seetharaman, S. . Dept. of Metallurgy)

    1994-06-01

    In the present work, the kinetics of reduction of nickel tungstate, NiWO[sub 4], by hydrogen was investigated by a thermogravimetric method in the temperature range 891 to 1,141 K. The experiments were conducted under both isothermal and nonisothermal conditions. The products were examined by X-ray diffraction analysis. The results indicate that the reduction reaction proceeds in two steps; first, reduction of NiWO[sub 4] to nickel as well as WO[sub 2] and then WO[sub 2] to tungsten. From the isothermal experiments, the activation energies of the two reaction steps were calculated to be 95.3 [+-] 4.9 and 80.8 [+-] 6.4 kJ [center dot] mol[sup [minus]1], respectively. The activation energy value obtained from nonisothermal experiments for the first step is in agreement with the isothermal experiments. The values are compared with the activation energies reported in other literature for the individual oxides.

  7. The chemical kinetics and thermodynamics of sodium species in oxygen-rich hydrogen flames

    NASA Technical Reports Server (NTRS)

    Hynes, A. J.; Steinberg, M.; Schofield, K.

    1984-01-01

    Results are presented which, it is claimed, lead to a correction of previous misconceptions over the relative importance and kinetics of NaO2. It is shown that its rapid conversion to NaO and NaOH is such that it can severely perturb the NaOH/Na ratio and produce significant concentration overshoots over that predicted from the balance of the reaction of Na with H2O. This becomes increasingly the case in flames of large O2 concentrations and temperatures below 2500 K; and the corresponding large rate constants for the termolecular formation of the other alkali peroxides imply that similar considerations will be necessary for them. Depending on the rate constants for the exothermic conversions of MO2 to MO or MOH, the steady-state concentrations of MO2 could be more or less significant than for sodium. Owing to numerous reactions that produce these conversions, the MOH species will probably be the dominant species in all cases in oxygen-rich hydrogen or hydrocarbon flames, with MO concentrations at not greater than 1 percent of the bound metal.

  8. Kinetics of 1,4-hydrogen migration in the alkyl radical reaction class.

    PubMed

    Bankiewicz, Barbara; Huynh, Lam K; Ratkiewicz, Artur; Truong, Thanh N

    2009-02-26

    The kinetics of the 1,4-intramolecular hydrogen migration in the alkyl radicals reaction class has been studied using reaction class transition-state theory combined with the linear energy relationship (LER) and barrier height grouping (BHG) approach. The rate constants for the reference reaction of n-C(4)H(9) were obtained by canonical variational transition-state theory (CVT) with the small curvature tunnelling (SCT) correction in the temperature range 300-3000 K with potential-energy surface information computed at the CCSD(T)/cc-pVDZ//BH&HLYP/cc-pVDZ level of theory. Error analyses indicate that RC-TST/LER, where only reaction energy is needed, and RC-TST/BHG, where no other information is needed, can predict rate constants for any reaction in this reaction class with excellent accuracy. Specifically, for this reaction class the RC-TST/LER method has less than 65% systematic errors in the predicted rate constants, while the RC-TST/BHG method has less than 80% error when compared to explicit rate calculations.

  9. Kinetics of oxidation of bilirubin and its protein complex by hydrogen peroxide in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Solomonov, A. V.; Rumyantsev, E. V.; Antina, E. V.

    2010-12-01

    A comparative study of oxidation reactions of bilirubin and its complex with albumin was carried out in aqueous solutions under the action of hydrogen peroxide and molecular oxygen at different pH values. Free radical oxidation of the pigment in both free and bound forms at pH 7.4 was shown not to lead to the formation of biliverdin, but to be associated with the decomposition of the tetrapyrrole chromophore into monopyrrolic products. The effective and true rate constants of the reactions under study were determined. It was assumed that one possible mechanism of the oxidation reaction is associated with the interaction of peroxyl radicals and protons of the NH groups of bilirubin molecules at the limiting stage with the formation of a highly reactive radical intermediate. The binding of bilirubin with albumin was found to result in a considerable reduction in the rate of the oxidation reaction associated with the kinetic manifestation of the protein protection effect. It was found that the autoxidation of bilirubin by molecular oxygen with the formation of biliverdin at the intermediate stage can be observed with an increase in the pH of solutions.

  10. Zirconium-nickel crystals—hydrogen accumulators: Dissolution and penetration of hydrogen atoms in alloys

    NASA Astrophysics Data System (ADS)

    Matysina, Z. A.; Zaginaichenko, S. Yu.; Shchur, D. V.; Gabdullin, M. T.; Kamenetskaya, E. A.

    2016-07-01

    The calculation of the free energy, thermodynamic equilibrium equations, and kinetic equations of the intermetallic compound Zr2NiH x has been carried out based on molecular-kinetic concepts. The equilibrium hydrogen concentration depending on the temperature, pressure, and energy parameters has been calculated. The absorption-desorption of hydrogen has been studied, and the possibility of the realization of the hysteresis effect has been revealed. The kinetics of the dissolution and permeability of hydrogen is considered, the time dependence of these values has been found, and conditions for the extremum character of their time dependence have been determined. Relaxation times of the dissolution and permeability of hydrogen into the alloy have been calculated. The calculation results are compared with the experimental data available in the literature.

  11. Hydrogen storage development

    SciTech Connect

    Thomas, G.J.; Guthrie, S.E.

    1998-08-01

    A summary of the hydride development efforts for the current program year (FY98) are presented here. The Mg-Al-Zn alloy system was studied at low Zn levels (2--4 wt%) and midrange Al contents (40--60 wt%). Higher plateau pressures were found with Al and Zn alloying in Mg and, furthermore, it was found that the hydrogen desorption kinetics were significantly improved with small additions of Zn. Results are also shown here for a detailed study of the low temperature properties of Mg{sub 2}NiH{sub 4}, and a comparison made between conventional melt cast alloy and the vapor process material.

  12. Kinetic solvent effects on hydrogen abstraction reactions from carbon by the cumyloxyl radical. The importance of solvent hydrogen-bond interactions with the substrate and the abstracting radical.

    PubMed

    Salamone, Michela; Giammarioli, Ilaria; Bietti, Massimo

    2011-06-03

    A kinetic study of the hydrogen atom abstraction reactions from propanal (PA) and 2,2-dimethylpropanal (DMPA) by the cumyloxyl radical (CumO•) has been carried out in different solvents (benzene, PhCl, MeCN, t-BuOH, MeOH, and TFE). The corresponding reactions of the benzyloxyl radical (BnO•) have been studied in MeCN. The reaction of CumO• with 1,4-cyclohexadiene (CHD) also has been investigated in TFE solution. With CHD a 3-fold increase in rate constant (k(H)) has been observed on going from benzene, PhCl, and MeCN to TFE. This represents the first observation of a sizable kinetic solvent effect for hydrogen atom abstraction reactions from hydrocarbons by alkoxyl radicals and indicates that strong HBD solvents influence the hydrogen abstraction reactivity of CumO•. With PA and DMPA a significant decrease in k(H) has been observed on going from benzene and PhCl to MeOH and TFE, indicative of hydrogen-bond interactions between the carbonyl lone pair and the solvent in the transition state. The similar k(H) values observed for the reactions of the aldehydes in MeOH and TFE point toward differential hydrogen bond interactions of the latter solvent with the substrate and the radical in the transition state. The small reactivity ratios observed for the reactions of CumO• and BnO• with PA and DMPA (k(H)(BnO•)/k(H)(CumO•) = 1.2 and 1.6, respectively) indicate that with these substrates alkoxyl radical sterics play a minor role.

  13. Kinetic model for photoinduced and thermally induced creation and annihilation of metastable defects in hydrogenated amorphous silicon

    NASA Astrophysics Data System (ADS)

    Abdulhalim, I.

    1995-03-01

    A microscopic many-body model is proposed for the kinetics of metastable defects (MSDs) in hydrogenated amorphous silicon (a-Si:H). It is based on the existence of short-lived large energy fluctuations which induce transient traps for carriers that release their energy and enhance the creation or annihilation of MSDs. The expressions found for the photoinduced and thermally induced creation and annihilation rates' coefficients explain the dependence on the variety of parameters.

  14. Technical and economic aspects of hydrogen storage in metal hydrides

    NASA Technical Reports Server (NTRS)

    Schmitt, R.

    1981-01-01

    The recovery of hydrogen from such metal hydrides as LiH, MgH2, TiH2, CaH2 and FeTiH compounds is studied, with the aim of evaluating the viability of the technique for the storage of hydrogen fuel. The pressure-temperature dependence of the reactions, enthalpies of formation, the kinetics of the hydrogen absorption and desorption, and the mechanical and chemical stability of the metal hydrides are taken into account in the evaluation. Economic aspects are considered. Development of portable metal hydride hydrogen storage reservoirs is also mentioned.

  15. Kinetics and mechanism of the degradation of methyl parathion in aqueous hydrogen sulfide solution: investigation of natural organic matter effects.

    PubMed

    Guo, Xiaofen; Jans, Urs

    2006-02-01

    The kinetics of the transformation of methyl parathion have been investigated in aqueous solution containing reduced sulfur species and small concentrations of natural organic matter (NOM) from different sources such as soil, river, and peat. It was shown that NOM mediates the degradation of methyl parathion in aqueous solutions containing hydrogen sulfide. After evaluating and quantifying the effect of the NOM concentration on the degradation kinetics of methyl parathion in the presence of hydrogen sulfide, it was found that the observed pseudo-first-order reaction rate constants (k(obs)) were proportional to NOM concentrations. The influence of pH on the degradation of methyl parathion in the aqueous solutions containing hydrogen sulfide and NOM has been studied. The rate of degradation of methyl parathion was strongly pH dependent. The results indicate k(obs) with a commercially available humic acid has a maximum value at approximately pH 8.3. Two main reaction mechanisms are identified to dominate the degradation of methyl parathion in aqueous solution containing hydrogen sulfide and NOM based on the products aminomethyl parathion and desmethyl methyl parathion. The two mechanisms are nitro-group reduction and nucleophilic attack at the methoxy-carbon. The reduction of the nitro-group is only observed in the presence of NOM. The results of this study form an important base for the evaluation and interpretation of transformation processes of methyl parathion in the environment.

  16. Effects of pH and ORP on microbial ecology and kinetics for hydrogen production in continuously dark fermentation.

    PubMed

    Song, Jiaxiu; An, Dong; Ren, Nanqi; Zhang, Yongming; Chen, Ying

    2011-12-01

    The microbial structure and kinetic characteristics of the hydrogen producing strains in two fermentative continuous stirred-tank reactors (CSTRs) were studied by controlling pH and oxidation and reduction potential (ORP). The fluorescence in situ hybridization (FISH) tests were conducted to investigate the fermentative performance of Clostridium histolyticum (C. histolyticum), Clostridium lituseburense (C. lituseburense) and Enterobacteriaceae. The experimental results showed that in ethanol-type reactor 1#, the relative abundance of the strains was 48%, 30% and 22%. Comparatively, the relative abundance in butyric acid-type reactor 2# was 24%, 55% and 19% with butyric acids and hydrogen as the main products. The kinetic results indicated that the hydrogen yield coefficients YP/X in both reactors were 8.357 and 5.951 l-H2/g, while the coefficients of the cellular yield were 0.0268 and 0.0350 g-Cell/g, respectively. At the same biomass, the hydrogen yield in ethanol-type reactors was more than that in butyric acid reactors. However, the cellular synthesis rate in ethanol-type reactors was low when the same carbon source was used.

  17. Intrinsic Kinetics of Dimethyl Ether Synthesis from Plasma Activation of CO2 Hydrogenation over Cu-Fe-Ce/HZSM-5.

    PubMed

    Su, Tongming; Zhou, Xinhui; Qin, Zuzeng; Ji, Hongbing

    2017-02-02

    CO2 is activated in a plasma reactor followed by hydrogenation over a Cu-Fe-Ce/HZSM-5 catalyst, and the intrinsic kinetics of the plasma catalytic process are studied. Compared with CO2 hydrogenation using Cu-Fe-Ce/HZSM-5 alone, the CO2 conversion and the dimethyl ether selectivity for the plasma catalytic process are increased by 16.3 %, and 10.1 %, respectively, indicating that the CO2 was activated by the plasma to promote hydrogenation. A study of the intrinsic kinetics shows that the activation energies of methanol formation, the reverse water-gas shift reaction, and methanol dehydration to dimethyl ether are 149.34, 75.47, and 73.18 kJ mol(-1) , respectively, which are lower than if Cu-Fe-Ce/HZSM-5 is used without plasma, indicating that the activation of CO2 in the plasma reduces the activation energy of the hydrogenation reaction and improves the yield of dimethyl ether.

  18. The kinetics of the hydrogen/deuterium exchange of epidermal growth factor receptor ligands.

    PubMed

    Iloro, Ibon; Narváez, Daniel; Guillén, Nancy; Camacho, Carlos M; Guillén, Lalisse; Cora, Elsa; Pastrana-Ríos, Belinda

    2008-05-15

    Five highly homologous epidermal growth factor receptor ligands were studied by mass spectral analysis, hydrogen/deuterium (H/D) exchange via attenuated total reflectance Fourier transform-infrared spectroscopy, and two-dimensional correlation analysis. These studies were performed to determine the order of events during the exchange process, the extent of H/D exchange, and associated kinetics of exchange for a comparative analysis of these ligands. Furthermore, the secondary structure composition of amphiregulin (AR) and heparin-binding-epidermal growth factor (HB-EGF) was determined. All ligands were found to have similar contributions of 3(10)-helix and random coil with varying contributions of beta-sheets and beta-turns. The extent of exchange was 40%, 65%, 55%, 65%, and 98% for EGF, transforming growth factor-alpha (TGF-alpha), AR, HB-EGF, and epiregulin (ER), respectively. The rate constants were determined and classified as fast, intermediate, and slow: for EGF the 0.20 min(-1) (Tyr), 0.09 min(-1) (Arg, beta-turns), and 1.88 x 10(-3) min(-1) (beta-sheets and 3(10)-helix); and for TGF-alpha 0.91 min(-1) (Tyr), 0.27 min(-1) (Arg, beta-turns), and 1.41 x 10(-4) min(-1) (beta-sheets). The time constants for AR 0.47 min(-1) (Tyr), 0.04 min(-1) (Arg), and 1.00 x 10(-4) min(-1) (buried 3(10)-helix, beta-turns, and beta-sheets); for HB-EGF 0.89 min(-1) (Tyr), 0.14 min(-1) (Arg and 3(10)-helix), and 1.00 x 10(-3) min(-1) (buried 3(10)-helix, beta-sheets, and beta-turns); and for epiregulin 0.16 min(-1) (Tyr), 0.03 min(-1) (Arg), and 1.00 x 10(-4) min(-1) (3(10)-helix and beta-sheets). These results provide essential information toward understanding secondary structure, H/D exchange kinetics, and solvation of these epidermal growth factor receptor ligands in their unbound state.

  19. Metal Hydride Nanoparticles with Ultrahigh Structural Stability and Hydrogen Storage Activity Derived from Microencapsulated Nanoconfinement.

    PubMed

    Zhang, Jiguang; Zhu, Yunfeng; Lin, Huaijun; Liu, Yana; Zhang, Yao; Li, Shenyang; Ma, Zhongliang; Li, Liquan

    2017-06-01

    Metal hydrides (MHs) have recently been designed for hydrogen sensors, switchable mirrors, rechargeable batteries, and other energy-storage and conversion-related applications. The demands of MHs, particular fast hydrogen absorption/desorption kinetics, have brought their sizes to nanoscale. However, the nanostructured MHs generally suffer from surface passivation and low aggregation-resisting structural stability upon absorption/desorption. This study reports a novel strategy named microencapsulated nanoconfinement to realize local synthesis of nano-MHs, which possess ultrahigh structural stability and superior desorption kinetics. Monodispersed Mg2 NiH4 single crystal nanoparticles (NPs) are in situ encapsulated on the surface of graphene sheets (GS) through facile gas-solid reactions. This well-defined MgO coating layer with a thickness of ≈3 nm efficiently separates the NPs from each other to prevent aggregation during hydrogen absorption/desorption cycles, leading to excellent thermal and mechanical stability. More interestingly, the MgO layer shows superior gas-selective permeability to prevent further oxidation of Mg2 NiH4 meanwhile accessible for hydrogen absorption/desorption. As a result, an extremely low activation energy (31.2 kJ mol(-1) ) for the dehydrogenation reaction is achieved. This study provides alternative insights into designing nanosized MHs with both excellent hydrogen storage activity and thermal/mechanical stability exempting surface modification by agents. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. A Kinetic Platform to Determine the Fate of Hydrogen Peroxide in Escherichia coli

    PubMed Central

    Adolfsen, Kristin J.; Brynildsen, Mark P.

    2015-01-01

    Hydrogen peroxide (H2O2) is used by phagocytic cells of the innate immune response to kill engulfed bacteria. H2O2 diffuses freely into bacteria, where it can wreak havoc on sensitive biomolecules if it is not rapidly detoxified. Accordingly, bacteria have evolved numerous systems to defend themselves against H2O2, and the importance of these systems to pathogenesis has been substantiated by the many bacteria that require them to establish or sustain infections. The kinetic competition for H2O2 within bacteria is complex, which suggests that quantitative models will improve interpretation and prediction of network behavior. To date, such models have been of limited scope, and this inspired us to construct a quantitative, systems-level model of H2O2 detoxification in Escherichia coli that includes detoxification enzymes, H2O2-dependent transcriptional regulation, enzyme degradation, the Fenton reaction and damage caused by •OH, oxidation of biomolecules by H2O2, and repair processes. After using an iterative computational and experimental procedure to train the model, we leveraged it to predict how H2O2 detoxification would change in response to an environmental perturbation that pathogens encounter within host phagosomes, carbon source deprivation, which leads to translational inhibition and limited availability of NADH. We found that the model accurately predicted that NADH depletion would delay clearance at low H2O2 concentrations and that detoxification at higher concentrations would resemble that of carbon-replete conditions. These results suggest that protein synthesis during bolus H2O2 stress does not affect clearance dynamics and that access to catabolites only matters at low H2O2 concentrations. We anticipate that this model will serve as a computational tool for the quantitative exploration and dissection of oxidative stress in bacteria, and that the model and methods used to develop it will provide important templates for the generation of comparable

  1. Thermodynamic and kinetic considerations for the reaction of semiquinone radicals to form superoxide and hydrogen peroxide.

    PubMed

    Song, Yang; Buettner, Garry R

    2010-09-15

    The quinone/semiquinone/hydroquinone triad (Q/SQ(*-)/H(2)Q) represents a class of compounds that has great importance in a wide range of biological processes. The half-cell reduction potentials of these redox couples in aqueous solutions at neutral pH, E degrees ', provide a window to understanding the thermodynamic and kinetic characteristics of this triad and their associated chemistry and biochemistry in vivo. Substituents on the quinone ring can significantly influence the electron density "on the ring" and thus modify E degrees' dramatically. E degrees' of the quinone governs the reaction of semiquinone with dioxygen to form superoxide. At near-neutral pH the pK(a)'s of the hydroquinone are outstanding indicators of the electron density in the aromatic ring of the members of these triads (electrophilicity) and thus are excellent tools to predict half-cell reduction potentials for both the one-electron and two-electron couples, which in turn allow estimates of rate constants for the reactions of these triads. For example, the higher the pK(a)'s of H(2)Q, the lower the reduction potentials and the higher the rate constants for the reaction of SQ(*-) with dioxygen to form superoxide. However, hydroquinone autoxidation is controlled by the concentration of di-ionized hydroquinone; thus, the lower the pK(a)'s the less stable H(2)Q to autoxidation. Catalysts, e.g., metals and quinone, can accelerate oxidation processes; by removing superoxide and increasing the rate of formation of quinone, superoxide dismutase can accelerate oxidation of hydroquinones and thereby increase the flux of hydrogen peroxide. The principal reactions of quinones are with nucleophiles via Michael addition, for example, with thiols and amines. The rate constants for these addition reactions are also related to E degrees'. Thus, pK(a)'s of a hydroquinone and E degrees ' are central to the chemistry of these triads. Copyright 2010 Elsevier Inc. All rights reserved.

  2. Phosphorus seasonal sorption-desorption kinetics in suspended sediment in response to land use and management in the Guaporé catchment, Southern Brazil.

    PubMed

    Zafar, Mohsin; Tiecher, Tales; de Castro Lima, José Augusto Monteiro; Schaefer, Gilmar Luiz; Santanna, Maria Alice; Dos Santos, Danilo Rheinheimer

    2016-11-01

    Phosphate sorption-desorption parameters like maximum phosphorus (P) adsorption capacity (P max), equilibrium phosphorus concentration (EPC), water desorbable P (α), potentially bioavailable P (β), and mobility index (α/β ratio) were determined in order to understand the sediment source-sink nature in Guaporé catchment in southern Brazil during summer and winter 2013 and 2014. The result showed a significant (p = 0.05) variation across sediment site or seasons and revealed the most sorption-desorption parameters (P max, α, β) with the increments following the order urban sediments > intensive agriculture under CT > intensive agriculture under NT > low agriculture sub-catchments (sub1 and sub2) > native forest. In the main river points, these parameters decreased along the river (P1 to P5). The results were more obvious in winter than the summer season. In contrast, the low values of λ and α/β ratio in the sediment from native forest and relatively less polluted catchment (sub1) during summer season show the quick P desorption when compared to specific Fe and Al oxides bound to stable P in intensive agriculture sediments. These findings clearly indicated that agricultural practices, sediment characteristics, and hydrological factors have a major impact on seasonal sediment P bioavailability and mobility. The urban untreated discharges may be a single major P source and, if it is not wisely managed, proves a major threat to water quality. These results have serious implications for the river ecosystem and will be of great importance to improve the environmental and economic performance of agricultural practices aiming to reduce soil-based P legacy to surface waters.

  3. Kinetic and Mechanistic Studies of Carbon-to-Metal Hydrogen Atom Transfer Involving Os-Centered Radicals: Evidence for Tunneling

    SciTech Connect

    Lewandowska-Androlojc, Anna; Grills, David C.; Zhang, Jie; Bullock, R. Morris; Miyazawa, Akira; Kawanishi, Yuji; Fujita, Etsuko

    2014-03-05

    We have investigated the kinetics of novel carbon-to-metal hydrogen atom transfer reactions, in which homolytic cleavage of a C-H bond is accomplished by a single metal-centered radical. Studies by means of time-resolved IR spectroscopic measurements revealed efficient hydrogen atom transfer from xanthene, 9,10-dihydroanthracene and 1,4-cyclohexadiene to Cp(CO)2Os• and (n5-iPr4C5H)(CO)2Os• radicals, formed by photoinduced homolysis of the corresponding osmium dimers. The rate constants for hydrogen abstraction from these hydrocarbons were found to be in the range 1.54 × 105 M 1 s 1 -1.73 × 107 M 1 s-1 at 25 °C. For the first time, kinetic isotope effects for carbon-to-metal hydrogen atom transfer were determined. Large primary kinetic isotope effects of 13.4 ± 1.0 and 16.6 ± 1.4 were observed for the hydrogen abstraction from xanthene to form Cp(CO)2OsH and (n5-iPr4C5H)(CO)2OsH, respectively, at 25 °C. Temperature-dependent measurements of the kinetic isotope effects over a 60 -C temperature range were carried out to obtain the difference in activation energies and the pre-exponential factor ratio. For hydrogen atom transfer from xanthene to (n5-iPr4C5H)(CO)2Os•, the (ED - EH) = 3.25 ± 0.20 kcal/mol and AH/AD = 0.056 ± 0.018 values are greater than the semi-classical limits and thus suggest a quantum mechanical tunneling mechanism. The work at BNL was carried out under contract DE-AC02-98CH10886 with the U.S. Department of Energy and supported by its Division of Chemical Sciences, Geosciences & Biosciences, Office of Basic Energy Sciences. RMB also thanks the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences for support. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

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

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

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

  5. Dynamic effects of promoters on associative desorption.

    PubMed

    Sales, J L; Uñac, R O; Gargiulo, M V; Zgrablich, G

    2000-04-04

    The kinetics of the associative desorption of A(2) in the presence of coadsorbed promoter species B is studied under conditions of nonequilibrium by the analysis of thermal desorption spectra obtained by Monte Carlo simulation. A rich variety of behaviors is found and discussed with regard to the interplay between the concentrations of promoter species, the surface mobility of A and B, and the interparticle interactions.

  6. Cation-induced kinetic trapping and enhanced hydrogen adsorption in a modulated anionic metal-organic framework.

    PubMed

    Yang, Sihai; Lin, Xiang; Blake, Alexander J; Walker, Gavin S; Hubberstey, Peter; Champness, Neil R; Schröder, Martin

    2009-09-01

    Metal-organic frameworks (MOFs)--microporous materials constructed by bridging metal centres with organic ligands--show promise for applications in hydrogen storage, which is a key challenge in the development of the 'hydrogen economy'. Their adsorption capacities, however, have remained insufficient for practical applications, and thus strategies to enhance hydrogen-MOF interactions are required. Here we describe an anionic MOF material built from In(III) centres and tetracarboxylic acid ligands (H(4)L) in which kinetic trapping behaviour--where hydrogen is adsorbed at high pressures but not released immediately on lowering the pressure--is modulated by guest cations. With piperazinium dications in its pores, the framework exhibits hysteretic hydrogen adsorption. On exchange of these dications with lithium cations, no hysteresis is seen, but instead there is an enhanced adsorption capacity coupled to an increase in the isosteric heat of adsorption. This is rationalized by the different locations of the cations within the pores, determined with precision by X-ray crystallography.

  7. Carbon Dioxide Hydrogenation into Higher Hydrocarbons and Oxygenates: Thermodynamic and Kinetic Bounds and Progress with Heterogeneous and Homogeneous Catalysis.

    PubMed

    Prieto, Gonzalo

    2017-03-22

    Under specific scenarios, the catalytic hydrogenation of CO2 with renewable hydrogen is considered a suitable route for the chemical recycling of this environmentally harmful and chemically refractory molecule into added-value energy carriers and chemicals. The hydrogenation of CO2 into C1 products, such as methane and methanol, can be achieved with high selectivities towards the corresponding hydrogenation product. More challenging, however, is the selective production of high (C2+ ) hydrocarbons and oxygenates. These products are desired as energy vectors, owing to their higher volumetric energy density and compatibility with the current fuel infrastructure than C1 compounds, and as entry platform chemicals for existing value chains. The major challenge is the optimal integration of catalytic functionalities for both reductive and chain-growth steps. This Minireview summarizes the progress achieved towards the hydrogenation of CO2 to C2+ hydrocarbons and oxygenates, covering both solid and molecular catalysts and processes in the gas and liquid phases. Mechanistic aspects are discussed with emphasis on intrinsic kinetic limitations, in some cases inevitably linked to thermodynamic bounds through the concomitant reverse water-gas-shift reaction, which should be considered in the development of advanced catalysts and processes.

  8. H2 Desorption from MgH2 Surfaces with Steps and Catalyst-Dopants

    SciTech Connect

    Reich, Jason M.; Wang, Lin-Lin; Johnson, Duane D.

    2014-03-10

    Light-metal hydrides, like MgH2, remain under scrutiny as prototypes for reversible H-storage materials. For MgH2, we assess hydrogen desorption/adsorption properties (enthalpy and kinetic barriers) for stepped, catalyst-doped surfaces occurring, e.g., from ball-milling in real samples. Employing density functional theory and simulated annealing in a slab model, we studied initial H2 desorption from stepped surfaces with(out) titanium (Ti) catalytic dopant. Extensive simulated annealing studies were performed to find the dopant’s site preferences. For the most stable initial and final (possibly magnetic) states, nudged elastic band (NEB) calculations were performed to determine the H2-desorption activation energy. We used a moment-transition NEB method to account for the dopant’s transition to the lowest-energy magnetic state at each image along the band. We identify a dopant-related surface-desorption mechanism that reloads via bulk H diffusion. While reproducing the observed bulk enthalpy of desorption, we find a decrease of 0.24 eV (a 14% reduction) in the activation energy on doped stepped surface; together with a 22% reduction on a doped flat surface, this brackets the assessed 18% reduction in kinetic barrier for ball-milled MgH2 samples with low concentration of Ti from experiment.

  9. Variations in protein/flavin hydrogen bonding in a LOV domain produce non-Arrhenius kinetics of adduct decay†

    PubMed Central

    Zoltowski, Brian D.; Nash, Abigail I.; Gardner, Kevin H.

    2011-01-01

    Light Oxygen Voltage (LOV) domains utilize a conserved blue light-dependent mechanism to control a diverse array of effector domains in biological and engineered proteins. Variations in the kinetics and efficiency of LOV photochemistry fine tune various aspects of the photic response. Characterization of the kinetics of a key aspect of this photochemical mechanism in EL222, a blue-light responsive DNA binding protein from Erythrobacter litoralis HTCC2594, reveals unique non-Arrhenius behavior in the rate of dark state cleavage of the photochemically-generated adduct. Sequence analysis and mutagenesis studies establish that this effect stems from a Gln to Ala mutation unique to EL222 and homologous proteins from marine bacteria. Kinetic and spectroscopic analyses reveal that hydrogen bonding interactions between the FMN N1, O2 and ribityl hydroxyls with the surrounding protein regulate photocycle kinetics and stabilize the LOV active site from temperature-induced alteration in local structure. Substitution of residues interacting with the N1-O2 locus modulates adduct stability, structural flexibility and sequestration of the active site from bulk solvent without perturbation of light-activated DNA binding. Together, these variants link non-Arrhenius behavior to specific alteration of an H-bonding network, while affording tunability of photocycle kinetics. PMID:21923139

  10. Temperature effect on water desorption from methylcellulose films studied by thermal FT-IR microspectroscopy

    NASA Astrophysics Data System (ADS)

    Lin, Shan-Yang; Wang, Shun-Li; Wei, Yen-Shan; Li, Mei-Jane

    2007-02-01

    Temperature-induced desorption behavior of water from methylcellulose (MC) film was investigated by a novel microscopic Fourier transform infrared (FT-IR) spectroscopy equipped with thermal analyzer (thermal FT-IR microscopic system) and thermogravimetric analysis (TGA). The result indicates that the weight loss of water from MC film was markedly correlated to the IR spectral changes of OH stretching (3000-3800 cm -1) and bending (1649 cm -1) modes of water molecules. The shift of OH stretching mode from 3461 to 3481 cm -1 was accompanied with the water loss from MC film induced by temperature effect. Two stages of water desorption from MC film were proposed: the first stage within the 35-65 °C had a dramatic IR peak shift from 3461 to 3477 cm -1 and accompanied with a largest weight loss of water from MC film, which might be mainly due to the desorption of free water with minor weakly hydrogen-bonded water; the second stage beyond 65 °C would be desorption of moderately hydrogen-bonded bound water, due to the gradual IR spectral shift from 3477 to 3481 cm -1 and a slower weight loss of water from MC film. The changes in peak area ratio of 1649 cm -1/1374 cm -1 with the temperature also confirmed the IR spectral peak shift of the OH stretching mode via the water loss from MC film. The temperature-dependent dissociation of intermolecular and intramolecular hydrogen bonds within water molecules and/or between water/MC interaction might be responsible for the desorption kinetics of water from MC film.

  11. Gas-Phase Hydrogen-Deuterium Exchange Labeling of Select Peptide Ion Conformer Types: a Per-Residue Kinetics Analysis.

    PubMed

    Khakinejad, Mahdiar; Kondalaji, Samaneh Ghassabi; Tafreshian, Amirmahdi; Valentine, Stephen J

    2015-07-01

    The per-residue, gas-phase hydrogen deuterium exchange (HDX) kinetics for individual amino acid residues on selected ion conformer types of the model peptide KKDDDDDIIKIIK have been examined using ion mobility spectrometry (IMS) and HDX-tandem mass spectrometry (MS/MS) techniques. The [M + 4H](4+) ions exhibit two major conformer types with collision cross sections of 418 Å(2) and 446 Å(2); the [M + 3H](3+) ions also yield two different conformer types having collision cross sections of 340 Å(2) and 367 Å(2). Kinetics plots of HDX for individual amino acid residues reveal fast- and slow-exchanging hydrogens. The contributions of each amino acid residue to the overall conformer type rate constant have been estimated. For this peptide, N- and C-terminal K residues exhibit the greatest contributions for all ion conformer types. Interior D and I residues show decreased contributions. Several charge state trends are observed. On average, the D residues of the [M + 3H](3+) ions show faster HDX rate contributions compared with [M + 4H](4+) ions. In contrast the interior I8 and I9 residues show increased accessibility to exchange for the more elongated [M + 4H](4+) ion conformer type. The contribution of each residue to the overall uptake rate showed a good correlation with a residue hydrogen accessibility score model calculated using a distance from charge site and initial incorporation site for nominal structures obtained from molecular dynamic simulations (MDS).

  12. Gas-Phase Hydrogen-Deuterium Exchange Labeling of Select Peptide Ion Conformer Types: a Per-Residue Kinetics Analysis

    NASA Astrophysics Data System (ADS)

    Khakinejad, Mahdiar; Kondalaji, Samaneh Ghassabi; Tafreshian, Amirmahdi; Valentine, Stephen J.

    2015-07-01

    The per-residue, gas-phase hydrogen deuterium exchange (HDX) kinetics for individual amino acid residues on selected ion conformer types of the model peptide KKDDDDDIIKIIK have been examined using ion mobility spectrometry (IMS) and HDX-tandem mass spectrometry (MS/MS) techniques. The [M + 4H]4+ ions exhibit two major conformer types with collision cross sections of 418 Å2 and 446 Å2; the [M + 3H]3+ ions also yield two different conformer types having collision cross sections of 340 Å2 and 367 Å2. Kinetics plots of HDX for individual amino acid residues reveal fast- and slow-exchanging hydrogens. The contributions of each amino acid residue to the overall conformer type rate constant have been estimated. For this peptide, N- and C-terminal K residues exhibit the greatest contributions for all ion conformer types. Interior D and I residues show decreased contributions. Several charge state trends are observed. On average, the D residues of the [M + 3H]3+ ions show faster HDX rate contributions compared with [M + 4H]4+ ions. In contrast the interior I8 and I9 residues show increased accessibility to exchange for the more elongated [M + 4H]4+ ion conformer type. The contribution of each residue to the overall uptake rate showed a good correlation with a residue hydrogen accessibility score model calculated using a distance from charge site and initial incorporation site for nominal structures obtained from molecular dynamic simulations (MDS).

  13. Kinetics of self-decomposition and hydrogen atom transfer reactions of substituted phthalimide N-oxyl radicals in acetic acid.

    PubMed

    Cai, Yang; Koshino, Nobuyoshi; Saha, Basudeb; Espenson, James H

    2005-01-07

    Kinetic data have been obtained for three distinct types of reactions of phthalimide N-oxyl radicals (PINO(.)) and N-hydroxyphthalimide (NHPI) derivatives. The first is the self-decomposition of PINO(.) which was found to follow second-order kinetics. In the self-decomposition of 4-methyl-N-hydroxyphthalimide (4-Me-NHPI), H-atom abstraction competes with self-decomposition in the presence of excess 4-Me-NHPI. The second set of reactions studied is hydrogen atom transfer from NHPI to PINO(.), e.g., PINO(.) + 4-Me-NHPI <=> NHPI + 4-Me-PINO(.). The substantial KIE, k(H)/k(D) = 11 for both forward and reverse reactions, supports the assignment of H-atom transfer rather than stepwise electron-proton transfer. These data were correlated with the Marcus cross relation for hydrogen-atom transfer, and good agreement between the experimental and the calculated rate constants was obtained. The third reaction studied is hydrogen abstraction by PINO(.) from p-xylene and toluene. The reaction becomes regularly slower as the ring substituent on PINO(.) is more electron donating. Analysis by the Hammett equation gave rho = 1.1 and 1.8 for the reactions of PINO(.) with p-xylene and toluene, respectively.

  14. USING METHANOL-WATER SYSTEMS TO INVESTIGATE PHENANTHRENE SORPTION-DESORPTION ON SEDIMENT

    EPA Science Inventory

    Sorption isotherm nonlinearity, sorption-desorption hysteresis, slow desorption kinetics, and other nonideal phenomena have been attributed to the differing sorptive characteristics of the natural organic matter (NOM) polymers associated with soils and sediments. A conceptualizat...

  15. USING METHANOL-WATER SYSTEMS TO INVESTIGATE PHENANTHRENE SORPTION-DESORPTION ON SEDIMENT

    EPA Science Inventory

    Sorption isotherm nonlinearity, sorption-desorption hysteresis, slow desorption kinetics, and other nonideal phenomena have been attributed to the differing sorptive characteristics of the natural organic matter (NOM) polymers associated with soils and sediments. A conceptualizat...

  16. The complex kinetics of the ice VI to ice XV hydrogen ordering phase transition

    NASA Astrophysics Data System (ADS)

    Shephard, Jacob J.; Salzmann, Christoph G.

    2015-09-01

    The reversible phase transition from hydrochloric-acid-doped ice VI to its hydrogen-ordered counterpart ice XV is followed using differential scanning calorimetry. Upon cooling at ambient pressure fast hydrogen ordering is observed at first followed by a slower process which manifests as a tail to the initial sharp exotherm. The residual hydrogen disorder in H2O and D2O ice XV is determined as a function of the cooling rate. We conclude that it will be difficult to obtain fully hydrogen-ordered ice XV by cooling at ambient pressure. Our new experimental findings are discussed in the context of recent computational work on ice XV.

  17. Role of vacancies in the relaxation of Pd-5.3 at % In-0.5 at % Ru alloy foil after hydrogen desorption

    NASA Astrophysics Data System (ADS)

    Akimova, O. V.; Avdyukhina, V. M.; Shchetinin, I. V.

    2016-02-01

    The Pd-5.3 at % In-0.5 at % Ru foil subjected to electrolytic hydrogenation and subsequent prolonged relaxation (for 55 000 h) has been studied by X-ray diffraction analysis. Diffraction reflections belonging to phases with different indium concentrations and palladium phases enriched in vacancies were found. Phase transformations observed in the absence of hydrogen occur mainly due to the vacancy migration; the vacancies formed during hydrogenation and remained in vacancy complexes and alloy matrix up to the moment of the study.

  18. Kinetics and mechanisms of heterogeneous reaction of gaseous hydrogen peroxide on mineral oxide particles.

    PubMed

    Zhao, Yue; Chen, Zhongming; Shen, Xiaoli; Zhang, Xuan

    2011-04-15

    Recent studies have shown that heterogeneous reactions of hydrogen peroxide (H(2)O(2)) on aerosol surfaces may play an important role in tropospheric chemistry. The data concerning the kinetics and mechanisms of these reactions, however, are quite scarce so far. Here, we investigated, for the first time, the heterogeneous reactions of gaseous H(2)O(2) on SiO(2) and α-Al(2)O(3) particles, two major components of mineral dust aerosol, using transmission-Fourier Transform Infrared (T-FTIR) spectroscopy, and high-performance liquid chromatography (HPLC). It is found that H(2)O(2) molecularly adsorbs on SiO(2), and a small amount of molecularly adsorbed H(2)O(2) decomposes due to its thermal instability. For α-Al(2)O(3), catalytic decomposition of H(2)O(2) evidently occurs, but there is also a small amount of H(2)O(2) molecularly adsorbed on the particle surface. The BET uptake coefficients of H(2)O(2) on both particles appear to be independent of gaseous H(2)O(2) concentration (1.27-13.8 ppmv) and particle sample mass (2.8-6.5 mg for SiO(2) and 8.6-18.9 mg for α-Al(2)O(3)), but are strongly dependent on relative humidity with the values ranging from (1.55 ± 0.14) × 10(-8) and (1.21 ± 0.04) × 10(-7) at 2% RH to (0.61 ± 0.06) × 10(-8) and (0.76 ± 0.09) × 10(-7) at 76% RH for SiO(2) and α-Al(2)O(3), respectively. On the basis of the experimental results and literature data, the potential mechanisms for heterogeneous decomposition of H(2)O(2) were proposed, and the atmospheric implications of these reactions were discussed. It is found that heterogeneous reaction of H(2)O(2) on both mineral oxides plays a significant role in processing mineral aerosols, although its role as a sink for ambient H(2)O(2) is probably limited.

  19. Fast hydrogen sorption from MgH2-VO2(B) composite materials

    NASA Astrophysics Data System (ADS)

    Milošević, Sanja; Kurko, Sandra; Pasquini, Luca; Matović, Ljiljana; Vujasin, Radojka; Novaković, Nikola; Novaković, Jasmina Grbović

    2016-03-01

    The hydrogen sorption kinetics of MgH2‒VO2(B) composites synthesised by mechanical milling have been studied. The microstructural properties of composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, Scanning electron microscopy (SEM), Particle size analysis (PSD), while sorption behaviour was followed by differential scanning calorimetry (DSC) and Sievert measurements. Results have shown that although desorption temperature reduction is moderate; there is a substantial improvement in hydrogen sorption kinetics. The complete desorption of pure MgH2 at elevated temperature takes place in more than 30 min while the composite fully desorbs in less than 2 min even at lower temperatures. It has been shown that the metastable γ-MgH2 phase and the point defects have a decisive role in desorption process only in the first sorption cycle, while the second and the subsequent sorption cycles are affected by microstructural and morphological characteristics of the composite.

  20. Kinetic and spectroscopic requirements for the inference of chemical heating rates and atomic hydrogen densities from OH Meinel band measurements

    NASA Astrophysics Data System (ADS)

    Mlynczak, Martin G.; Zhou, Daniel K.; Adler-Golden, Steven M.

    We present the accuracy requirements for specific kinetic and spectroscopic parameters used in modeling populations of vibrationally excited hydroxyl. The requirements are based on simulations of the inference of chemical energy deposition rates and atomic hydrogen densities from satellite observations of the hydroxyl Meinel band emission rates. Improvement in the rate constants which describe the collisional removal of the high-lying υ states of OH and the reaction of highlying υ states with atomic oxygen is required in addition to improved specification of the nascent distribution of energy within OH upon reaction of atomic hydrogen and ozone. These improvements are necessary for the interpretation of Meinel band measurements to be made from a new spaceflight experiment in less than 3 years.

  1. Effect of electrolytical hydrogenation on the thermal stability and crystallization kinetics of metallic glass Fe79Si9B12

    NASA Astrophysics Data System (ADS)

    Górecki, Cz; Górecki, T.

    2011-04-01

    The effect of electrolytical hydrogenation on both the surface and volume crystallization kinetics and thermal stability of amorphous alloy Fe79Si9B12 has been investigated. The parameters of the surface and volume crystallization (temperature, activation energy) have been determined applying the exoelectron emission (EEE) and differential thermal analysis (DTA) methods, respectively. It has been found that the surface crystallization of investigated material occurs at temperature much lower and with activation energy smaller than the volume crystallization. The determination of the activation energies for the volume and surface crystallization by the combination of DTA and EEE techniques enables the determination of activation energies for both the nucleation and growth of the crystalline phase in metallic glasses and other amorphous materials. Hydrogenation of the investigated metallic glass reduces its thermal stability, what is manifested by an decrease in the activation energies for both the surface and volume crystallization.

  2. Growth kinetics of hydrogen sulfide oxidizing bacteria in corroded concrete from sewers.

    PubMed

    Jensen, Henriette Stokbro; Lens, Piet N L; Nielsen, Jeppe L; Bester, Kai; Nielsen, Asbjørn Haaning; Hvitved-Jacobsen, Thorkild; Vollertsen, Jes

    2011-05-30

    Hydrogen sulfide oxidation by microbes present on concrete surfaces of sewer pipes is a key process in sewer corrosion. The growth of aerobic sulfur oxidizing bacteria from corroded concrete surfaces was studied in a batch reactor. Samples of corrosion products, containing sulfur oxidizing bacteria, were suspended in aqueous solution at pH similar to that of corroded concrete. Hydrogen sulfide was supplied to the reactor to provide the source of reduced sulfur. The removal of hydrogen sulfide and oxygen was monitored. The utilization rates of both hydrogen sulfide and oxygen suggested exponential bacterial growth with median growth rates of 1.25 d(-1) and 1.33 d(-1) as determined from the utilization rates of hydrogen sulfide and oxygen, respectively. Elemental sulfur was found to be the immediate product of the hydrogen sulfide oxidation. When exponential growth had been achieved, the addition of hydrogen sulfide was terminated leading to elemental sulfur oxidation. The ratio of consumed sulfur to consumed oxygen suggested that sulfuric acid was the ultimate oxidation product. To the knowledge of the authors, this is the first study to determine the growth rate of bacteria involved in concrete corrosion with hydrogen sulfide as source of reduced sulfur.

  3. Chemical Kinetics of Hydrogen Atom Abstraction from Allylic Sites by (3)O2; Implications for Combustion Modeling and Simulation.

    PubMed

    Zhou, Chong-Wen; Simmie, John M; Somers, Kieran P; Goldsmith, C Franklin; Curran, Henry J

    2017-03-09

    Hydrogen atom abstraction from allylic C-H bonds by molecular oxygen plays a very important role in determining the reactivity of fuel molecules having allylic hydrogen atoms. Rate constants for hydrogen atom abstraction by molecular oxygen from molecules with allylic sites have been calculated. A series of molecules with primary, secondary, tertiary, and super secondary allylic hydrogen atoms of alkene, furan, and alkylbenzene families are taken into consideration. Those molecules include propene, 2-butene, isobutene, 2-methylfuran, and toluene containing the primary allylic hydrogen atom; 1-butene, 1-pentene, 2-ethylfuran, ethylbenzene, and n-propylbenzene containing the secondary allylic hydrogen atom; 3-methyl-1-butene, 2-isopropylfuran, and isopropylbenzene containing tertiary allylic hydrogen atom; and 1-4-pentadiene containing super allylic secondary hydrogen atoms. The M06-2X/6-311++G(d,p) level of theory was used to optimize the geometries of all of the reactants, transition states, products and also the hinder rotation treatments for lower frequency modes. The G4 level of theory was used to calculate the electronic single point energies for those species to determine the 0 K barriers to reaction. Conventional transition state theory with Eckart tunnelling corrections was used to calculate the rate constants. The comparison between our calculated rate constants with the available experimental results from the literature shows good agreement for the reactions of propene and isobutene with molecular oxygen. The rate constant for toluene with O2 is about an order magnitude slower than that experimentally derived from a comprehensive model proposed by Oehlschlaeger and coauthors. The results clearly indicate the need for a more detailed investigation of the combustion kinetics of toluene oxidation and its key pyrolysis and oxidation intermediates. Despite this, our computed barriers and rate constants retain an important internal consistency. Rate constants

  4. Site-Specific Hydrogen Isotope Composition of Propane: Mass spectrometric methods, equilibrium temperature dependence, and kinetics of exchange

    NASA Astrophysics Data System (ADS)

    Xie, H.; Ponton, C.; Kitchen, N.; Lloyd, M. K.; Lawson, M.; Formolo, M. J.; Eiler, J. M.

    2016-12-01

    Intramolecular isotope ordering can constrain temperatures of synthesis, mechanisms of formation, and/or source substrates of organic compounds. Here we explore site-specific hydrogen isotope variations of propane. Statistical thermodynamic models predict that at equilibrium methylene hydrogen (-CH2-) in propane will be 10's of per mil higher in D/H ratio than methyl hydrogen (-CH3) at geologically relevant temperatures, and that this difference is highly temperature dependent ( 0.5-1 ‰/°C). Chemical-kinetic controls on site-specific D/H in propane could constrain the mechanisms, conditions and extents of propane synthesis or destruction. We have developed a method for measuring the difference in D/H ratio between methylene and methyl hydrogen in propane by gas source mass spectrometry. The data were measured using the Thermo Fisher Double Focusing Sector high resolution mass spectrometer (DFS), and involve comparison of the D/H ratios of molecular ion (C3H8+) and the ethyl fragmental ion (C2H5+). We demonstrate the accuracy and precision of this method through analysis of D-labeled and independently analyzed propanes. In the exchange experiments, propane was heated (100-200 oC) either alone or in the presence of D-enriched water (δD=1,1419 ‰ SMOW), with or without one of several potentially catalytic substrates for hours to weeks. Propane was found to exchange hydrogen with water vigorously at 200 °C in the presence of metal catalysts. In the presence of Ni catalyst, methylene hydrogen exchanges 2.5 times faster than methyl hydrogen. Hydrogen exchange in the presence of Pd catalyst is more effective and can equilibrate hydrogen isotope distribution on propane on the order of 7 days. Isotopic exchange in the presence of natural materials have also been tested, but is only measurable in the methylene group at 200 °C. High catalytic activity of Pd permits attainment of a bracketed, time-invariant equilibrium state that we use to calibrate the site

  5. Kinetic and spectroscopic studies of the [palladium(Ar-bian)]-catalyzed semi-hydrogenation of 4-octyne.

    PubMed

    Kluwer, Alexander M; Koblenz, Tehila S; Jonischkeit, Thorsten; Woelk, Klaus; Elsevier, Cornelis J

    2005-11-09

    The kinetics of the stereoselective semi-hydrogenation of 4-octyne in THF by the highly active catalyst [Pd{(m,m'-(CF(3))(2)C(6)H(3))-bian}(ma)] (2) (bian = bis(imino)acenaphthene; ma = maleic anhydride) has been investigated. The rate law under hydrogen-rich conditions is described by r = k[4-octyne](0.65)[Pd][H(2)], showing first order in palladium and dihydrogen and a broken order in substrate. Parahydrogen studies have shown that a pairwise transfer of hydrogen atoms occurs in the rate-limiting step. In agreement with recent theoretical results, the proposed mechanism consists of the consecutive steps: alkyne coordination, heterolytic dihydrogen activation (hydrogenolysis of one Pd-N bond), subsequent hydro-palladation of the alkyne, followed by addition of N-H to palladium, reductive coupling of vinyl and hydride and, finally, substitution of the product alkene by the alkyne substrate. Under hydrogen-limiting conditions, side reactions occur, that is, formation of catalytically inactive palladacycles by oxidative alkyne coupling. Furthermore, it has been shown that (Z)-oct-4-ene is the primary reaction product, from which the minor product (E)-oct-4-ene is formed by an H(2)-assisted, palladium-catalyzed isomerization reaction.

  6. Influence of different types of effectors on the kinetic parameters of suicide inactivation of catalase by hydrogen peroxide.

    PubMed

    Ghadermarzi, M; Moosavi-Movahedi, A A

    1999-04-12

    The effects of cyanide and azide ions (class A), sodium-n-dodecyl sulphate (SDS) and 2-mercaptoethanol (class B), 3-aminotriazole (class C) and NADPH (class D) on the initial activity (ai), inactivation rate constant (ki) and the partition ratio (r) of bovine liver catalase reaction with its suicide substrate, hydrogen peroxide, were studied in 50 mM sodium phosphate buffer, pH 7.0 at 27 degrees C. The above kinetic parameters were determined by processing the progress curve data. In class A, which contains fast and reversible inhibitors of catalase, a proportional decrease in ai and ki was observed by inhibitors, so that the r remained constant. In class B, which contains slow and irreversible inactivators, a decrease in ai and constancy of ki and r were observed when catalase was incubated in the presence of such inactivators for a determined time. In class C, containing effector which can combine with intermediate compound I, ai was relatively unchanged but an increase in ki and a decrease in r were observed. In class D, containing effector which reduces compound I to ferricatalase, ai was not affected significantly but some decrease in ki was detected which was linked with an increase in r. These results demonstrate that different classes of effectors affect the determined kinetic parameters of catalase in various ways. Thus, determination of such parameters by simple kinetic experiments can be carried out for classification of the agents which have an effect on the kinetics of catalase.

  7. A Conserved Helical Capping Hydrogen Bond in PAS Domains Controls Signaling Kinetics in the Superfamily Prototype Photoactive Yellow Protein

    PubMed Central

    Kumauchi, Masato; Kaledhonkar, Sandip; Philip, Andrew F.; Wycoff, James; Hara, Miwa; Li, Yunxing; Xie, Aihua; Hoff, Wouter D.

    2010-01-01

    PAS domains form a divergent protein superfamily with more than 20,000 members that perform a wide array of sensing and regulatory functions in all three domains of life. Only 9 residues are well-conserved in PAS domains, with an Asn residue at the start of α-helix 3 showing the strongest conservation. The molecular functions of these 9 conserved residues are unknown. We use static and time-resolved visible and FTIR spectroscopy to investigate receptor activation in the photosensor photoactive yellow protein (PYP), a PAS domain prototype. The N43A and N43S mutants allow an investigation of the role of side chain hydrogen bonding at this conserved position. The mutants exhibit a blue-shifted visible absorbance maximum and up-shifted chromophore pKa. Disruption of the hydrogen bonds in N43A PYP causes both a reduction in protein stability and a 3,400-fold increase in the lifetime of the signaling state of this photoreceptor. A significant part of this increase in lifetime can be attributed to the helical capping interaction of Asn43. This extends the known importance of helical capping for protein structure to regulating functional protein kinetics. A model for PYP activation has been proposed in which side chain hydrogen bonding of Asn43 is critical for relaying light-induced conformational changes. However, FTIR spectroscopy shows that both Asn43 mutants retain full allosteric transmission of structural changes. Analysis of 30 available high resolution structures of PAS domains reveals that the side chain hydrogen bonding of residue 43 but not residue identity is highly conserved, and suggests that its helical cap affects signaling kinetics in other PAS domains. PMID:20954744

  8. First-principles-based kinetic Monte Carlo studies of diffusion of hydrogen in Ni–Al and Ni–Fe binary alloys

    DOE PAGES

    Tafen, De Nyago

    2015-02-14

    The diffusion of dilute hydrogen in fcc Ni–Al and Ni–Fe binary alloys was examined using kinetic Monte Carlo method with input kinetic parameters obtained from first-principles density functional theory. The simulation involves the implementation of computationally efficient energy barrier model that describes the configuration dependence of the hydrogen hopping. The predicted hydrogen diffusion coefficients in Ni and Ni89.4Fe10.6 are compared well with the available experimental data. In Ni–Al, the model predicts lower hydrogen diffusivity compared to that in Ni. Overall, diffusion prefactors and the effective activation energies of H in Ni–Fe and Ni–Al are concentration dependent of the alloying element.more » Furthermore, the changes in their values are the results of the short-range order (nearest-neighbor) effect on the interstitial diffusion of hydrogen in fcc Ni-based alloys.« less

  9. First-principles-based kinetic Monte Carlo studies of diffusion of hydrogen in Ni–Al and Ni–Fe binary alloys

    SciTech Connect

    Tafen, De Nyago

    2015-02-14

    The diffusion of dilute hydrogen in fcc Ni–Al and Ni–Fe binary alloys was examined using kinetic Monte Carlo method with input kinetic parameters obtained from first-principles density functional theory. The simulation involves the implementation of computationally efficient energy barrier model that describes the configuration dependence of the hydrogen hopping. The predicted hydrogen diffusion coefficients in Ni and Ni89.4Fe10.6 are compared well with the available experimental data. In Ni–Al, the model predicts lower hydrogen diffusivity compared to that in Ni. Overall, diffusion prefactors and the effective activation energies of H in Ni–Fe and Ni–Al are concentration dependent of the alloying element. Furthermore, the changes in their values are the results of the short-range order (nearest-neighbor) effect on the interstitial diffusion of hydrogen in fcc Ni-based alloys.

  10. Ultrasonic irradiation as a tool to modify the H-desorption from hydrides: MgH(2) suspended in decane.

    PubMed

    Ares, J R; Leardini, F; Díaz-Chao, P; Bodega, J; Fernández, J F; Ferrer, I J; Sánchez, C

    2009-08-01

    Effects of ultrasonic irradiation on magnesium hydride (MgH(2)) suspended in decane were investigated with the purpose of improving its hydrogen desorption process. Firstly, we have found that the presence of MgH(2) improves the sonolysis of decane enhancing the amount of hydrogen evolved during the sonication process. The sonicated-MgH(2) maintains its microstructural properties practically unaltered but a drastic reduction of the particle size of MgH(2) (down to approximately 20mum) as well as a high pressure MgH(2) phase are observed. However, no substantial modifications of H-kinetic properties of hydride occur as is determined by thermal desorption measurements. This could be attributed to decomposition of decane during sonication which leads to the formation of carbon compounds that hinder the thermal decomposition of MgH(2).

  11. Estimation of kinetic parameters related to biochemical interactions between hydrogen peroxide and signal transduction proteins

    PubMed Central

    Brito, Paula M.; Antunes, Fernando

    2014-01-01

    The lack of kinetic data concerning the biological effects of reactive oxygen species is slowing down the development of the field of redox signaling. Herein, we deduced and applied equations to estimate kinetic parameters from typical redox signaling experiments. H2O2-sensing mediated by the oxidation of a protein target and the switch-off of this sensor, by being converted back to its reduced form, are the two processes for which kinetic parameters are determined. The experimental data required to apply the equations deduced is the fraction of the H2O2 sensor protein in the reduced or in the oxidized state measured in intact cells or living tissues after exposure to either endogenous or added H2O2. Either non-linear fittings that do not need transformation of the experimental data or linearized plots in which deviations from the equations are easily observed can be used. The equations were shown to be valid by fitting to them virtual time courses simulated with a kinetic model. The good agreement between the kinetic parameters estimated in these fittings and those used to simulate the virtual time courses supported the accuracy of the kinetic equations deduced. Finally, equations were successfully tested with real data taken from published experiments that describe redox signaling mediated by the oxidation of two protein tyrosine phosphatases, PTP1B and SHP-2, which are two of the few H2O2-sensing proteins with known kinetic parameters. Whereas for PTP1B estimated kinetic parameters fitted in general the present knowledge, for SHP-2 results obtained suggest that reactivity toward H2O2 as well as the rate of SHP-2 regeneration back to its reduced form are higher than previously thought. In conclusion, valuable quantitative kinetic data can be estimated from typical redox signaling experiments, thus improving our understanding about the complex processes that underlie the interplay between oxidative stress and redox signaling responses. PMID:25325054

  12. Estimation of kinetic parameters related to biochemical interactions between hydrogen peroxide and signal transduction proteins

    NASA Astrophysics Data System (ADS)

    Brito, Paula; Antunes, Fernando

    2014-10-01

    The lack of kinetic data concerning the biological effects of reactive oxygen species is slowing down the development of the field of redox signaling. Herein, we deduced and applied equations to estimate kinetic parameters from typical redox signaling experiments. H2O2-sensing mediated by the oxidation of a protein target and the switch-off of this sensor, by being converted back to its reduced form, are the two processes for which kinetic parameters are determined. The experimental data required to apply the equations deduced is the fraction of the H2O2 sensor protein in the reduced or in the oxidized state measured in intact cells or living tissues after exposure to either endogenous or added H2O2. Either non-linear fittings that do not need transformation of the experimental data or linearized plots in which deviations from the equations are easily observed can be used. The equations were shown to be valid by fitting to them virtual time courses simulated with a kinetic model. The good agreement between the kinetic parameters estimated in these fittings and those used to simulate the virtual time courses supported the accuracy of the kinetic equations deduced. Finally, equations were successfully tested with real data taken from published experiments that describe redox signaling mediated by the oxidation of two protein tyrosine phosphatases, PTP1B and SHP-2, which are two of the few H2O2-sensing proteins with known kinetic parameters. Whereas for PTP1B estimated kinetic parameters fitted in general the present knowledge, for SHP-2 results obtained suggest that reactivity towards H2O2 as well as the rate of SHP-2 regeneration back to its reduced form are higher than previously thought. In conclusion, valuable quantitative kinetic data can be estimated from typical redox signaling experiments, thus improving our understanding about the complex processes that underline the interplay between oxidative stress and redox signaling responses.

  13. Application of electron stimulated desorption techniques to measure the isotherm and the mean residence time of hydrogen physisorbed on a metal surface

    SciTech Connect

    Arakawa, Ichiro Shimizu, Hideyuki; Kawarabuki, Taku; Yamakawa, Koichiro; Miura, Takashi

    2015-03-15

    Electron stimulated desorption techniques were applied to probe the density of H{sub 2} physisorbed on a cold surface. The adsorption isotherm of H{sub 2} on a copper surface was measured in the equilibrium pressure range between 10{sup −9} and 10{sup −4} Pa at surface temperatures of 6.5 and 4.2 K. The mean residence times of H{sub 2} on copper were obtained from the observation of the time development of the surface density in a transitional state approaching equilibrium, and are 50–500 s for the coverage between 1 and 0.18 at 4.2 K of the substrate temperature. The adsorption energies of 1.18–1.27 kJ/mol, and the condensation coefficient of 0.074–0.018 were also deduced.

  14. Reduced and Validated Kinetic Mechanisms for Hydrogen-CO-sir Combustion in Gas Turbines

    SciTech Connect

    Yiguang Ju; Frederick Dryer

    2009-02-07

    Rigorous experimental, theoretical, and numerical investigation of various issues relevant to the development of reduced, validated kinetic mechanisms for synthetic gas combustion in gas turbines was carried out - including the construction of new radiation models for combusting flows, improvement of flame speed measurement techniques, measurements and chemical kinetic analysis of H{sub 2}/CO/CO{sub 2}/O{sub 2}/diluent mixtures, revision of the H{sub 2}/O{sub 2} kinetic model to improve flame speed prediction capabilities, and development of a multi-time scale algorithm to improve computational efficiency in reacting flow simulations.

  15. Features of the kinetics of 4-nitroaniline and azoxybenzene hydrogenation in 2-propanol aqueous solutions

    NASA Astrophysics Data System (ADS)

    Kha, Nguen Tkhi Tkhu; Lefedova, O. V.; Merkin, A. A.

    2013-04-01

    It is shown experimentally that the hydrogenation of 4-nitroaniline and azoxybenzene over a skeletal nickel catalyst in 2-propanol aqueous solutions proceeds selectively with the formation of the corresponding amines without the accumulation of side products in the bulk phase. It is concluded that during reduction, considerable participation of hydrogen bonded with active centers of a catalyst surface was observed. The competitive character of adsorption between the initial azoxybenzene and aniline formed as a result of reaction is established. It is ascertained that the character of changes in the rates of hydrogenation of nitro and azoxy groups is identical in the presence of additions of acid or base. It is demonstrated that a targeted change in the hydrogenation rates of these compounds is possible by introducing additions of acetic acid or sodium hydroxide into 2-propanol aqueous solution.

  16. PAH desorption from river floodplain soils using supercritical fluid extraction.

    PubMed

    Yang, Yi; Cajthaml, Tomás; Hofmann, Thilo

    2008-12-01

    Sequential supercritical fluid extraction (SFE) was performed in order to estimate desorption of PAHs from river floodplain soils which contain coal and coal-derived particles. Original soils, soils' light fractions (rho<2 g cm(-3)), and <63 microm fractions were studied for PAHs' desorption kinetics. Desorption data were successfully described using a two-site model. Desorption rate constants were one order of magnitude lower than those of "slow" and "very slow" desorption rates from other studies. This suggests very slow and extremely slow desorption. Estimated time scales releasing 99% of total extractable contaminants ranged from decades for 2-4-ring PAHs and hundreds of years for 5-6-ring PAHs. We demonstrate that, despite high soil PAH concentrations which are due to coal and coal-derived particles, the general environmental risk is reduced by the very slow and extremely slow desorption rates.

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

    NASA Astrophysics Data System (ADS)

    Ganesh, Karthik

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

  18. Systematic evaluation of nitrate and perchlorate bioreduction kinetics in groundwater using a hydrogen-based membrane biofilm reactor.

    PubMed

    Ziv-El, Michal C; Rittmann, Bruce E

    2009-01-01

    To evaluate the simultaneous reduction kinetics of the oxidized compounds, we treated nitrate-contaminated groundwater (approximately 9.4 mg-N/L) containing low concentrations of perchlorate (approximately 12.5 microg/L) and saturated with dissolved oxygen (approximately 8 mg/L) in a hydrogen-based membrane biofilm reactor (MBfR). We systematically increased the hydrogen availability and simultaneously varied the surface loading of the oxidized compounds on the biofilm in order to provide a comprehensive, quantitative data set with which to evaluate the relationship between electron donor (H(2)) availability, surface loading of the electron acceptors (oxidized compounds), and simultaneous bioreduction of the electron acceptors. Increasing the H(2) pressure delivered more H(2) gas, and the total H(2) flux increased linearly from approximately 0.04 mg/cm(2)-d for 0.5 psig (0.034 atm) to 0.13 mg/cm(2)-d for 9.5 psig (0.65 atm). This increased rate of H(2) delivery allowed for continued reduction of the acceptors as their surface loading increased. The electron acceptors had a clear hydrogen-utilization order when the availability of hydrogen was limited: oxygen, nitrate, nitrite, and then perchlorate. Spiking the influent with perchlorate or nitrate allowed us to identify the maximum surface loadings that still achieved more than 99.5% reduction of both oxidized contaminants: 0.21 mg NO(3)-N/cm(2)-d and 3.4 microg ClO(4)/cm(2)-d. Both maximum values appear to be controlled by factors other than hydrogen availability.

  19. Probing hydrogen peroxide oxidation kinetics of wild-type Synechocystis catalase-peroxidase (KatG) and selected variants.

    PubMed

    Vlasits, Jutta; Furtmüller, Paul G; Jakopitsch, Christa; Zamocky, Marcel; Obinger, Christian

    2010-04-01

    Catalase-peroxidases (KatGs) are unique bifunctional heme peroxidases that exhibit peroxidase and substantial catalase activities. Nevertheless, the reaction pathway of hydrogen peroxide dismutation, including the electronic structure of the redox intermediate that actually oxidizes H(2)O(2), is not clearly defined. Several mutant proteins with diminished overall catalase but wild-type-like peroxidase activity have been described in the last years. However, understanding of decrease in overall catalatic activity needs discrimination between reduction and oxidation reactions of hydrogen peroxide. Here, by using sequential-mixing stopped-flow spectroscopy, we have investigated the kinetics of the transition of KatG compound I (produced by peroxoacetic acid) to its ferric state by trapping the latter as cyanide complex. Apparent bimolecular rate constants (pH 6.5, 20 degrees C) for wild-type KatG and the variants Trp122Phe (lacks KatG-typical distal adduct), Asp152Ser (controls substrate access to the heme cavity) and Glu253Gln (channel entrance) are reported to be 1.2x10(4)M(-1)s(-1), 30M(-1)s(-1), 3.4x10(3)M(-1)s(-1), and 8.6x10(3)M(-1)s(-1), respectively. These findings are discussed with respect to steady-state kinetic data and proposed reaction mechanism(s) for KatG. Assets and drawbacks of the presented method are discussed. Copyright 2009 Elsevier B.V. All rights reserved.

  20. Access of hydrogen-radicals to the peptide-backbone as a measure for estimating the flexibility of proteins using matrix-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Takayama, Mitsuo; Nagoshi, Keishiro; Iimuro, Ryunosuke; Inatomi, Kazuma

    2014-05-13

    A factor for estimating the flexibility of proteins is described that uses a cleavage method of "in-source decay (ISD)" coupled with matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS). The MALDI-ISD spectra of bovine serum albumin (BSA), myoglobin and thioredoxin show discontinuous intense ion peaks originating from one-side preferential cleavage at the N-Cα bond of Xxx-Asp, Xxx-Asn, Xxx-Cys and Gly-Xxx residues. Consistent with these observations, Asp, Asn and Gly residues are also identified by other flexibility measures such as B-factor, turn preference, protection and fluorescence decay factors, while Asp, Asn, Cys and Gly residues are identified by turn preference factor based on X-ray crystallography. The results suggest that protein molecules embedded in/on MALDI matrix crystals partly maintain α-helix and that the reason some of the residues are more susceptible to ISD (Asp, Asn, Cys and Gly) and others less so (Ile and Val) is because of accessibility of the peptide backbone to hydrogen-radicals from matrix molecules. The hydrogen-radical accessibility in MALDI-ISD could therefore be adopted as a factor for measuring protein flexibility.

  1. Access of Hydrogen-Radicals to the Peptide-Backbone as a Measure for Estimating the Flexibility of Proteins Using Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

    PubMed Central

    Takayama, Mitsuo; Nagoshi, Keishiro; Iimuro, Ryunosuke; Inatomi, Kazuma

    2014-01-01

    A factor for estimating the flexibility of proteins is described that uses a cleavage method of “in-source decay (ISD)” coupled with matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS). The MALDI-ISD spectra of bovine serum albumin (BSA), myoglobin and thioredoxin show discontinuous intense ion peaks originating from one-side preferential cleavage at the N-Cα bond of Xxx-Asp, Xxx-Asn, Xxx-Cys and Gly-Xxx residues. Consistent with these observations, Asp, Asn and Gly residues are also identified by other flexibility measures such as B-factor, turn preference, protection and fluorescence decay factors, while Asp, Asn, Cys and Gly residues are identified by turn preference factor based on X-ray crystallography. The results suggest that protein molecules embedded in/on MALDI matrix crystals partly maintain α-helix and that the reason some of the residues are more susceptible to ISD (Asp, Asn, Cys and Gly) and others less so (Ile and Val) is because of accessibility of the peptide backbone to hydrogen-radicals from matrix molecules. The hydrogen-radical accessibility in MALDI-ISD could therefore be adopted as a factor for measuring protein flexibility. PMID:24828203

  2. In-situ catalyzation approach for enhancing the hydrogenation/dehydrogenation kinetics of MgH2 powders with Ni particles

    NASA Astrophysics Data System (ADS)

    El-Eskandarany, M. Sherif; Shaban, Ehab; Ali, Naser; Aldakheel, Fahad; Alkandary, Abdullah

    2016-11-01

    One practical solution for utilizing hydrogen in vehicles with proton-exchange fuel cells membranes is storing hydrogen in metal hydrides nanocrystalline powders. According to its high hydrogen capacity and low cost of production, magnesium hydride (MgH2) is a desired hydrogen storage system. Its slow hydrogenation/dehydrogenation kinetics and high thermal stability are the major barriers restricting its usage in real applications. Amongst the several methods used for enhancing the kinetics behaviors of MgH2 powders, mechanically milling the powders with one or more catalyst species has shown obvious advantages. Here we are proposing a new approach for gradual doping MgH2 powders with Ni particles upon ball milling the powders with Ni-balls milling media. This proposed is-situ method showed mutually beneficial for overcoming the agglomeration of catalysts and the formation of undesired Mg2NiH4 phase. Moreover, the decomposition temperature and the corresponding activation energy showed low values of 218 °C and 75 kJ/mol, respectively. The hydrogenation/dehydrogenation kinetics examined at 275 °C of the powders milled for 25 h took place within 2.5 min and 8 min, respectively. These powders containing 5.5 wt.% Ni performed 100-continuous cycle-life time of hydrogen charging/discharging at 275 °C within 56 h without failure or degradation.

  3. In-situ catalyzation approach for enhancing the hydrogenation/dehydrogenation kinetics of MgH2 powders with Ni particles.

    PubMed

    El-Eskandarany, M Sherif; Shaban, Ehab; Ali, Naser; Aldakheel, Fahad; Alkandary, Abdullah

    2016-11-16

    One practical solution for utilizing hydrogen in vehicles with proton-exchange fuel cells membranes is storing hydrogen in metal hydrides nanocrystalline powders. According to its high hydrogen capacity and low cost of production, magnesium hydride (MgH2) is a desired hydrogen storage system. Its slow hydrogenation/dehydrogenation kinetics and high thermal stability are the major barriers restricting its usage in real applications. Amongst the several methods used for enhancing the kinetics behaviors of MgH2 powders, mechanically milling the powders with one or more catalyst species has shown obvious advantages. Here we are proposing a new approach for gradual doping MgH2 powders with Ni particles upon ball milling the powders with Ni-balls milling media. This proposed is-situ method showed mutually beneficial for overcoming the agglomeration of catalysts and the formation of undesired Mg2NiH4 phase. Moreover, the decomposition temperature and the corresponding activation energy showed low values of 218 °C and 75 kJ/mol, respectively. The hydrogenation/dehydrogenation kinetics examined at 275 °C of the powders milled for 25 h took place within 2.5 min and 8 min, respectively. These powders containing 5.5 wt.% Ni performed 100-continuous cycle-life time of hydrogen charging/discharging at 275 °C within 56 h without failure or degradation.

  4. In-situ catalyzation approach for enhancing the hydrogenation/dehydrogenation kinetics of MgH2 powders with Ni particles

    PubMed Central

    El-Eskandarany, M. Sherif; Shaban, Ehab; Ali, Naser; Aldakheel, Fahad; Alkandary, Abdullah

    2016-01-01

    One practical solution for utilizing hydrogen in vehicles with proton-exchange fuel cells membranes is storing hydrogen in metal hydrides nanocrystalline powders. According to its high hydrogen capacity and low cost of production, magnesium hydride (MgH2) is a desired hydrogen storage system. Its slow hydrogenation/dehydrogenation kinetics and high thermal stability are the major barriers restricting its usage in real applications. Amongst the several methods used for enhancing the kinetics behaviors of MgH2 powders, mechanically milling the powders with one or more catalyst species has shown obvious advantages. Here we are proposing a new approach for gradual doping MgH2 powders with Ni particles upon ball milling the powders with Ni-balls milling media. This proposed is-situ method showed mutually beneficial for overcoming the agglomeration of catalysts and the formation of undesired Mg2NiH4 phase. Moreover, the decomposition temperature and the corresponding activation energy showed low values of 218 °C and 75 kJ/mol, respectively. The hydrogenation/dehydrogenation kinetics examined at 275 °C of the powders milled for 25 h took place within 2.5 min and 8 min, respectively. These powders containing 5.5 wt.% Ni performed 100-continuous cycle-life time of hydrogen charging/discharging at 275 °C within 56 h without failure or degradation. PMID:27849033

  5. TiO(OH)2 - highly effective catalysts for optimizing CO2 desorption kinetics reducing CO2 capture cost: A new pathway.

    PubMed

    Yao, Hongbao; Toan, Sam; Huang, Liang; Fan, Maohong; Wang, Yujun; Russell, Armistead G; Luo, Guangsheng; Fei, Weiyang

    2017-06-07

    The objective is to find a new pathway for significant reduction in CO2 capture energy consumption. Specifically, nanoporous TiO(OH)2 was used to realize the objective, which was desired as a catalyst to significantly accelerate the decomposition of aqueous NaHCO3, essentially CO2 desorption - the key step of Na2CO3/NaHCO3 based CO2 capture technologies from overall CO2 energy consumption perspective. Effects of several important factors on TiO(OH)2-catalyzed NaHCO3 decomposition were investigated. The quantity of CO2 generated from 0.238 mol/L NaHCO3 at 65 °C with catalyst is ~800% of that generated without the presence of catalyst. When a 12 W vacuum pump was used for carrying the generated CO2 out of reactor, the total amount of CO2 released was improved by ~2,500% under the given experimental conditions. No significant decrease in the catalytic effect of TiO(OH)2 was observed after five cyclic CO2 activated tests. In addition, characterizations with in-situ Fourier transform infrared spectroscopy, thermal gravity analysis and Brunauer-Emmett-Teller of TiO(OH)2 indicate that TiO(OH)2 is quite stable. The discovery in this research could inspire scientists' interests in starting to focus on a new pathway instead of making huge effort or investment in designing high-capacity but expensive CO2 sorbent for developing practical or cost-effective CO2 technologies.

  6. Tuning the Hydrogen Storage in Magnesium Alloys

    NASA Astrophysics Data System (ADS)

    Er, Suleyman; de Wijs, Gilles A.; Brocks, Geert

    2011-03-01

    We investigate the hydrogen storage properties of promising magnesium alloys. Mg H2 (7.6 wt % H) would be a very useful storage material if the (de)hydrogenation kinetics can be improved and the desorption temperature is markedly lowered. Using first principles calculations, we show that hydrides of Mg-transition metal (TM) alloys adopt a structure that promotes faster (de)hydrogenation kinetics, as is also observed in experiment. Within the lightweight TMs, the most promising alloying element is titanium. Alloying Mg with Ti alone, however, is not sufficient to decrease the stability of the hydride phases, which is necessary to reduce the hydrogen desorption temperature. We find that adding aluminium or silicon markedly destabilizes Mg-Ti hydrides and stabilizes Mg-Ti alloys. Finally, we show that controlling the structure of Mg-Ti-Al(Si) system by growing it as multilayers, has a beneficial influence on the thermodynamic properties and makes it a stronger candidate for hydrogen storage.

  7. Enhanced Kinetics of Electrochemical Hydrogen Uptake and Release by Palladium Powders Modified by Electrochemical Atomic Layer Deposition

    DOE PAGES

    Benson, David M.; Tsang, Chu F.; Sugar, Joshua Daniel; ...

    2017-04-28

    One method for the formation of nanofilms of materials, is Electrochemical atomic layer deposition (E-ALD), one atomic layer at a time. It uses the galvanic exchange of a less noble metal, deposited using underpotential deposition (UPD), to produce an atomic layer of a more noble element by reduction of its ions. This process is referred to as surface limited redox replacement and can be repeated in a cycle to grow thicker deposits. Previously, we performed it on nanoparticles and planar substrates. In the present report, E-ALD is applied for coating a submicron-sized powder substrate, making use of a new flowmore » cell design. E-ALD is used to coat a Pd powder substrate with different thicknesses of Rh by exchanging it for Cu UPD. Furthermore, cyclic voltammetry and X-ray photoelectron spectroscopy indicate an increasing Rh coverage with increasing numbers of deposition cycles performed, in a manner consistent with the atomic layer deposition (ALD) mechanism. Cyclic voltammetry also indicated increased kinetics of H sorption and desorption in and out of the Pd powder with Rh present, relative to unmodified Pd.« less

  8. Electrical and mechanical controlling of the kinetic and magnetic properties of hydrogen atoms on free-standing silicene

    NASA Astrophysics Data System (ADS)

    Podsiadły-Paszkowska, Agata; Krawiec, Mariusz

    2016-07-01

    Effects of strain, charge doping and external electric field on kinetic and magnetic properties of hydrogen atoms on a free-standing silicene layer are investigated by first-principles density functional theory. It was found that the charge doping and strain are the most effective ways of changing the hydrogen-silicene binding energy, but they can only raise its value. The perpendicular external electric field can also lower it albeit in a narrower range. The strain has also the strongest impact on diffusion processes, and the diffusion barrier can be modified up to 50% of its unstrained value. The adsorption of hydrogen atoms results in a locally antiferromagnetic ground state with the effective exchange constant of approximately 1 eV. The system can easily be driven into a nonmagnetic phase by the charge doping and strain. The obtained results are very promising in view of the silicene functionalization and potential applications of silicene in fields of modern nanoelectronics and spintronics.

  9. A mathematical model for the kinetics of Methanobacterium bryantii M.o.H. considering hydrogen thresholds.

    PubMed

    Karadagli, Fatih; Rittmann, Bruce E

    2007-08-01

    We develop a kinetic model that builds on the foundation of classic Monod kinetics, but incorporates new phenomena such as substrate thresholds and survival mode observed in experiments with the H2-oxidizing methanogen Methanobacterium bryantii M.o.H. We apply our model to the experimental data presented in our companion paper on H2 thresholds. The model accurately describes H2 consumption, CH4 generation, biomass growth, substrate thresholds, and survival state during batch experiments. Methane formation stops when its Gibbs free energy is equal zero, although this does not interrupt H2 oxidation. The thermodynamic threshold for H2 oxidation occurs when the free energy for oxidizing H2 and transferring electrons to biomass is no longer negative, at approximately 0.4 nM. This threshold is not controlled by the Gibbs free energy equation of methanogenesis from H2 + HCO3- as we show in our companion paper. Beyond this threshold, the microorganisms shift to a low-maintenance metabolism called "the survival state" in response to extended H2 starvation; adding the starvation response as another new feature of the kinetic model. A kinetic threshold (or S (min)), a natural feature of the Monod kinetics, is also captured by the model at H2 concentration of around approximately 2,400 nM. S (min) is the minimum substrate concentration to maintain steady-state biomass concentration. Our model will be useful for interpreting threshold results and designing new studies to understand thresholds and their ecological implications.

  10. Thermal decomposition pathway and desorption study of isopropanol and tert-butanol on Si(100)

    NASA Astrophysics Data System (ADS)

    Kim, Jaehyun; Kim, Kwansoo; Yong, Kijung

    2002-09-01

    Thermal decomposition pathway and desorption of isopropanol (IPA) and tert-butanol on Si(100) were studied using temperature programed desorption. Adsorbed alcohols studied were decomposed into atomic hydrogen and alkoxy on the surface. During heating the sample up to 1000 K, acetone, propylene, and hydrogen were desorbed as decomposition products of IPA on Si(100). Desorption pathways of IPA on Si(100) were largely consistent with those on metal surfaces: beta-hydride elimination reaction to acetone and C-O scission to propylene. For tert-butanol, which has no beta-hydrogen, isobutene and hydrogen were observed as main desorption products. copyright 2002 American Vacuum Society.

  11. Destabilization of Mg-H bonding through nano-interfacial confinement by unsaturated carbon for hydrogen desorption from MgH2.

    PubMed

    Jia, Yi; Sun, Chenghua; Cheng, Lina; Abdul Wahab, Md; Cui, Jie; Zou, Jin; Zhu, Min; Yao, Xiangdong

    2013-04-28

    We propose a new mechanism for destabilizing Mg-H bonding by means of a combination of the size effect and MgH2-carbon scaffold interfacial bonding, and experimentally realize low temperature hydrogen release starting from 50 °C using an MgH2@CMK-3 nanoconfinement system (37.5 wt% MgH2 loading amount). Based on computational calculations, it is found that the charge transfer from MgH2 to the carbon scaffold plays a critical role in the significant reduction of thermodynamics of MgH2 dehydrogenation. Our results suggest how to explore an alternative route for the enhancement of nano-interfacial confinement to destabilize the Mg-H hydrogen storage system.

  12. Nucleation kinetics, crystal growth and optical studies on lithium hydrogen oxalate monohydrate single crystal

    NASA Astrophysics Data System (ADS)

    Chandran, Senthilkumar; Paulraj, Rajesh; Ramasamy, P.

    2017-06-01

    Semi-organic lithium hydrogen oxalate monohydrate non-linear optical single crystals have been grown by slow evaporation solution technique at 40 °C. The nucleation parameters such as critical radius, interfacial tension, and critical free energy change have been evaluated using the experimental data. The solubility and the nucleation curve of the crystal at different temperatures have been analyzed. The crystal has a positive temperature coefficient of solubility. The metastable zone width and induction period have been determined for the aqueous solution growth of lithium hydrogen oxalate monohydrate. The UV-vis-NIR spectrum showed this crystal has high transparency. The photoconductivity studies indicate lithium hydrogen oxalate monohydrate has positive photoconductivity behaviour. The low etch pit density observed on (0 0 1) crystal surface and the high resolution x-ray difraction analysis indicate the good quality of the grown crystals

  13. Role of nano in catalysis: Pd catalyzed H desorption from MgH2

    NASA Astrophysics Data System (ADS)

    Xie, Weiyu; West, Damien; Sun, Yiyang; Zhang, Shengbai

    2012-02-01

    Magnesium hydride (MgH2) is promising for on-board hydrogen (H) storage with the major hurdle being the slow desorption kinetics. H desorption from ball-milled MgH2 peaks at two slightly different temperatures, which further split in the presence of palladium catalyst. It has been experimentally demonstrated that nanostructuring can eliminate the high temperature peak. However, the effect of nanostructuring cannot be explained by thermodynamic destabilization due to quantum size effect. Our first-principles calculation reveals that there exist two reaction pathways for H desorption from MgH2. One involves H vacancy (SV) diffusion at surface, while the other one involves H atom diffusion in bulk. The SV pathway self-terminates as dehydrogenation eventually eliminates the exposed MgH2 region. Therefore, it is size-sensitive and fully functions only when the surface-to-bulk ratio is large, which is available only in nanostructures. Our calculation further shows that the SV pathway significantly lowers the desorption barrier, because it decouples the H transport process with the surface liftoff process and benefits from a fact that diffusion of vacancies at surface can have significantly lower barrier than that in bulk.

  14. Microstructure and tailoring hydrogenation performance of Y-doped Mg2Ni alloys

    NASA Astrophysics Data System (ADS)

    Song, Wenjie; Li, Jinshan; Zhang, Tiebang; Kou, Hongchao; Xue, Xiangyi

    2014-01-01

    In this work, the microstructure and the hydrogenation properties of melt-spun Mg67Ni33-xYx alloys are studied with the purpose to investigate the influence of Y doping and rapid solidification on hydrogenation performance of Mg2Ni. Mg67Ni33-xYx (x = 0, 1, 3, 6) alloys are firstly prepared in an electric resistance furnace under the protection of a covering reagent. Then, the as-cast alloys are re-melted and spun on a rotating copper roller. The phase compositions and microstructures of as-cast and melt-spun alloys are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) with an energy dispersive spectrometer (EDS). The hydrogen activation properties and absorption/desorption kinetics of melt-spun Mg67Ni33-xYx (x = 0, 1, 3, 6) ribbons are evaluated using an automatic Sieverts apparatus. The melt-spun Mg67Ni32Y alloy preserves high hydrogen absorption capacity and kinetics and absorbs 96% of the maximum capacity (3.79 wt. %) within 8 min. The lattice distortion caused by Y doping and the shrinkage porosity by melt-spun not only raise the hydrogen absorption/desorption rate, but significantly improve the hydrogen storage capacity of Mg67Ni33-xYx (x = 0, 1, 3, 6) alloys. The activation and hydrogen absorption/desorption mechanisms are also discussed based on a nucleation and growth theory.

  15. An exceptional kinetic quantum sieving separation effect of hydrogen isotopes on commercially available carbon molecular sieves.

    PubMed

    Xing, Yanlong; Cai, Jinjun; Li, Liangjun; Yang, Menglong; Zhao, Xuebo

    2014-08-14

    The quantum sieving effect of H2/D2 at 77 K on commercially available carbon molecular sieves (1.5GN-H and 3KT-172) was studied. An exceptional reverse kinetic quantum effect is observed on 1.5GN-H where D2 diffuses much faster than H2 with a ratio of up to 5.83 at low pressure, and the difference is still very evident even as the pressure increases up to 1 bar. D2 also diffuses faster than H2 on 3KT-172 with a ratio of up to 1.86. However, the reverse kinetic sieving disappears in a polymer-based carbon (PC). The present kinetic quantum sieving effect of H2 and D2 at 77 K on 1.5GN-H is the highest to date.

  16. Kinetics of the Oxidation of Hydrazine by Hydrogen Peroxide, Catalyzed by Copper (II)

    DTIC Science & Technology

    1975-08-01

    the reaction involves copper ion and hydrogen peroxide. Since copp~er(II) has been shawn to react slowly with hydrogen peroxide,5’,10 the miore...NUMBER 7. AUTHOR(s) 0 CONTRACT OR GRANT NUMBER(a) Carl R. Wellman J. Richard Ward !.ester P. Kuhn 9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM...NAME AND ADDRESS 12. REPORT DATE U.S. Army Materiel Command AUGUST 1975) 5001 Eisenhower Av’enue .NUEROPAS AlexandriaV ; 2 IC. MONITORING ASANC NAME

  17. FUNDAMENTAL KINETICS OF SUPERCRITICAL COAL LIQUEFACTION: EFFECT OF CATALYSTS AND HYDROGEN-DONOR SOLVENTS

    SciTech Connect

    Benjamin J. McCoy; J.M. Smith

    1998-08-01

    This report outlines a distribution kinetics approach to macromolecular reactions that has been applied to several processes. The objective was to develop an understanding of high-temperature, dense-phase thermolytic processes for complex macromolecular systems, such as coal. Experiments and theory are described for chemical models that simulate depolymerization of coal. The approach has been exceptionally successful for the model macromolecular systems. Development of a novel chemical reaction engineering analysis, based on distribution kinetics, was a major accomplishment of the current research.

  18. Dynamic kinetic resolution in the stereoselective synthesis of 4,5-diaryl cyclic sulfamidates by using chiral rhodium-catalyzed asymmetric transfer hydrogenation.

    PubMed

    Han, Juae; Kang, Soyeong; Lee, Hyeon-Kyu

    2011-04-07

    The dynamic kinetic resolution of 4,5-diaryl cyclic sulfamidate imines was achieved via asymmetric transfer hydrogenation using a HCO(2)H/Et(3)N mixture as the hydrogen source and chiral Rh catalysts (R,R)- or (S,S)-RhCl(TsDPEN)Cp* affording the corresponding cyclic sulfamidates in good yields with up to >20 : 1 dr and up to >99% ee.

  19. Stereoselective Synthesis of 4-Substituted Cyclic Sulfamidate-5-Phosphonates by Using Rh-Catalyzed, Asymmetric Transfer Hydrogenation with Accompanying Dynamic Kinetic Resolution.

    PubMed

    Seo, Yeon Ji; Kim, Jin-ah; Lee, Hyeon-Kyu

    2015-09-04

    Dynamic kinetic resolution driven, asymmetric transfer hydrogenation of 4-substituted cyclic sulfamidate imine-5-phosphonates produces the corresponding cyclic sulfamidate-5-phosphonates. The process employs a HCO2H/Et3N mixture as the hydrogen source and the chiral Rh catalysts, (R,R)- or (S,S)-Cp*RhCl(TsDPEN), and it takes place at room temperature within 1 h with high yields and high levels of stereoselectivity.

  20. New analytical potential energy surface for the F(2P)+CH4 hydrogen abstraction reaction: kinetics and dynamics.

    PubMed

    Espinosa-García, J; Bravo, J L; Rangel, C

    2007-04-12

    A new potential energy surface for the gas-phase F(2P)+CH4 reaction and its deuterated analogues is reported, and its kinetics and dynamics are studied exhaustively. This semiempirical surface is completely symmetric with respect to the permutation of the four methane hydrogen atoms, and it is calibrated to reproduce the topology of the reaction and the experimental thermal rate constants. For the kinetics, the thermal rate constants were calculated using variational transition-state theory with semiclassical transmission coefficients over a wide temperature range, 180-500 K. The theoretical results reproduce the experimental variation with temperature. The influence of the tunneling factor is negligible, due to the flattening of the surface in the entrance valley, and we found a direct dependence on temperature, and therefore positive and small activation energies, in agreement with experiment. Two sets of kinetic isotope effects were calculated, and they show good agreement with the sparse experimental data. The coupling between the reaction coordinate and the vibrational modes shows qualitatively that the FH stretching and the CH3 umbrella bending modes in the products appear vibrationally excited. The dynamics study was performed using quasi-classical trajectory calculations, including corrections to avoid zero-point energy leakage along the trajectories. First, we found that the FH(nu',j') rovibrational distributions agree with experiment. Second, the excitation function presents an oscillatory pattern, reminiscent of a reactive resonance. Third, the state specific scattering distributions present reasonable agreement with experiment, and as the FH(nu') vibrational state increases the scattering angle becomes more forward. These kinetics and dynamics results seem to indicate that a single, adiabatic potential energy surface is adequate to describe this reaction, and the reasonable agreement with experiment (always qualitative and sometimes quantitative) lends

  1. An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures

    DOE PAGES

    Keromnes, Alan; Metcalfe, Wayne K.; Heufer, Karl A.; ...

    2013-03-12

    The oxidation of syngas mixtures was investigated experimentally and simulated with an updated chemical kinetic model. Ignition delay times for H2/CO/O2/N2/Ar mixtures have been measured using two rapid compression machines and shock tubes at pressures from 1 to 70 bar, over a temperature range of 914–2220 K and at equivalence ratios from 0.1 to 4.0. Results show a strong dependence of ignition times on temperature and pressure at the end of the compression; ignition delays decrease with increasing temperature, pressure, and equivalence ratio. The reactivity of the syngas mixtures was found to be governed by hydrogen chemistry for CO concentrationsmore » lower than 50% in the fuel mixture. For higher CO concentrations, an inhibiting effect of CO was observed. Flame speeds were measured in helium for syngas mixtures with a high CO content and at elevated pressures of 5 and 10 atm using the spherically expanding flame method. A detailed chemical kinetic mechanism for hydrogen and H2/CO (syngas) mixtures has been updated, rate constants have been adjusted to reflect new experimental information obtained at high pressures and new rate constant values recently published in the literature. Experimental results for ignition delay times and flame speeds have been compared with predictions using our newly revised chemical kinetic mechanism, and good agreement was observed. In the mechanism validation, particular emphasis is placed on predicting experimental data at high pressures (up to 70 bar) and intermediate- to high-temperature conditions, particularly important for applications in internal combustion engines and gas turbines. The reaction sequence H2 + HO˙2 ↔ H˙+H2O2 followed by H2O2(+M) ↔ O˙H+O˙H(+M) was found to play a key role in hydrogen ignition under high-pressure and intermediate-temperature conditions. The rate constant for H2+HO˙2 showed strong sensitivity to high-pressure ignition times and has considerable uncertainty, based on literature values

  2. An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures

    SciTech Connect

    Keromnes, Alan; Metcalfe, Wayne K.; Heufer, Karl A.; Donohoe, Nicola; Das, Apurba K.; Sung, Chih -Jen; Herzler, Jurgen; Naumann, Clemens; Griebel, Peter; Mathieu, Olivier; Krejci, Michael C.; Petersen, Eric L.; Pitz, William J.; Curran, Henry J.

    2013-03-12

    The oxidation of syngas mixtures was investigated experimentally and simulated with an updated chemical kinetic model. Ignition delay times for H2/CO/O2/N2/Ar mixtures have been measured using two rapid compression machines and shock tubes at pressures from 1 to 70 bar, over a temperature range of 914–2220 K and at equivalence ratios from 0.1 to 4.0. Results show a strong dependence of ignition times on temperature and pressure at the end of the compression; ignition delays decrease with increasing temperature, pressure, and equivalence ratio. The reactivity of the syngas mixtures was found to be governed by hydrogen chemistry for CO concentrations lower than 50% in the fuel mixture. For higher CO concentrations, an inhibiting effect of CO was observed. Flame speeds were measured in helium for syngas mixtures with a high CO content and at elevated pressures of 5 and 10 atm using the spherically expanding flame method. A detailed chemical kinetic mechanism for hydrogen and H2/CO (syngas) mixtures has been updated, rate constants have been adjusted to reflect new experimental information obtained at high pressures and new rate constant values recently published in the literature. Experimental results for ignition delay times and flame speeds have been compared with predictions using our newly revised chemical kinetic mechanism, and good agreement was observed. In the mechanism validation, particular emphasis is placed on predicting experimental data at high pressures (up to 70 bar) and intermediate- to high-temperature conditions, particularly important for applications in internal combustion engines and gas turbines. The reaction sequence H2 + HO˙2 ↔ H˙+H2O2 followed by H2O2(+M) ↔ O˙H+O˙H(+M) was found to play a key role in hydrogen ignition under high-pressure and intermediate-temperature conditions. The rate constant for H2+HO˙2

  3. Dual Studies on a Hydrogen-Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect

    ERIC Educational Resources Information Center

    Giles, Richard; Kim, Iris; Chao, Weyjuin Eric; Moore, Jennifer; Jung, Kyung Woon

    2014-01-01

    An efficient laboratory experiment has been developed for undergraduate students to conduct hydrogen-deuterium (H-D) exchange of resorcinol by electrophilic aromatic substitution using D[subscript 2]O and a catalytic amount of H[subscript 2]SO[subscript 4]. The resulting labeled product is characterized by [superscript 1]H NMR. Students also…

  4. Dual Studies on a Hydrogen-Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect

    ERIC Educational Resources Information Center

    Giles, Richard; Kim, Iris; Chao, Weyjuin Eric; Moore, Jennifer; Jung, Kyung Woon

    2014-01-01

    An efficient laboratory experiment has been developed for undergraduate students to conduct hydrogen-deuterium (H-D) exchange of resorcinol by electrophilic aromatic substitution using D[subscript 2]O and a catalytic amount of H[subscript 2]SO[subscript 4]. The resulting labeled product is characterized by [superscript 1]H NMR. Students also…

  5. An investigation of the kinetics of hydrogen chemisorption on iron metal surfaces

    NASA Technical Reports Server (NTRS)

    Shanabarger, M. R.

    1982-01-01

    The isothermal kinetics of H2, H2S, and O2 chemisorption onto epitaxially grown (III) oriented Fe films were studied. The measurements were made using the techniques of chemisorption induced resistance change and Auger electron spectroscopy (for adsorbed sulfur and oxygen). Also the origin of the chemisorption induced resistance change for these systems and its applicability to kinetic measurements were established. The chemisorption kinetics were interpreted as dissociative chemisorption via an adsorbed molecular species. The applicable rate constants were established. In none of the studies were the rate constants observed to be coverage dependent. By comparing the temperature dependence of the rate constants with absolute rate theory, the binding energies and activation energies of all the kinetic processes were obtained for the H2/Fe system. The initial sticking coefficient was pressure dependent for both the H2/Fe and H2S/Fe systems. This results from the step between the adsorbed molecular state and the dissociated chemisorbed state being the rate limiting step for absorption at certain pressures and temperatures. Estimates were obtained for the temperature dependence of the rate constants for the O2/Fe system.

  6. Kinetics and the mass transfer mechanism of hydrogen sulfide removal by biochar derived from rice hull.

    PubMed

    Shang, Guofeng; Liu, Liang; Chen, Ping; Shen, Guoqing; Li, Qiwu

    2016-05-01

    The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H2S) from gas phase. The surface area and pH of the biochar were compared. The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H2S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperature has great influence on the adsorption of H2S. At the different pyrolysis temperature, the H2S removal efficiency of rice hull-derived biochar was different. The adsorption capacities of biochar were 2.09 mg·g(-1), 2.65 mg·g(-1), 16.30 mg·g(-1), 20.80 mg·g(-1), and 382.70 mg·g(-1), which their pyrolysis temperatures were 100 °C, 200 °C, 300 °C, 400 °C and 500 °C respectively. Based on the Yoon-Nelson model, it analyzed the mass transfer mechanism of hydrogen sulfide adsorption by biochar. The paper focuses on the biochar derived from rice hull-removed hydrogen sulfide (H2S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperatures have great influence on the adsorption of H2S. At the different pyrolysis temperatures, the H2S removal efficiency of rice hull-derived biohar was different. The adsorption capacities of biochar were 2.09, 2.65, 16.30, 20.80, and 382.70 mg·g(-1), and their pyrolysis temperatures were 100, 200, 300, 400, and 500 °C, respectively. Based on the Yoon-Nelson model, the mass transfer mechanism of hydrogen sulfide adsorption by biochar was analyzed.

  7. A kinetic model for thermally induced hydrogen and carbon isotope fractionation of individual n-alkanes in crude oil

    NASA Astrophysics Data System (ADS)

    Tang, Yongchun; Huang, Yongsong; Ellis, Geoffrey S.; Wang, Yi; Kralert, Paul G.; Gillaizeau, Bruno; Ma, Qisheng; Hwang, Rong

    2005-09-01

    A quantitative kinetic model has been proposed to simulate the large D and 13C isotope enrichments observed in individual n-alkanes (C 13-C 21) during artificial thermal maturation of a North Sea crude oil under anhydrous, closed-system conditions. Under our experimental conditions, average n-alkane δ 13C values increase by ˜4‰ and δD values increase by ˜50‰ at an equivalent vitrinite reflectance value of 1.5%. While the observed 13C-enrichment shows no significant dependence on hydrocarbon chain length, thermally induced D-enrichment increases with increasing n-alkane carbon number. This differential fractionation effect is speculated to be due to the combined effect of the greater extent of thermal cracking of higher molecular weight, n-alkanes compared to lower molecular weight homologues, and the generation of isotopically lighter, lower molecular weight compounds. This carbon-number-linked hydrogen isotopic fractionation behavior could form the basis of a new maturity indicator to quantitatively assess the extent of oil cracking in petroleum reservoirs. Quantum mechanical calculations of the average change in enthalpy (ΔΔH ‡) and entropy (ΔΔS ‡) as a result of isotopic substitution in n-alkanes undergoing homolytic cleavage of C-C bonds lead to predictions of isotopic fractionation that agree quite well with our experimental results. For n-C 20 ( n-icosane), the changes in enthalpy are calculated to be ˜1340 J mol -1 (320 cal mol -1) and 230 J mol -1 (55 cal mol -1) for D-H and 13C- 12C, respectively. Because the enthalpy term associated with hydrogen isotope fractionation is approximately six times greater than that for carbon, variations in δD values for individual long-chain hydrocarbons provide a highly sensitive measure of the extent of thermal alteration experienced by the oil. Extrapolation of the kinetic model to typical geological heating conditions predicts significant enrichment in 13C and D for n-icosane at equivalent vitrinite

  8. Strategies for the improvement of the hydrogen storage properties of metal hydride materials.

    PubMed

    Wu, Hui

    2008-10-24

    Metal hydrides are an important family of materials that can potentially be used for safe, efficient and reversible on-board hydrogen storage. Light-weight metal hydrides in particular have attracted intense interest due to their high hydrogen density. However, most of these hydrides have rather slow absorption kinetics, relatively high thermal stability, and/or problems with the reversibility of hydrogen absorption/desorption cycling. This paper discusses a number of different approaches for the improvement of the hydrogen storage properties of these materials, with emphasis on recent research on tuning the ionic mobility in mixed hydrides. This concept opens a promising pathway to accelerate hydrogenation kinetics, reduce the activation energy for hydrogen release, and minimize deleterious possible by-products often associated with complex hydride systems.

  9. An Investigation of the Effect of Surface Impurities on the Adsorption Kinetics of Hydrogen Chemisorbed onto Iron

    NASA Technical Reports Server (NTRS)

    Shanabarger, M. R.

    1997-01-01

    The original goal of this program was to investigate the effect surface impurities have on the heterogeneous kinetic processes of those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. However, shortly after the initiation of the original program, the program's NASA Technical Monitor, Dr. Howard Nelson, requested that the effort supported by this Co-operative Agreement be redirected to study more pressing materials issues associated to the development of the National Aero-Space Plane (NASP). The results of these efforts are outlined in this report. Detailed discussions of specific work, including experimental techniques and procedures, will be found in the publications listed with the subsection discussing that specific work as well and in Section 5. No inventions were generated or disclosed within this Agreement.

  10. Enantiodivergent Atroposelective Synthesis of Chiral Biaryls by Asymmetric Transfer Hydrogenation: Chiral Phosphoric Acid Catalyzed Dynamic Kinetic Resolution.

    PubMed

    Mori, Keiji; Itakura, Tsubasa; Akiyama, Takahiko

    2016-09-12

    Reported herein is an enantiodivergent synthesis of chiral biaryls by a chiral phosphoric acid catalyzed asymmetric transfer hydrogenation reaction. Upon treatment of biaryl lactols with aromatic amines and a Hantzsch ester in the presence of chiral phosphoric acid, dynamic kinetic resolution (DKR) involving a reductive amination reaction proceeded smoothly to furnish both R and S isomers of chiral biaryls with excellent enantioselectivities by proper choice of hydroxyaniline derivative. This trend was observed in wide variety of substrates, and various chiral biphenyl and phenyl naphthyl adducts were synthesized with satisfactory enantioselectivities in enantiodivergent fashion. The enantiodivergent synthesis of synthetically challenging, chiral o-tetrasubstituted biaryls were also accomplished, and suggests high synthetic potential of the present method.

  11. First-principles study of adsorption-desorption kinetics of aqueous V(2+)/V(3+) redox species on graphite in a vanadium redox flow battery.

    PubMed

    Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

    2017-06-14

    Vanadium redox flow batteries (VRFBs) represent a promising solution to grid-scale energy storage, and understanding the reactivity of electrode materials is crucial for improving the power density of VRFBs. However, atomistic details about the interactions between vanadium ions and electrode surfaces in aqueous electrolytes are still lacking. Here, we examine the reactivity of the basal (0001) and edge (112[combining macron]0) graphite facets with water and aqueous V(2+)/V(3+) redox species at 300 K employing Car-Parrinello molecular dynamics (CPMD) coupled with metadynamics simulations. The results suggest that the edge surface is characterized by the formation of ketonic C[double bond, length as m-dash]O functional groups due to complete water dissociation into the H/O/H configuration with surface O atoms serving as active sites for adsorption of V(2+)/V(3+) species. The formation of V-O bonds at the surface should significantly improve the kinetics of electron transfer at the edge sites, which is not the case for the basal surface, in agreement with the experimentally hypothesized mechanism.

  12. Electrocatalysis of hydrogen peroxide reactions on perovskite oxides: experiment versus kinetic modeling.

    PubMed

    Poux, T; Bonnefont, A; Ryabova, A; Kéranguéven, G; Tsirlina, G A; Savinova, E R

    2014-07-21

    Hydrogen peroxide has been identified as a stable intermediate of the electrochemical oxygen reduction reaction on various electrodes including metal, metal oxide and carbon materials. In this article we study the hydrogen peroxide oxidation and reduction reactions in alkaline medium using a rotating disc electrode (RDE) method on oxides of the perovskite family (LaCoO3, LaMnO3 and La0.8Sr0.2MnO3) which are considered as promising electrocatalytic materials for the cathode of liquid and solid alkaline fuel cells. The experimental findings, such as the higher activity of Mn-compared to that of Co-perovskites, the shape of RDE curves, and the influence of the H2O2 concentration, are rationalized with the help of a microkinetic model.

  13. Small-Scale Kinetic Study of the Catalyzed Decomposition of Hydrogen Peroxide

    NASA Astrophysics Data System (ADS)

    Ragsdale, Ronald O.; Vanderhooft, Jan C.; Zipp, Arden P.

    1998-02-01

    The rate of decomposition of hydrogen peroxide with pyrolusite as a catalyst was studied directly by following the formation of oxygen bubbles. The apparatus consisted of a barrel from a 2-ml Beral pipet inserted over a micropipet tip which was fitted into a one-hole stopper. The stopper assembly was placed in a 20-mL glass bottle reaction vessel. The hydrogen peroxide can be obtained from the super market and the catalyst, a piece of pyrolusite, can be recycled. The reaction order was found to be 1.1 + 0.2 by 240 pairs of students. The activation energy was 35 + 14 kJ. Reproducible data have also been obtained with the minerals, psilomelane, maganite, and groutite as catalysts.

  14. Thermochemical and kinetics studies of the CH3SH+S (3P) hydrogen abstraction and insertion reactions.

    PubMed

    Cardoso, Daniely V V; Cunha, Leonardo A; Spada, Rene F K; Ferrão, Luiz F A; Roberto-Neto, Orlando; Machado, Francisco B C

    2014-09-01

    Sulfur-containing molecules have a significant impact on atmosphere and biosphere. In this work we studied, from the point of view of electronic structure and chemical kinetics methods, the elementary reactions between a methanethiol molecule and a sulfur atom leading to hydrogen abstraction C-S bond cleavage (CH(3)SH+S; R1:→ CH(3)S+SH; R2: → CH(2)SH+SH; R3:→ CH(3)+HS(2)). The geometrical structures of the reactants, products, and saddle points for the three reaction paths were optimized using the BB1K method with the aug-cc-pV(T+d)Z basis set. The thermochemical properties were improved using single point coupled-cluster (CCSD(T)) calculations on the BB1K geometries followed by extrapolation to the complete basis set (CBS) limit. This methodology was previously applied and has given accurate values of thermochemical and kinetics properties when compared to benchmark calculations and experimental data. For each reaction, the thermal rate constants were calculated using the improved canonical variational theory (ICVT) including the zero-curvature (ICVT/ZCT) and small-curvature (ICVT/SCT) tunneling corrections. For comparison, the overall ICVT/SCT reaction rate constant at 300 K obtained with single-point CCSD(T)/CBS calculations for the CH(3)SH+S reaction is approximately 1400 times lower than the isovalent CH(3)SH+O reaction, obtained with CVT/SCT. The reaction path involving the hydrogen abstraction from the thiol group is the most important reactive path in all temperatures.

  15. Implementation of steady state approximation for modelling of reaction kinetic of UV catalysed hydrogen peroxide oxidation of starch

    NASA Astrophysics Data System (ADS)

    Kumoro, Andri Cahyo; Retnowati, Diah Susetyo; Ratnawati, Budiyati, Catarina Sri

    2015-12-01

    With regard to its low viscosity, high stability, clarity, film forming and binding properties, oxidised starch has been widely used in various applications specifically in the food, paper, textile, laundry finishing and binding materials industries. A number of methods have been used to produce oxidised starch through reactions with various oxidizing agents, such as hydrogen peroxide, air oxygen, ozone, bromine, chromic acid, permanganate, nitrogen dioxide and hypochlorite. Unfortunately, most of previous works reported in the literatures were focused on the study of reaction mechanism and physicochemical properties characterization of the oxidised starches produced without investigation of the reaction kinetics of the oxidation process. This work aimed to develop a simple kinetic model for UV catalysed hydrogen peroxide oxidation of starch through implementation of steady state approximation for the radical reaction rates. The model was then verified using experimental data available in the literature. The model verification revealed that the proposed model shows its good agreement with the experimental data as indicated by an average absolute relative error of only 2.45%. The model also confirmed that carboxyl groups are oxidised further by hydroxyl radical. The carbonyl production rate was found to follow first order reaction with respect to carbonyl concentration. Similarly, carboxyl production rate also followed first order reaction with respect to carbonyl concentration. The apparent reaction rate constant for carbonyl formation and oxidation were 6.24 × 104 s-1 and 1.01 × 104 M-1.s-1, respectively. While apparent reaction rate constant for carboxyl oxidation was 4.86 × 104 M-1.s-1.

  16. Kinetic studies on enzyme-catalyzed reactions: oxidation of glucose, decomposition of hydrogen peroxide and their combination.

    PubMed

    Tao, Zhimin; Raffel, Ryan A; Souid, Abdul-Kader; Goodisman, Jerry

    2009-04-08

    The kinetics of the glucose oxidase-catalyzed reaction of glucose with O2, which produces gluconic acid and hydrogen peroxide, and the catalase-assisted breakdown of hydrogen peroxide to generate oxygen, have been measured via the rate of O2 depletion or production. The O2 concentrations in air-saturated phosphate-buffered salt solutions were monitored by measuring the decay of phosphorescence from a Pd phosphor in solution; the decay rate was obtained by fitting the tail of the phosphorescence intensity profile to an exponential. For glucose oxidation in the presence of glucose oxidase, the rate constant determined for the rate-limiting step was k = (3.0 +/- 0.7) x 10(4) M(-1) s(-1) at 37 degrees C. For catalase-catalyzed H2O2 breakdown, the reaction order in [H2O2] was somewhat greater than unity at 37 degrees C and well above unity at 25 degrees C, suggesting different temperature dependences of the rate constants for various steps in the reaction. The two reactions were combined in a single experiment: addition of glucose oxidase to glucose-rich cell-free media caused a rapid drop in [O2], and subsequent addition of catalase caused [O2] to rise and then decrease to zero. The best fit of [O2] to a kinetic model is obtained with the rate constants for glucose oxidation and peroxide decomposition equal to 0.116 s(-1) and 0.090 s(-1) respectively. Cellular respiration in the presence of glucose was found to be three times as rapid as that in glucose-deprived cells. Added NaCN inhibited O2 consumption completely, confirming that oxidation occurred in the cellular mitochondrial respiratory chain.

  17. The kinetics of iodide oxidation by hydrogen peroxide in acid solution

    NASA Astrophysics Data System (ADS)

    Milenković, M. C.; Stanisavljev, D. R.

    2011-12-01

    The kinetics of the complex reaction between I- and H2O2 in acid media was investigated. The particular attention was focused on the determination of the rate constant of the reaction between HIO and H2O2 involved in the investigated complex process. The examination of the whole kinetics was performed by simultaneously monitoring the evolution of O2 pressure, I{3/-} and I- concentrations. We modeled the behavior of experimentally followed components based on Liebhafsky's research. Our preliminary results suggest a significantly higher rate constant (3.5 × 107 M-1 s-1) of the reaction between HIO and H2O2 as those proposed in the literature.

  18. One-step reduced kinetics for lean hydrogen-air deflagration

    SciTech Connect

    Fernandez-Galisteo, D.; Sanchez, A.L.; Linan, A.; Williams, F.A.

    2009-05-15

    A short mechanism consisting of seven elementary reactions, of which only three are reversible, is shown to provide good predictions of hydrogen-air lean-flame burning velocities. This mechanism is further simplified by noting that over a range of conditions of practical interest, near the lean flammability limit all reaction intermediaries have small concentrations in the important thin reaction zone that controls the hydrogen-air laminar burning velocity and therefore follow a steady state approximation, while the main species react according to the global irreversible reaction 2H{sub 2} + O{sub 2} {yields} 2H{sub 2}O. An explicit expression for the non-Arrhenius rate of this one-step overall reaction for hydrogen oxidation is derived from the seven-step detailed mechanism, for application near the flammability limit. The one-step results are used to calculate flammability limits and burning velocities of planar deflagrations. Furthermore, implications concerning radical profiles in the deflagration and reasons for the success of the approximations are clarified. It is also demonstrated that adding only two irreversible direct recombination steps to the seven-step mechanism accurately reproduces burning velocities of the full detailed mechanism for all equivalence ratios at normal atmospheric conditions and that an eight-step detailed mechanism, constructed from the seven-step mechanism by adding to it the fourth reversible shuffle reaction, improves predictions of O and OH profiles. The new reduced-chemistry descriptions can be useful for both analytical and computational studies of lean hydrogen-air flames, decreasing required computation times. (author)

  19. Ab initio study of the kinetics of hydrogen abstraction reactions on toluene and tetralin

    SciTech Connect

    Beste, Ariana; Britt, Phillip F; Buchanan III, A C; Harrison, Robert J; Hathorn, Bryan C

    2008-01-01

    Hydrogen abstraction reactions play a key role in many thermal and catalytic processes involved in the production of fuels and chemicals. In this paper, the reaction barriers and rate constants for the hydrogen abstraction reactions on toluene and tetralin by the benzyl radical are calculated by ab initio methods. These reactions are representatives of similar reactions occurring in the thermolysis of lignin model compounds containing the phenethyl phenyl ether (PPE) structural moiety. Thermolysis of PPE occurs by a free radical chain mechanism in which the product selectivity arises from competitive hydrogen abstraction at the benzylic and nonbenzylic methylen sites by chain carrying benzyl and phenoxyl radicals. The title reactions serve to calibrate the theoretical methods to be used in the study of PPE through comparison of the rate constants and the reaction enthalpies with reliable experimental values. In this study, we used two different hybrid density functionals (BHandHLYP, B3LYP) and second-order perturbation theory to obtain equilibrium and transition state geometries. Multiple transition states were found for both reactions. BHandHLYP underestimates and second-order perturbation theory overestimates the reaction barriers; B3LYP energy barriers agree well with experiment. Absolute and relative rate constants were calculated using transition state theory. We found that the relative rate constant using the B3LYP functional agrees within a factor of 2.0 with experiment at the experimental temperature of 333 K, indicating that the B3LYP functional will be successful in predicting relative rate constants for hydrogen abstraction reactions participating in the pyrolysis of PPE.

  20. Quantitative kinetic analysis of hydrogen transfer reactions from dietary polyphenols to the DPPH radical.

    PubMed

    Goupy, Pascale; Dufour, Claire; Loonis, Michele; Dangles, Olivier

    2003-01-29

    Diphenylpicrylhydrazyl (DPPH) is widely used for quickly assessing the ability of polyphenols to transfer labile H atoms to radicals, a likely mechanism of antioxidant protection. This popular test generally pays no attention to the kinetics of H atom transfer, which however could be even more important than the total H-atom-donating capacities (stoichiometry, EC50) typically evaluated. In the present work, a series of dietary polyphenols belonging to the most representative families (flavonols from onion, flavanol monomers and oligomers from barley, and caffeic acid and caffeoyl esters from artichoke and endive) are characterized not only by their total stoichiometries (n(tot)) but also by their rate constants of first H atom abstraction by DPPH (k(1)), deduced from the kinetic analysis of the decay of the DPPH visible band following addition of the antioxidant. The mildly reactive DPPH radical allows a good discrimation between polyphenols, as demonstrated by the relatively large ranges of k(1) (ca. 400-5000 M(-)(1) s(-)(1)) and n(tot) (ca. 1-5) values typically measured with antioxidants having a single polyphenolic nucleus. With antioxidants displaying more than one polyphenolic nucleus (procyanidin oligomers, dicaffeoyl esters), the kinetic analysis makes it possible to demonstrate significant differences in reactivity between the subunits (two distinct k(1) values whose ratio lies in the range 3-10) and nonadditive stoichiometries.

  1. Kinetic study of the effects of calcium ions on cationic artichoke (Cynara scolymus L.) peroxidase: calcium binding, steady-state kinetics and reactions with hydrogen peroxide.

    PubMed

    Hiner, Alexander N P; Sidrach, Lara; Chazarra, Soledad; Varón, Ramón; Tudela, José; García-Cánovas, Francisco; Rodríguez-López, José Neptuno

    2004-01-01

    The apparent catalytic constant (k(cat)) of artichoke (Cynara scolymus L.) peroxidase (AKPC) with 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS) increased 130-fold in the presence of calcium ions (Ca2+) but the affinity (K(m)) of the enzyme for ABTS was 500 times lower than for Ca2+-free AKPC. AKPC is known to exhibit an equilibrium between 6-aquo hexa-coordinate and penta-coordinate forms of the haem iron that is modulated by Ca2+ and affects compound I formation. Measurements of the Ca2+ dissociation constant (K(D)) were complicated by the water-association/dissociation equilibrium yielding a global value more than 1000 times too high. The value for the Ca2+ binding step alone has now been determined to be K(D) approximately 10 nM. AKPC-Ca2+ was more resistant to inactivation by hydrogen peroxide (H(2)O(2)) and exhibited increased catalase activity. An analysis of the complex H(2)O(2) concentration dependent kinetics of Ca2+-free AKPC is presented.

  2. High-yield hydrogen production from biomass by in vitro metabolic engineering: Mixed sugars coutilization and kinetic modeling

    SciTech Connect

    Rollin, Joseph A.; Martin del Campo, Julia; Myung, Suwan; Sun, Fangfang; You, Chun; Bakovic, Allison; Castro, Roberto; Chandrayan, Sanjeev K.; Wu, Chang-Hao; Adams, Michael W. W.; Senger, Ryan S.; Zhang, Y. -H. Percival

    2015-04-06

    The use of hydrogen (H2) as a fuel offers enhanced energy conversion efficiency and tremendous potential to decrease greenhouse gas emissions, but producing it in a distributed, carbon-neutral, low-cost manner requires new technologies. Herein we demonstrate the complete conversion of glucose and xylose from plant biomass to H2 and CO2 based on an in vitro synthetic enzymatic pathway. Glucose and xylose were simultaneously converted to H2 with a yield of two H2 per carbon, the maximum possible yield. Parameters of a nonlinear kinetic model were fitted with experimental data using a genetic algorithm, and a global sensitivity analysis was used to identify the enzymes that have the greatest impact on reaction rate and yield. After optimizing enzyme loadings using this model, volumetric H2 productivity was increased 3-fold to 32 mmol H2∙L₋1∙h₋1. The productivity was further enhanced to 54 mmol H2∙L₋1∙h₋1 by increasing reaction temperature, substrate, and enzyme concentrations—an increase of 67-fold compared with the initial studies using this method. The production of hydrogen from locally produced biomass is a promising means to achieve global green energy production.

  3. High-yield hydrogen production from biomass by in vitro metabolic engineering: Mixed sugars coutilization and kinetic modeling

    PubMed Central

    Rollin, Joseph A.; Martin del Campo, Julia; Myung, Suwan; Sun, Fangfang; You, Chun; Bakovic, Allison; Castro, Roberto; Chandrayan, Sanjeev K.; Wu, Chang-Hao; Adams, Michael W. W.; Senger, Ryan S.; Zhang, Y.-H. Percival

    2015-01-01

    The use of hydrogen (H2) as a fuel offers enhanced energy conversion efficiency and tremendous potential to decrease greenhouse gas emissions, but producing it in a distributed, carbon-neutral, low-cost manner requires new technologies. Herein we demonstrate the complete conversion of glucose and xylose from plant biomass to H2 and CO2 based on an in vitro synthetic enzymatic pathway. Glucose and xylose were simultaneously converted to H2 with a yield of two H2 per carbon, the maximum possible yield. Parameters of a nonlinear kinetic model were fitted with experimental data using a genetic algorithm, and a global sensitivity analysis was used to identify the enzymes that have the greatest impact on reaction rate and yield. After optimizing enzyme loadings using this model, volumetric H2 productivity was increased 3-fold to 32 mmol H2⋅L−1⋅h−1. The productivity was further enhanced to 54 mmol H2⋅L−1⋅h−1 by increasing reaction temperature, substrate, and enzyme concentrations—an increase of 67-fold compared with the initial studies using this method. The production of hydrogen from locally produced biomass is a promising means to achieve global green energy production. PMID:25848015

  4. High-yield hydrogen production from biomass by in vitro metabolic engineering: Mixed sugars coutilization and kinetic modeling

    DOE PAGES

    Rollin, Joseph A.; Martin del Campo, Julia; Myung, Suwan; ...

    2015-04-06

    The use of hydrogen (H2) as a fuel offers enhanced energy conversion efficiency and tremendous potential to decrease greenhouse gas emissions, but producing it in a distributed, carbon-neutral, low-cost manner requires new technologies. Herein we demonstrate the complete conversion of glucose and xylose from plant biomass to H2 and CO2 based on an in vitro synthetic enzymatic pathway. Glucose and xylose were simultaneously converted to H2 with a yield of two H2 per carbon, the maximum possible yield. Parameters of a nonlinear kinetic model were fitted with experimental data using a genetic algorithm, and a global sensitivity analysis was usedmore » to identify the enzymes that have the greatest impact on reaction rate and yield. After optimizing enzyme loadings using this model, volumetric H2 productivity was increased 3-fold to 32 mmol H2∙L₋1∙h₋1. The productivity was further enhanced to 54 mmol H2∙L₋1∙h₋1 by increasing reaction temperature, substrate, and enzyme concentrations—an increase of 67-fold compared with the initial studies using this method. The production of hydrogen from locally produced biomass is a promising means to achieve global green energy production.« less

  5. Hydrogen peroxide release kinetics into saliva from different whitening products: a double-blind, randomized clinical trial.

    PubMed

    Marques, Duarte Nuno da Silva; da Mata, António Duarte Sola Pereira; Silveira, João Miguel Lourenço; Marques, Joana Rita Oliveira Faria; Amaral, João Pedro de Almeida Rato; Guilherme, Nuno Filipe Rito Parada Marques

    2012-02-01

    The objective of this study is to compare salivary hydrogen peroxide (HP) release kinetics and potential toxicity of systemic exposure of four different whitening products. A double-blind, randomized controlled trial was conducted in a Portuguese dental faculty clinic. Two hundred forty volunteers were randomized to eight intervention groups. Participants were randomly assigned to receive active or placebo applications of one of four different products: Opalescence 10% PF™ (OPL), Vivastyle® 10%™ (VS10%), Vivadent Paint On Plus™ (PO+), and Trés White Supreme™ (TWS). Saliva collection was obtained by established methods at different times. The HP salivary content was determined by a photometric method. Salivary HP variations, total amount of salivary HP, and counts of subjects above the safe daily HP dose were the main outcome measures. All whitening systems significantly released HP to the saliva when compared to placebo, and all showed different release kinetics. The adaptable tray system (TWS) presented a risk increase of 37% [20-54%, 95% confidence interval] when compared to the other systems. The use of an adaptable tray whitening system with higher concentration of HP increases the toxicity potential.

  6. Degradation kinetics and mechanism of trace nitrobenzene by granular activated carbon enhanced microwave/hydrogen peroxide system.

    PubMed

    Tan, Dina; Zeng, Honghu; Liu, Jie; Yu, Xiaozhang; Liang, Yanpeng; Lu, Lanjing

    2013-07-01

    The kinetics of the degradation of trace nitrobenzene (NB) by a granular activated carbon (GAC) enhanced microwave (MW)/hydrogen peroxide (H202) system was studied. Effects of pH, NB initial concentration and tert-butyl alcohol on the removal efficiency were examined. It was found that the reaction rate fits well to first-order reaction kinetics in the MW/GAC/H202 process. Moreover, GAC greatly enhanced the degradation rate of NB in water. Under a given condition (MW power 300 W, H202 dosage 10 mg/L, pH 6.85 and temperature (60 +/- 5)degrees C), the degradation rate of NB was 0.05214 min-1when 4 g/L GAC was added. In general, alkaline pH was better for NB degradation; however, the optimum pH was 8.0 in the tested pH value range of 4.0-12.0. At H202 dosage of 10 mg/L and GAC dosage of 4 g/L, the removal of NB was decreased with increasing initial concentrations of NB, indicating that a low initial concentration was beneficial for the degradation of NB. These results indicated that the MW/GAC/H202 process was effective for trace NB degradation in water. Gas chromatography-mass spectrometry analysis indicated that a hydroxyl radical addition reaction and dehydrogenation reaction enhanced NB degradation.

  7. Desorption in Mass Spectrometry.

    PubMed

    Usmanov, Dilshadbek Tursunbayevich; Ninomiya, Satoshi; Chen, Lee Chuin; Saha, Subhrakanti; Mandal, Mridul Kanti; Sakai, Yuji; Takaishi, Rio; Habib, Ahsan; Hiraoka, Kenzo; Yoshimura, Kentaro; Takeda, Sen; Wada, Hiroshi; Nonami, Hiroshi

    2017-01-01

    In mass spectrometry, analytes must be released in the gas phase. There are two representative methods for the gasification of the condensed samples, i.e., ablation and desorption. While ablation is based on the explosion induced by the energy accumulated in the condensed matrix, desorption is a single molecular process taking place on the surface. In this paper, desorption methods for mass spectrometry developed in our laboratory: flash heating/rapid cooling, Leidenfrost phenomenon-assisted thermal desorption (LPTD), solid/solid friction, liquid/solid friction, electrospray droplet impact (EDI) ionization/desorption, and probe electrospray ionization (PESI), will be described. All the methods are concerned with the surface and interface phenomena. The concept of how to desorb less-volatility compounds from the surface will be discussed.

  8. Desorption in Mass Spectrometry

    PubMed Central

    Usmanov, Dilshadbek Tursunbayevich; Ninomiya, Satoshi; Chen, Lee Chuin; Saha, Subhrakanti; Mandal, Mridul Kanti; Sakai, Yuji; Takaishi, Rio; Habib, Ahsan; Hiraoka, Kenzo; Yoshimura, Kentaro; Takeda, Sen; Wada, Hiroshi; Nonami, Hiroshi

    2017-01-01

    In mass spectrometry, analytes must be released in the gas phase. There are two representative methods for the gasification of the condensed samples, i.e., ablation and desorption. While ablation is based on the explosion induced by the energy accumulated in the condensed matrix, desorption is a single molecular process taking place on the surface. In this paper, desorption methods for mass spectrometry developed in our laboratory: flash heating/rapid cooling, Leidenfrost phenomenon-assisted thermal desorption (LPTD), solid/solid friction, liquid/solid friction, electrospray droplet impact (EDI) ionization/desorption, and probe electrospray ionization (PESI), will be described. All the methods are concerned with the surface and interface phenomena. The concept of how to desorb less-volatility compounds from the surface will be discussed. PMID:28337398

  9. Kinetics of hydrogen-oxygen and methane-oxygen ignition sensitized by NO or NO2

    NASA Technical Reports Server (NTRS)

    Slack, M. W.; Grillo, A. R.

    1978-01-01

    In a study of methane ignition sensitized by NO2, the induction period chemical kinetics were examined by monitoring reactants and intermediates (CH4, NO2, OH, NO, CO, CO2, and H2O) prior to ignition. Data were obtained at pressure of 2-4 atm, temperatures of 1300-1900 K, equivalence ratios of 0.5-1.0, and NO2 up to 3.4 mole %. A tentative NO2 sensitization mechanism was deduced from the analysis of photometric observations and the comparison of computer modeling with observations.

  10. Ultrafast electron kinetics in short pulse laser-driven dense hydrogen

    SciTech Connect

    Zastrau, U.; Sperling, P.; Fortmann-Grote, C.; Bornath, T.; Bredow, R.; Do