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Sample records for hydrogen sorption kinetics

  1. Effect of the strong metal-support interaction on hydrogen sorption kinetics of Pd-capped switchable mirrors

    NASA Astrophysics Data System (ADS)

    Borgschulte, A.; Westerwaal, R. J.; Rector, J. H.; Dam, B.; Griessen, R.; Schoenes, J.

    2004-10-01

    The morphology and electronic structure of Pd clusters grown on oxidized yttrium surfaces are investigated by scanning tunneling microscopy and ultraviolet photoelectron spectroscopy. The hydrogen sorption mediated by the Pd clusters is determined from the optically monitored switching kinetics of the underlying yttrium film. A strong thickness dependence of the hydrogen uptake is found. The electronic structure of the as-grown Pd clusters depends only weakly on their size. Strong changes of the photoemission spectra are found after hydrogenation, in particular the oxide peak shifts and the Pd peaks vanish. Both phenomena are due to a strong metal-support interaction (SMSI) state, characterized by a complete encapsulation of the clusters by a reduced yttrium oxide layer. Scanning tunneling spectroscopy confirms the SMSI state of small Pd clusters after hydrogen exposure. The SMSI effect is less important with increasing Pd thickness. This explains the critical thickness for the catalyzed hydrogen uptake by the Pd/YOx/Y system. The results shed light on the mechanism of hydrogen absorption at the triple point gas-catalyst-oxide, which also plays an important role in today’s fuel cell technology.

  2. Nucleation and growth mechanisms of nano magnesium hydride from the hydrogen sorption kinetics.

    PubMed

    Mooij, Lennard; Dam, Bernard

    2013-07-21

    We use a combination of hydrogenography and Johnson-Mehl-Avrami-Kolmogorov (JMAK) analyses to identify (1) the driving force dependence of the nucleation and growth mechanism of MgH2 in thin film multilayers of Mg (10 nm) and (2) the nucleation and growth mechanism of Mg in the earlier formed MgH2, i.e. the hydrogen desorption process. We conclude that JMAK may be successfully applied to obtain the nucleation and growth mechanism of hydrogen absorption. The desorption mechanism, however, is not simply the reverse of the absorption mechanism. We find evidence that the barrier for nucleation of Mg is small. The dehydrogenation probably involves the formation of voids, which is energetically more favorable than elastic and plastic deformation of the multilayer. PMID:23749082

  3. Understanding the role of few-layer graphene nanosheets in enhancing the hydrogen sorption kinetics of magnesium hydride.

    PubMed

    Liu, Guang; Wang, Yijing; Jiao, Lifang; Yuan, Huatang

    2014-07-23

    The catalytic effects of few-layer, highly wrinkled graphene nanosheet (GNS) addition on the dehydrogenation/rehydrogenation performance of MgH2 were investigated. It was found that MgH2-5 wt %GNSs nanocomposites prepared by ball milling exhibit relatively lower sorption temperature, faster sorption kinetics, and more stable cycling performance than that of pure-milled MgH2. The dehydrogenation step confirms that the Avrami exponent n increases from 1.22 to 2.20 by the Johnson-Mehl-Avrami (JMA) formalism when the desorption temperature is reduced from 350 °C to 320 °C and 300 °C, implying that a change in the decomposition temperature can alter the mechanism during the dehydrogenation process. For rehydrogenation, the Avrami value n is close to 1; further study by several models coincident with n = 1 reveals that the absorption process of the MgH2-5 wt %GNSs sample conforms to the Mampel equation formulated through the random nucleation approach and that the nature of the absorption mechanism does not change within the temperature range studied. Furthermore, microstructure analysis demonstrated that the defective GNSs are distributed uniformly among the MgH2 particles and that the grain size of the MgH2-5 wt %GNSs nanocomposite is approximately 5-9 nm. The efficient metal-free catalytic dehydrogenation/rehydrogenation of MgH2 can be attributed to the coupling of the nanosize effect and defective GNSs. PMID:24941011

  4. Hydrogen sorption rate by intermetallic compounds suitable for tritium storage

    SciTech Connect

    Penzhorn, R.D.; Sirch, M.; Perevezentsev, A.N.; Borisenko, A.N.

    1995-10-01

    The kinetics of the sorption of molecular hydrogen by ZrCo and Zr{sub 0.8}Ti{sub 0.3}Mn{sub 1.9} was investigated as function of temperature at several constant pressures of hydrogen. A comparison between the isothermal hydrogen sorption rates by ZrCo, Zr{sub 0.8}Ti{sub 0.3}Mn{sub 1.9} and LaNi{sub 4.7}Al{sub 0.3} is given and reaction mechanisms are discussed. From fittings of the experimental results to well known gas/solid reaction rate laws it was concluded that the reaction mechanisms of the reaction with ZrCo is complex and dependent upon the prevailing reaction conditions. The hydrogen sorption rate by the powder of all three IMC`s was found to be second order in hydrogen pressure. 8 refs., 7 figs., 1 tab.

  5. Sorption kinetics of hexadecyltrimethylammonium on natural clinoptilolite

    SciTech Connect

    Li, Z.

    1999-09-14

    Sorption kinetics of hexadecyltrimethylammonium (HDTMA) chloride on a natural clinoptilolite was studied in this research. The amount of HDTMA sorbed is a function of the initial HDTMA input and the sorption time. When the initial HDTMA input is less than the external cation-exchange capacity of the clinoptilolite, the HDTMA sorption is fast and equilibrium can be established in 1 h. As the initial HDTMA input is greater than the external cation-exchange capacity of clinoptilolite, which will result in more than a monolayer HDTMA surface coverage, the time for HDTMA sorption to reach equilibrium increases exponentially. The HDTMA sorption maximum on clinoptilolite increases logarithmically with mixing time. The counterion solution concentration data suggest that at the initial stage HDTMA molecules sorb on the zeolite via micelle forms, which is manifested by a decrease in chloride solution concentration with time. When HDTMA solution concentration is depleted to less than its critical micelle concentration, the adsorbed micelles (admicelles) rearrange themselves to a more stable monolayer or bilayer configuration, which is reflected by an increase in counterion solution concentration due to the desorption of chloride from admicelles. The time required for the surface rearrangement increases exponentially as the HDTMA input increases. The data of HDTMA sorption kinetics were fitted to different kinetic models, and the parabolic diffusion model fits the data best for the HDTMA sorption, counterion sorption at the initial stage and counterion desorption at the rearrangement stage. Thus, the sorption of HDTMA on clinoptilolite surfaces is diffusion controlled. The results also indicate that it is incomplete to discuss surfactant sorption without counterion concentration data.

  6. Hydrogen peroxide modified sodium titanates with improved sorption capabilities

    DOEpatents

    Nyman, May D.; Hobbs, David T.

    2009-02-24

    The sorption capabilities (e.g., kinetics, selectivity, capacity) of the baseline monosodium titanate (MST) sorbent material currently being used to sequester Sr-90 and alpha-emitting radioisotopes at the Savannah River Site are significantly improved when treated with hydrogen peroxide; either during the original synthesis of MST, or, as a post-treatment step after the MST has been synthesized. It is expected that these peroxide-modified MST sorbent materials will have significantly improved sorption capabilities for non-radioactive cations found in industrial processes and waste streams.

  7. Sorption kinetics and its effects on retention and leaching.

    PubMed

    de Wilde, Tineke; Mertens, Jan; Spanoghe, Pieter; Ryckeboer, Jaak; Jaeken, Peter; Springael, Dirk

    2008-06-01

    Sorption of pesticides to substrates used in biopurification systems is important as it controls the system's efficiency. Ideally, pesticide sorption should occur fast so that leaching of the pesticide in the biopurification system is minimized. Although modeling of pesticide transport commonly assumes equilibrium, this may not always be true in practice. Sorption kinetics have to be taken into account. This study investigated the batch sorption kinetics of linuron, isoproturon, metalaxyl, isoxaben and lenacil on substrates commonly used in a biopurification system, i.e. cow manure, straw, willow chopping, sandy loam soil, coconut chips, garden waste compost and peat mix. The first-order sorption kinetics model was fitted to the observed pesticide concentrations versus time resulting in an estimated kinetic rate constant alpha. Sorption appeared to be fast for the pesticides linuron and isoxaben, pesticides which were classified as immobile, while less mobile pesticides displayed an overall slower sorption. However, the substrate does not seem to be the main parameter influencing the sorption kinetics. Coconut chips, which is a substrate with a high organic matter content showed slow sorption for most of the pesticides. The effect of different estimated alpha values on the breakthrough of pesticides through a biopurification system was evaluated using the HYDRUS 1D model. Significant differences in leaching behavior were observed as a result of the obtained differences in sorption kinetics. PMID:18413279

  8. 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.

  9. Sorption Enhanced Reaction Process (SERP) for production of hydrogen

    SciTech Connect

    Anand, M.; Hufton, J.; Mayorga, S.

    1996-10-01

    Sorption Enhanced Reaction Process (SERP) is a novel process that is being developed for the production of lower cost hydrogen by steam-methane reforming (SMR). In this process the reaction of methane with steam is carried out in the presence of an admixture of a catalyst and a selective adsorbent for carbon dioxide. The key consequences of SERP are: (i) reformation reaction is carried out at a significantly lower temperature (300-500{degrees}C) than that in a conventional SMR reactor (800-1100{degrees}C), while achieving the same conversion of methane to hydrogen, (ii) the product hydrogen is obtained at reactor pressure (200-400 psig) and at 98+% purity directly from the reactor (compared to only 70-75% H{sub 2} from conventional SMR reactor), (iii) downstream hydrogen purification step is either eliminated or significantly reduced in size. The first phase of the program has focused on the development of a sorbent for CO{sub 2} which has (a) reversible CO{sub 2} capacity >0.3 mmol/g at low partial pressures of CO{sub 2} (0.1 - 1.0 atm) in the presence of excess steam (pH{sub 2}O/pCO{sub 2}>20) at 400-500{degrees}C and (b) fast sorption-desorption kinetics for CO{sub 2}, at 400-500{degrees}C. Several families of supported sorbents have been identified that meet the target CO{sub 2} capacity. A few of these sorbents have been tested under repeated sorption/desorption cycles and extended exposure to high pressure steam at 400-500{degrees}C. One sorbent has been scaled up to larger quantities (2-3 kg) and tested in the laboratory process equipment for sorption and desorption kinetics of CO{sub 2}. The CO{sub 2}, sorption and desorption kinetics are desirably fast. This was a critical path item for the first phase of the program and now has been successfully demonstrated. A reactor has been designed that will allow nearly isothermal operation for SERP-SMR. This reactor was integrated into an overall process flow diagram for the SERP-SMR process.

  10. Sorption kinetics of heavy oil into porous carbons.

    PubMed

    Nishi, Yoko; Iwashita, Norio; Sawada, Yoshihiro; Inagaki, Michio

    2002-12-01

    Sorption kinetics of heavy oil into porous carbons was evaluated by a concept of liquid sorption coefficient obtained from the weight increase of heavy oil with sorption time, which was measured by a wicking test. Exfoliated graphite, carbonized fir fibers and carbon fiber felts were used as porous materials. It was found that the liquid sorption coefficient of fibrous carbons was twice larger than that of exfoliated graphite. Such a difference in the liquid sorption coefficient between the exfoliated graphite and two fibrous carbons was caused by a difference in effective sorption porosity and tortuosity between them. For the exfoliated graphite and carbonized fir fibers, the liquid sorption coefficient and the effective sorption porosity were strongly dependent on their density. The maximum values of both liquid sorption coefficient and effective sorption porosity of the exfoliated graphite were shown at the bulk density around 16 kg/m3. The liquid sorption coefficient of the carbonized fir fibers increased with increasing the density in the range from 6 to 30 kg/m3. When the carbonized fir fibers were densified above 30 kg/m3, the sorption rate was saturated. On the other hand, the sorption kinetics into the carbon fiber felt was almost independent of the bulk density, because the density of the carbon fiber felt is not effective for the pore structure. The effect of bulk density on the sorption kinetics could be supported from an analysis of pore structure of the porous carbons with different densities, which was measured by mercury porosimeter. PMID:12448551

  11. Kinetics of the sorption of triterpene saponin by hypercrosslinked polystyrene

    NASA Astrophysics Data System (ADS)

    Mironenko, N. V.; Brezhneva, T. A.; Selemenev, V. F.

    2013-03-01

    The kinetics of sorption of triterpene saponin by the polymer sorbent NM-200 is considered. The influence of the surface activity of glycoside on the rate of formation and structure of the adsorption layer on the sorbent's surface is established. The rate-determining step of sorption is found to be diffusion into the sorbent grain. The value of the activation energy demonstrates the determining role of dispersion forces in the interaction between triterpene saponin and the polymer sorbent MN-200.

  12. Heat and mass transfer in the sorption of hydrogen by intermetallic compounds

    SciTech Connect

    Svinarev, S.V.; Trushevskii, S.N.

    1984-06-01

    Intermetallic compounds (IMC), which reversibly absorb hydrogen, are currently the subject of many investigations re their possible use in hydrogen accumulators, thermal machines, thermal pumps and accumulators, sorptional compressors, etc. The dynamics of hydrogen sorption in IMC must be investigated for the analysis and design of such devices. Trends in such studies can be distinguished: the study of the true chemical kinetics of sorption; the investigation of the sorption dynamics in extended IMC layers of dimensions characteristic for practical applications. However, these do not give criteria by which the experimental conditions may be chosen, and often the conditions themselves are not completely described. In connection with this, calculations of the sorption process in which the heat liberation and filtration of hydrogen through the IMC layer are taken into account are of interest both for practical applications and for the elucidation of the conditions in which the process may be regarded as purely kinetic or controlled by the heat and mass transfer in the layer. The authors devote themselves to this aspect in this presentation.

  13. Incorporation of aqueous reaction and sorption kinetics andbiodegradation into TOUGHREACT

    SciTech Connect

    Xu, Tianfu

    2006-04-17

    The needs for considering aqueous and sorption kinetics and microbiological processes arises in many subsurface problems, such as environmental and acid mine remediation. A general rate expression has been implemented into TOUGHREACT, which considers multiple mechanisms(pathways) and includes multiple product, Monod, and inhibition terms. In this paper, the formulation for incorporating kinetic rates among primary species into the mass balance equations is presented. A batch sulfide oxidation problem is simulated. The resulting concentrations are consistent with simple hand calculations. A 1-D reactive transport problem with kinetic biodegradation and sorption was investigated, which models the processes when a pulse of water containing NTA (nitrylotriacetate) and cobalt is injected into a column. The problem has several interacting chemical processes that are common to many environmental problems: biologically-mediated degradation of an organic substrate, bacterial cell growth and decay, metal sorption and aqueous speciation including metal-ligand complexation. The TOUGHREACT simulation results agree very well with those obtained with other simulators.

  14. Modeling solute advection coupled with sorption kinetics in heterogeneous formations

    NASA Astrophysics Data System (ADS)

    Selroos, Jan-Olof; Cvetkovic, Vladimir

    1992-05-01

    A method for coupling sorption kinetics and solute advection in particle-tracking models is proposed; this method is efficient for the case where sorption rate coefficients can be assumed constant field scale parameters. A simulation example of reactive solute advection in two-dimensional heterogeneous porous media is presented. The effect of sorption kinetics on solute advection is investigated. Nonequilibrium effects are exhibited as enhanced tailing in the solute breakthrough. Because high variability in the hydraulic conductivity also yields enhanced tailing, the nonequilibrium effect is more pronounced for the case of low variability. Moreover, it may be difficult to distinguish cases of low variability with nonequilibrium sorption from cases of high variability with equilibrium sorption. A comparison of Monte Carlo ensemble results is made with an analytical model for the mass arrival of kinetically sorbing solute in heterogeneous porous media obtained using first-order perturbation. The comparison indicates that the analytical model provides reasonable approximations of the expected solute breakthrough if the variance of the natural logarithm of the hydraulic conductivity is smaller than 1.

  15. Sorption kinetics of diuron on volcanic ash derived soils.

    PubMed

    Cáceres-Jensen, Lizethly; Rodríguez-Becerra, Jorge; Parra-Rivero, Joselyn; Escudey, Mauricio; Barrientos, Lorena; Castro-Castillo, Vicente

    2013-10-15

    Diuron sorption kinetic was studied in Andisols, Inceptisol and Ultisols soils in view of their distinctive physical and chemical properties: acidic pH and variable surface charge. Two types of kinetic models were used to fit the experimental dates: those that allow to establish principal kinetic parameters and modeling of sorption process (pseudo-first-order, pseudo-second-order), and some ones frequently used to describe solute transport mechanisms of organic compounds on different sorbents intended for remediation purposes (Elovich equation, intraparticle diffusion, Boyd, and two-site nonequilibrium models). The best fit was obtained with the pseudo-second-order model. The rate constant and the initial rate constant values obtained through this model demonstrated the behavior of Diuron in each soil, in Andisols were observed the highest values for both parameters. The application of the models to describe solute transport mechanisms allowed establishing that in all soils the mass transfer controls the sorption kinetic across the boundary layer and intraparticle diffusion into macropores and micropores. The slowest sorption rate was observed on Ultisols, behavior which must be taken into account when the leaching potential of Diuron is considered. PMID:23995557

  16. Dependence of methane sorption kinetics on coal structure

    SciTech Connect

    B. Kovaleva; E.A. Solov'eva

    2006-01-15

    The data of experimental laboratory studies into the methane sorption kinetics in samples of mineral coals of different metamorphism grade and petrographic composition are presented. Their relation to the character of gas emission from gas-saturated coal seams is considered. The dependence of the gas emission type on the size of undisturbed fragment of coal and methane diffusion coefficient is revealed.

  17. Two hydrogen sorption cryocoolers for the Planck mission

    NASA Astrophysics Data System (ADS)

    Morgante, G.; Barber, D.; Bhandari, P.; Bowman, R. C.; Cowgill, P.; Crumb, D.; Loc, T.; Nash, A.; Pearson, D.; Prina, M.; Sirbi, A.; Schemlzel, M.; Sugimura, R.; Wade, L. A.

    2002-05-01

    Two continuous operation 18 K/20 K sorption cryocoolers are being developed by the Jet Propulsion Laboratory (JPL) as a NASA contribution to the European Space Agency (ESA) Planck mission, currently planned for a 2007 launch. Each individual sorption cooler will be capable of providing a total of about 200 mW of cooling power at 18 K and 1.2 W at 20 K, given a passive radiative precooling at 50 K. These coolers work by thermally cycling a metal-hydride to absorb and desorb hydrogen gas, used as the working fluid in a Joule-Thomson (J-T) refrigerator. The major advantage of the sorption coolers is their truly vibration-free operation capability together with the fact that they can be readily scaled to perform over a wide range of cooling powers. The hydrogen sorption coolers will directly cool the Planck Low Frequency Instrument (LFI) HEMT amplifiers to approximately 20 K and will provide precooling at 18 K to the RAL 4 K closed-cycle Helium J-T cooler for the High Frequency Instrument (HFI). The concept design, the cooler operations and the predicted performances of the flight models are here presented. .

  18. Kinetic Study of Denatonium Sorption to Smectite Clay Minerals

    PubMed Central

    Crosson, Garry S.; Sandmann, Emily

    2013-01-01

    Abstract The denatonium cation, as a benzoate salt, is the most bitter cation known to modern society and is frequently added to consumer products to reduce accidental and intentional consumption by humans and animals. Denatonium can enter the environment by accidental discharges, potentially rendering water supplies undrinkable. Interactions of denatonium with soil components (i.e., smectite minerals) ultimately control the environmental fate of denatonium, but the current literature is devoid of studies that evaluate denatonium sorption to smectite minerals. This study investigated the mechanism and kinetics of denatonium sorption to smectite clay minerals as a function of smectite type, temperature, pH and ionic strength. Uptake by synthetic mica montmorillonite (Syn-1), Wyoming montmorillonite (SWy-2), and Texas montmorillonite (STx-1b) at 305K was rapid, with equilibrium being reached within 2 min for all clays. Complete removal of denatonium was observed for STx-1b at pH 6.9, while partial removal was observed for Syn-1 and SWy-2. Kinetic behavior of SWy-2 and Syn-1 is consistent with a pseudo–second-order model at 305K. An activation energy of +25.9 kJ/mol was obtained for sorption to Syn-1 and was independent of temperature between 286K and 338K. Activation-free energy (ΔG*), activation enthalpy (ΔH*), and activation entropy (ΔS*) for Syn-1 were found to be +62.91 kJ/mol, +23.36 kJ/mol, and −0.130 kJ/(K·mol), respectively. Sorption capacities at pH 3.6, 6.9, and 8.2 were constant at 1.3×10−2 g denatonium/g clay; however, the kinetic rate constant increased by 56%, going from acidic to basic solution conditions. Distribution coefficients were negatively correlated with ionic strength, suggesting cation exchange. Collectively, results suggested that smectite minerals can serve as efficient sinks for denatonium cations. This is much-needed information for agencies developing regulations regarding denatonium usage and for water treatment

  19. Kinetic Study of Denatonium Sorption to Smectite Clay Minerals.

    PubMed

    Crosson, Garry S; Sandmann, Emily

    2013-06-01

    The denatonium cation, as a benzoate salt, is the most bitter cation known to modern society and is frequently added to consumer products to reduce accidental and intentional consumption by humans and animals. Denatonium can enter the environment by accidental discharges, potentially rendering water supplies undrinkable. Interactions of denatonium with soil components (i.e., smectite minerals) ultimately control the environmental fate of denatonium, but the current literature is devoid of studies that evaluate denatonium sorption to smectite minerals. This study investigated the mechanism and kinetics of denatonium sorption to smectite clay minerals as a function of smectite type, temperature, pH and ionic strength. Uptake by synthetic mica montmorillonite (Syn-1), Wyoming montmorillonite (SWy-2), and Texas montmorillonite (STx-1b) at 305K was rapid, with equilibrium being reached within 2 min for all clays. Complete removal of denatonium was observed for STx-1b at pH 6.9, while partial removal was observed for Syn-1 and SWy-2. Kinetic behavior of SWy-2 and Syn-1 is consistent with a pseudo-second-order model at 305K. An activation energy of +25.9 kJ/mol was obtained for sorption to Syn-1 and was independent of temperature between 286K and 338K. Activation-free energy (ΔG*), activation enthalpy (ΔH*), and activation entropy (ΔS*) for Syn-1 were found to be +62.91 kJ/mol, +23.36 kJ/mol, and -0.130 kJ/(K·mol), respectively. Sorption capacities at pH 3.6, 6.9, and 8.2 were constant at 1.3×10(-2) g denatonium/g clay; however, the kinetic rate constant increased by 56%, going from acidic to basic solution conditions. Distribution coefficients were negatively correlated with ionic strength, suggesting cation exchange. Collectively, results suggested that smectite minerals can serve as efficient sinks for denatonium cations. This is much-needed information for agencies developing regulations regarding denatonium usage and for water treatment professionals who may

  20. Kinetics of sorption of uranium(VI) compounds with zirconium-silica nanosorbents

    NASA Astrophysics Data System (ADS)

    Perlova, O. V.; Sazonova, V. F.; Perlova, N. A.; Yaroshenko, N. A.

    2014-06-01

    The kinetics of sorption of uranium(VI) compounds from sulfate and carbonate solutions using four samples of mesoporous zirconium-silica nanosorbents obtained by bitemplate (solubilization) synthesis was studied. The sorption equilibrium set-in time and the kinetic characteristics of sorption were shown to depend on the sorbent (its composition, specific surface area, dispersity, and pore size), the temperature, and the composition and pH of the solution from which uranium compounds are sorbed. The sorption kinetics was described by a first-order equation. The limiting stage of the process was found to be the external diffusion of uranium-containing particles to the sorbent surface.

  1. Kinetics and Equilibrium Sorption Models: Fitting Plutonium, Strontium, Uranium and Neptunium Loading on Monosodium Titanate (MST)

    SciTech Connect

    Fondeur, F

    2006-03-08

    The Dubinin-Astashov (DA) isotherm parameters for U, Pu, Sr and Np have been updated to include additional data obtained since the original derivation. The DA isotherms were modified to include a kinetic function derived by Rahn to describe sorbate loading from the beginning of sorption up to steady state. The final functions describe both kinetic and thermodynamic sorption.

  2. Kinetics of water sorption in packaging materials for food.

    PubMed

    Weisser, H; Liebenspacher, F

    1991-01-01

    The water content of paper and its time dependence are of great importance for the use of paper and cardboard as packaging materials. The physical process of water sorption and the mechanisms of water "binding" in paper, as fundamental principles of the kinetics, are discussed. Water exists in up to four different "states" (i.e. domains of mobility) in paper: the first layer at the primary sites on the surface of the fibers; the multimolecular layers, with less "binding" energy, on these inner surfaces; condensed water in the voids; and dissolved water in the cellulose fibers. All these "states" influence the shape of the sorption isotherm and correspond to a different water content and to different transport mechanisms. The various types of water "binding" on paper were studied by measuring the transversal relaxation rate, T2, using a pulsed Nuclear Magnetic Resonance spectrometer (minispec pc 120). In addition, a non-destructive, fast method of determining the water content in packaging materials with NMR spectroscopy is described. PMID:1746342

  3. AFFECTS OF MECHANICAL MILLING AND METAL OXIDE ADDITIVES ON SORPTION KINETICS OF 1:1 LiNH2/MgH2 MIXTURE

    SciTech Connect

    Erdy, C.; Anton, D.; Gray, J.

    2010-12-08

    The destabilized complex hydride system composed of LiNH{sub 2}:MgH{sub 2} (1:1 molar ratio) is one of the leading candidates of hydrogen storage with a reversible hydrogen storage capacity of 8.1 wt%. A low sorption enthalpy of {approx}32 kJ/mole H{sub 2} was first predicted by Alapati et al. utilizing first principle density function theory (DFT) calculations and has been subsequently confirmed empirically by Lu et al. through differential thermal analysis (DTA). This enthalpy suggests that favorable sorption kinetics should be obtainable at temperatures in the range of 160 C to 200 C. Preliminary experiments reported in the literature indicate that sorption kinetics are substantially lower than expected in this temperature range despite favorable thermodynamics. Systematic isothermal and isobaric sorption experiments were performed using a Sievert's apparatus to form a baseline data set by which to compare kinetic results over the pressure and temperature range anticipated for use of this material as a hydrogen storage media. Various material preparation methods and compositional modifications were performed in attempts to increase the kinetics while lowering the sorption temperatures. This paper outlines the results of these systematic tests and describes a number of beneficial additions which influence kinetics as well as NH{sub 3} formation.

  4. PCB Congener Sorption To Carbonaceous Sediment Components: Macroscopic Comparison And Characterization Of Sorption Kinetics And Mechanism

    EPA Science Inventory

    Sorption of polychlorinated biphenyls (PCBs) to sediment is a key process in determining their mobility, bioavailability, and chemical decomposition in aquatic environments. In order to examine the validity of currently used interpretation approaches for PCBs sorption, comparati...

  5. Sorption of perfluorooctane sulfonate and perfluorooctanoate on activated carbons and resin: Kinetic and isotherm study.

    PubMed

    Yu, Qiang; Zhang, Ruiqi; Deng, Shubo; Huang, Jun; Yu, Gang

    2009-03-01

    Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have increasingly attracted global concerns in recent years due to their global distribution, persistence, strong bioaccumulation and potential toxicity. The feasibility of using powder activated carbon (PAC), granular activated carbon (GAC) and anion-exchange resin (AI400) to remove PFOS and PFOA from water was investigated with regard to their sorption kinetics and isotherms. Sorption kinetic results show that the adsorbent size influenced greatly the sorption velocity, and both the GAC and AI400 required over 168h to achieve the equilibrium, much longer than 4h for the PAC. Two kinetic models were adopted to describe the experimental data, and the pseudo-second-order model well described the sorption of PFOS and PFOA on the three adsorbents. The sorption isotherms show that the GAC had the lowest sorption capacity both for PFOS and PFOA among the three adsorbents, while the PAC and AI400 possessed the highest sorption capacity of 1.04mmolg(-1) for PFOS and 2.92mmolg(-1) for PFOA according to the Langmuir fitting. Based on the sorption behaviors and the characteristics of the adsorbents and adsorbates, ion exchange and electrostatic interaction as well as hydrophobic interaction were deduced to be involved in the sorption, and some hemi-micelles and micelles possibly formed in the intraparticle pores. PMID:19095279

  6. INFLUENCE OF ORGANIC COSOLVENTS ON THE SORPTION KINETICS OF HYDROPHOBIC ORGANIC CHEMICALS

    EPA Science Inventory

    A quantitative examination of the kinetics of sorption of hydrophobic organic chemicals by soils from mixed solvents reveals that the reverse sorption rate constant (k2) increases log-linearly with increasing volume fraction of organic cosolvent (fc). This relationship was expec...

  7. Kinetic analysis of strontium and potassium sorption onto sands and gravels in a natural channel.

    USGS Publications Warehouse

    Bencala, K.E.; Jackman, A.P.; Kennedy, V.C.; Avanzino, R.J.; Zellweger, G.W.

    1983-01-01

    A kinetic, first-order mass transfer model was used to describe the sorption of strontium onto sand-and gravel-sized streambed sediments. Rate parameters, empirically determined for strontium, allowed for the prediction of potassium sorption with moderate success. The model parameters varied significantly with particle size. The sorption data were collected during an experimental injection of several elements into a small mountain pool-and- riffle stream. The sorption process onto sand- and gravel-sized sediment was relatively slow compared to changes in the dissolved concentrations. -Authors

  8. Sorption enhanced reaction process (SERP) for production of hydrogen

    SciTech Connect

    Sircar, S.; Anand, M.; Carvill, B.

    1995-09-01

    Sorption Enhanced Reaction (SER) is a novel process that is being developed for the production of lower cost hydrogen by steam-methane reforming (SMR). In this process, the reaction of methane with steam is carried out in the presence of an admixture of a catalyst and a selective adsorbent for carbon dioxide. The consequences of SER are: (1) reformation reaction at a significantly lower temperature (300-500{degrees}C) than conventional SMR (800-1100{degrees}C), while achieving the same conversion of methane to hydrogen, (2) the product hydrogen is obtained at reactor pressure (200-400 psig) and at 99+% purity directly from the reactor (compared to only 70-75% H{sub 2} from conventional SMR reactor), (3) downstream hydrogen purification step is either eliminated or significantly reduced in size. The early focus of the program will be on the identification of an adsorbent/chemisorbent for CO{sub 2} and on the demonstration of the SER concept for SMR in our state-of-the-art bench scale process. In the latter stages, a pilot plant will be built to scale-up the technology and to develop engineering data. The program has just been initiated and no significant results for SMR will be reported. However, results demonstrating the basic principles and process schemes of SER technology will be presented for reverse water gas shift reaction as the model reaction. If successful, this technology will be commercialized by Air Products and Chemicals, Inc. (APCI) and used in its existing hydrogen business. APCI is the world leader in merchant hydrogen production for a wide range of industrial applications.

  9. Kinetic modeling of antimony(III) oxidation and sorption in soils.

    PubMed

    Cai, Yongbing; Mi, Yuting; Zhang, Hua

    2016-10-01

    Kinetic batch and saturated column experiments were performed to study the oxidation, adsorption and transport of Sb(III) in two soils with contrasting properties. Kinetic and column experiment results clearly demonstrated the extensive oxidation of Sb(III) in soils, and this can in return influence the adsorption and transport of Sb. Both sorption capacity and kinetic oxidation rate were much higher in calcareous Huanjiang soil than in acid red Yingtan soil. The results indicate that soil serve as a catalyst in promoting oxidation of Sb(III) even under anaerobic conditions. A PHREEQC model with kinetic formulations was developed to simulate the oxidation, sorption and transport of Sb(III) in soils. The model successfully described Sb(III) oxidation and sorption data in kinetic batch experiment. It was less successful in simulating the reactive transport of Sb(III) in soil columns. Additional processes such as colloid facilitated transport need to be quantified and considered in the model. PMID:27214003

  10. 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

  11. Optimization of Nano-Carbon Materials for Hydrogen Sorption

    SciTech Connect

    Yakobson, Boris I

    2013-08-02

    Research undertaken has added to the understanding of several critical areas, by providing both negative answers (and therefore eliminating expensive further studies of unfeasible paths) and positive feasible options for storage. Theoretical evaluation of the early hypothesis of storage on pure carbon single wall nanotubes (SWNT) has been scrutinized with the use of comprehensive computational methods (and experimental tests by the Center partners), and demonstrated that the fundamentally weak binding energy of hydrogen is not sufficiently enhanced by the SWNT curvature or even defects, which renders carbon nanotubes not practical media. More promising direction taken was towards 3-dimensional architectures of high porosity where concurrent attraction of H2 molecule to surrounding walls of nano-scale cavities can double or even triple the binding energy and therefore make hydrogen storage feasible even at ambient or somewhat lower temperatures. An efficient computational tool has been developed for the rapid capacity assessment combining (i) carbon-foam structure generation, (ii) accurate empirical force fields, with quantum corrections for the lightweight H2, and (iii) grand canonical Monte Carlo simulation. This made it possible to suggest optimal designs for carbon nanofoams, obtainable via welding techniques from SWNT or by growth on template-zeolites. As a precursor for 3D-foams, we have investigated experimentally the synthesis of VANTA (Vertically Aligned NanoTube Arrays). This can be used for producing nano-foams. On the other hand, fluorination of VANTA did not show promising increase of hydrogen sorption in several tests and may require further investigation and improvements. Another significant result of this project was in developing a fundamental understanding of the elements of hydrogen spillover mechanisms. The benefit of developed models is the ability to foresee possible directions for further improvement of the spillover mechanism.

  12. Kinetics of sorption of lead on bed sediments of River Hindon, India.

    PubMed

    Sharma, M K; Jain, C K; Singhal, D C; Choubey, V K

    2009-10-01

    A number of low cost waste sorbent have been used for removal of heavy metals, however, few studies have been carried out on the sorption process on riverbed sediments in their natural state of occurrence. Stream sediments adsorb certain solutes from streams, thereby significantly changing the solute composition, but little is known about quantitatively describing sorption phenomena and rates of these processes. In the present investigation, sorption of lead ions on river bed sediments of river Hindon, a tributary of river Yamuna, India has been studied to demonstrate the role of bed sediments in controlling metal pollution. The effect of various operating variables, viz., initial concentration, solution pH, sediment dose, contact time and particle size has been studied. The sorption of lead ions increased with respect to pH and sorbent dose and decreased with sorbent particle size. Two important geochemical phases, iron and manganese oxide, also play important role in the sorption process. The sorption data were analysed using Langmuir and Freundlich isotherm models to determine the mechanistic parameters related to the sorption process. Further, although lead ions have more affinity for the fine fraction of the sediment, but the overall contribution of coarser fraction to sorption is more as compared to clay and silt fraction. The kinetic data suggest that the sorption of lead on bed sediments is an endothermic process, which is spontaneous at low temperature. The uptake of lead is controlled by both bulk and intraparticle diffusion mechanism. PMID:18791802

  13. 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.

  14. Sorption kinetics and mechanism of various oils into kapok assembly.

    PubMed

    Dong, Ting; Wang, Fumei; Xu, Guangbiao

    2015-02-15

    Sorption rates of kapok fibers on different oils, such as diesel, cooking oil, used motor oil, and motor oil, were quantitatively evaluated by using a wicking method. Kapok fibers absorbing different oils exhibited large differences in terms sorption coefficients. Microscopic observations of oil wetting on a single kapok showed that the four oils had varying wettability and adhesiveness to kapok, but that all of them penetrated into kapok lumens quickly because of the fiber's low surface energy, which was 40.64 mN/m, and extreme hydrophobicity, with a water contact angle up to 151°. After treatment with chloroform, there were slight changes in oil absorbencies to kapok, but the sorption coefficients for the four oils increased markedly. SEM demonstrated that chloroform treatments caused the smooth surface of the kapok fibers to become highly roughened, with densely vertical grooves that provided more available surface and a larger driving force for oil sorption through the fiber assembly. PMID:25528222

  15. Materials Down Select Decisions Made Within the Department of Energy Hydrogen Sorption Center of Excellence

    SciTech Connect

    Simpson, Lin

    2009-11-30

    Technical report describing DOE's Hydrogen Sorption Center of Excellence investigation into various adsorbent and chemisorption materials and progress towards meeting DOE's hydrogen storage targets. The report presents a review of the material status as related to DOE hydrogen storage targets and explains the basis for the down select decisions.

  16. SORPTION KINETICS OF PAHS IN METHANOL-WATER SYSTEMS

    EPA Science Inventory

    The objectives of this study were to evaluate the relationships between the equilibrium sorption constant (Kp), the first-order desorption rate coefficient (k2), and the volumetric fraction of water miscible solvent (fc); and to utilize SPARC-calculated (SPARC Performs Automatic ...

  17. Abamectin in soils: Analytical methods, kinetics, sorption and dissipation.

    PubMed

    Dionisio, Andreza Camilotti; Rath, Susanne

    2016-05-01

    Abamectin is a broad-spectrum antiparasitic agent that has been widely employed in veterinary medicine and has also been used as a pesticide in agriculture. Veterinary drugs may reach the soil and may be transported to surface and ground waters, posing risks to terrestrial and aquatic organisms. Sorption, transformation and transport processes are primarily responsible for the fate of these substances in the environment. In this study, the sorption and the aerobic dissipation of abamectin in Brazilian soils (sand, clay and sandy-clay) were evaluated. For sorption studies, batch equilibrium experiments were performed. Sorption and desorption isotherms were fitted to the Freundlich model. Abamectin showed a high affinity to soil particles, with Freundlich sorption and desorption coefficients ranging from 44 to 138 μg(1-1/n) (cm(3))(1/n) g(-1) and from 89 to 236 μg(1-1/n) (cm(3))(1/n) g(-1), respectively. Dissipation of abamectin was evaluated in sterile and non-sterile soils in an aerobic and dark environment under controlled temperature and humidity. The time required for a 50% reduction of the amount of abamectin present in non-sterile soils was up to 4 days, and the time period for 90% dissipation was up to 12 days. In sterilized soils, there was no reduction in the concentration of abamectin over 37 days of exposure, suggesting that aerobic microbial degradation must have been the primary mechanism responsible for the dissipation of abamectin in soils. PMID:26923238

  18. 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.

  19. Kinetics of Ni Sorption in Soils: Roles of Soil Organic Matter and Ni Precipitation

    SciTech Connect

    Shi, Zhenqing; Peltier, Edward; Sparks, Donald L.

    2012-12-10

    The kinetics of Ni sorption to two Delaware agricultural soils were studied to quantitatively assess the relative importance of Ni adsorption on soil organic matter (SOM) and the formation of Ni layered double hydroxide (Ni-LDH) precipitates using both experimental studies and kinetic modeling. Batch sorption kinetic experiments were conducted with both soils at pH 6.0, 7.0, and 7.5 from 24 h up to 1 month. Time-resolved Ni speciation in soils was determined by X-ray absorption spectroscopy (XAS) during the kinetic experiments. A kinetics model was developed to describe Ni kinetic reactions under various reaction conditions and time scales, which integrated Ni adsorption on SOM with Ni-LDH precipitation in soils. The soil Ni speciation (adsorbed phases and Ni-LDH) calculated using the kinetics model was consistent with that obtained through XAS analysis during the sorption processes. Under our experimental conditions, both modeling and XAS results demonstrated that Ni adsorption on SOM was dominant in the short term and the formation of Ni-LDH precipitates accounted for the long-term Ni sequestration in soils, and, more interestingly, that the adsorbed Ni may slowly transfer to Ni-LDH phases with longer reaction times.

  20. Hydrogen sorption in titanium alloys with a symmetric {Sigma}5(310) tilt grain boundary and a (310) surface

    SciTech Connect

    Kulkova, S. E.; Bakulin, A. V.; Kulkov, S. S.; Hocker, S.; Schmauder, S.

    2012-09-15

    The hydrogen sorption in intermetallic B2 TiM (M = Ni, Co, Pd) with a symmetric {Sigma}5(310) tilt grain boundary and a (310) surface is studied by density functional theory methods. The effect of hydrogen on the electronic characteristics of the alloys is analyzed as a function of a sorption position at the interfaces. The hydrogen sorption energy is shown to depend on the local environment of hydrogen; on the whole, hydrogen at the interfaces prefers titanium-rich positions. The hydrogen sorption energy in metal-rich positions decreases when the d shell of the second alloy component is filled with electrons. The grain-boundary energy, the surface energy, and the hydrogen segregation energies to the interfaces are calculated. Hydrogen sorption in titanium alloys is shown to decrease Griffith work and to favor brittle fracture along tilt grain boundaries.

  1. 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.

  2. Sorption enhanced reaction process (SERP) for the production of hydrogen

    SciTech Connect

    Hufton, J.; Mayorga, S.; Gaffney, T.; Nataraj, S.; Rao, M.; Sircar, S.

    1998-08-01

    The novel Sorption Enhanced Reaction Process has the potential to decrease the cost of hydrogen production by steam methane reforming. Current effort for development of this technology has focused on adsorbent development, experimental process concept testing, and process development and design. A preferred CO{sub 2} adsorbent, K{sub 2}CO{sub 3} promoted hydrotalcite, satisfies all of the performance targets and it has been scaled up for process testing. A separate class of adsorbents has been identified which could potentially improve the performance of the H{sub 2}-SER process. Although this material exhibits improved CO{sub 2} adsorption capacity compared to the HTC adsorbent, its hydrothermal stability must be improved. Single-step process experiments (not cyclic) indicate that the H{sub 2}-SER reactor performance during the reaction step improves with decreasing pressure and increasing temperature and steam to methane ratio in the feed. Methane conversion in the H{sub 2}-SER reactor is higher than for a conventional catalyst-only reactor operated at similar temperature and pressure. The reactor effluent gas consists of 90+% H{sub 2}, balance CH{sub 4}, with only trace levels (< 50 ppm) of carbon oxides. A best-case process design (2.5 MMSCFD of 99.9+% H{sub 2}) based on the HTC adsorbent properties and a revised SER process cycle has been generated. Economic analysis of this design indicates the process has the potential to reduce the H{sub 2} product cost by 25--31% compared to conventional steam methane reforming.

  3. Kinetic characteristic of phenanthrene sorption in aged soil amended with biochar

    NASA Astrophysics Data System (ADS)

    Kim, Chanyang; Kim, Yong-Seong; Hyun, Seunghun

    2015-04-01

    Biochar has been recently highlighted as an amendment that affects yield of the crops by increasing pH, cation exchange capacity and water retention, and reduces the lability of contaminants by increasing sorption capacity in the soil system. Biochar's physico-chemical properties, high CEC, surfaces containing abundant micropores and macropores, and various types of functional groups, play important roles in enhancing sorption capacity of contaminants. Aging through a natural weathering process might change physico-chemical properties of biochar amended in soils, which can affect the sorption behavior of contaminants. Thus, in this study, the sorption characteristics of phenanthrene (PHE) on biochar-amended soils were studied with various types of chars depending on aging time. To do this, 1) soil was amended with sludge waste char (SWC), wood char (WC), and municipal waste char (MWC) during 0, 6, and 12 month. Chars were applied to soil at 1% and 2.5% (w/w) ratio. 2) Several batch kinetic and equilibrium studies were conducted. One-compartment first order and two-compartment first order model apportioning the fraction of fast and slow sorbing were selected for kinetic models. Where, qt is PHE concentration in biochar-amended soils at each time t, qeis PHE concentration in biochar-amended soils at equilibrium. ff is fastly sorbing fraction and (1-ff) is slowly sorbing fraction. k is sorption rate constant from one-compartment first order model, k1 and k2 are sorption rate constant from two-compartment first order model, t is time (hr). The equilibrium sorption data were fitted with Fruendlich and Langmuir equation. 3) Change in physico-chemical properties of biochar-amended soils was investigated with aging time. Batch equilibrium sorption results suggested that sorbed amount of PHE on WC was greater than SWC and MWC. The more char contents added to soil, the greater sorption capacity of PHE. Sorption equilibrium was reached after 4 hours and equilibrium pH ranged

  4. Sorption kinetic studies of ammonium from aqueous solution on different inorganic and organic media.

    PubMed

    Kucić, Dajana; Cosić, Ivana; Vuković, Marija; Briski, Felicita

    2013-01-01

    In this study, the sorption of ammonium from aqueous solution onto activated carbon, natural zeolite, peat and potting soil was studied by performing batch kinetic sorption experiments. The activated carbon wasn't efficiently removing ammonium at concentrations higher than 50 mg L(-1). Sorption isotherms of ammonium on zeolite, peat and potting soil were determined at 25 degrees C and 200 rpm with the initial concentration of 50-7000 mg L(-1). Equilibrium data were fitted by Freundlich, Langmuir and Temkin isotherm and parameters were evaluated according these models. Langmuir model gives better fit to experimental data than Freundlich and Temkin models. Maximum adsorption capacities were for activated carbon 0.631 mg g(-1), zeolite 58 mg g(-1), peat 595 mg g(-1) and for potting soil 575 mg g(-1). The equilibrium kinetic data were analyzed using adsorption kinetic models: the pseudo-first and second-order equations and were found to follow the pseudo-second-order kinetic model. A comparison between linear and non-linear regression method for estimating the adsorption and kinetics parameters was examined. The obtained results showed that non-linear method may be a better way to determine the kinetic parameters. Thermodynamic studies showed exothermic and endothermic nature of the adsorption of NH4(+) on inorganic and organic adsorbents, respectively. From present results it can be seen that zeolite, peat and potting soil are good adsorbents for removal ammonium from aqueous solution. PMID:23841339

  5. Effect of γ-ray irradiation on the sorption of hydrogen by nanoporous carbon materials

    NASA Astrophysics Data System (ADS)

    Dolbin, A. V.; Manzhelii, V. G.; Esel'son, V. B.; Gavrilko, V. G.; Vinnikov, N. A.; Basnukaeva, R. M.; Khlistyuck, M. V.; Maletskii, V. P.; Nikolaev, V. G.; Kudriachenko, E. V.; Uvarova, I. Yu.; Tripachko, N. A.; Koda, V. Yu.

    2015-04-01

    The effects of radiation exposure in a hydrogen atmosphere on hydrogen sorption by a synthetic porous carbon nanosorbent, SCN (spherical carbonite saturated). The exposure was created by γ-rays from cobalt-60 (photon energy 1.2 MeV, irradiation dose 4.8 × 107 rad) in a normal hydrogen atmosphere at a pressure of 1 atm and a temperature of 300 K. The processes of hydrogen sorption-desorption by SCN samples before and after irradiation were studied in a temperature interval of 15-1173 K. It was found that the irradiation of SCN in a hydrogen atmosphere significantly increased the amount hydrogen sorbed in the sample. We conducted a comparison with the results of earlier studies investigating the influence of irradiation on the sorption of hydrogen by single-walled carbon nanotubes. The amount of physically sorbed hydrogen in the synthetic SCN sorbent that was irradiated in the hydrogen atmosphere, is four times greater than the amount of hydrogen that was physically sorbed by the single-walled carbon nanotubes that were irradiated under similar conditions. At a temperature below 25 K, the hydrogen diffusion in the SCN was almost temperature independent for the porous subsystem with the highest diffusion coefficients, which is typical for cases when the tunnel diffusion mechanism dominates the thermodynamic mechanism.

  6. Mechanisms and kinetics of coal hydrogenation

    SciTech Connect

    Baldwin, R M; Furlong, M W

    1981-05-01

    Colorado School of Mines is engaged in an experimental program to develop comprehensive models for the effects of coal composition upon the kinetics and mechanisms of coal hydrogenation, for the effects of mineral matter additives (disposable catalysts) upon kinetics and mechanisms of coal hydrogenation, and for the kinetics and mechanisms of the hydrogenation of coal derived products such as preasphaltenes, and asphaltenes. Experimental work was completed on a suite of bituminous coals, thus completing the initial phase of the coal reactivity study. Eleven of the 14 coals of the suite were successfully run in duplicate. Conversion to THF solubles was correlated well by pseudo-second order kinetics. The resulting kinetic rate constants correlated with H/C ratio, mean-max vitrinite reflectance, and a specially-defined fraction of reactive macerals. The data did not correlate well with O/C ratios of the parent coals. Computer-derived statistical fits of various kinetic models were limited in their effectiveness at fitting the experimental data. Experimental work on the first phase of the disposal catalyst studies was completed. Statistical significance testing of the experimental data showed: fractional conversion and yield of light hydrocarbon products increased with time; and mineral properties of the additives were more significant in increasing overall conversion than the additive surface areas. The relative effects of the additives are given.

  7. 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.

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

    DOE PAGESBeta

    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 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

  9. 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

    2015-03-01

    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. PMID:25607800

  10. The Hydriding Kinetics of Organic Hydrogen Getters

    SciTech Connect

    Powell, G. L.

    2002-02-11

    The aging of hermetically sealed systems is often accompanied by the gradual production of hydrogen gas that is a result of the decay of environmental gases and the degradation of organic materials. In particular, the oxygen, water, hydrogen ''equilibrium'' is affected by the removal of oxygen due the oxidation of metals and organic materials. This shift of the above ''equilibrium'' towards the formation of hydrogen gas, particularly in crevices, may eventually reach an explosive level of hydrogen gas or degrade metals by hydriding them. The latter process is generally delayed until the oxidizing species are significantly reduced. Organic hydrogen getters introduced by Allied Signal Aerospace Company, Kansas City Division have proven to be a very effective means of preventing hydrogen gas accumulation in sealed containers. These getters are relatively unaffected by air and environmental gases. They can be packaged in a variety of ways to fit particular needs such as porous pellets, fine or coarse [gravel] powder, or loaded into silicone rubber. The hydrogen gettering reactions are extremely irreversible since the hydrogen gas is converted into an organic hydrocarbon. These getters are based on the palladium-catalyzed hydrogenation of triple bonds to double and then single bonds in aromatic aryl compounds. DEB (1,4 bis (phenyl ethynyl) benzene) typically mixed with 25% by weight carbon with palladium (1% by weight of carbon) is one of the newest and best of these organic hydrogen getters. The reaction mechanisms are complex involving solid state reaction with a heterogeneous catalyst leading to the many intermediates, including mixed alkyl and aryl hydrocarbons with the possibilities of many isomers. The reaction kinetics mechanisms are also strongly influenced by the form in which they are packaged. For example, the hydriding rates for pellets and gravel have a strong dependence on reaction extent (i.e., DEB reduction) and a kinetic order in pressure of 0

  11. Sorption kinetics of zinc and nickel on modified chitosan.

    PubMed

    Tripathi, Nimisha; Choppala, Girish; Singh, Raj S; Srivastava, Prashant; Seshadri, Balaji

    2016-09-01

    This study was conducted to evaluate the effect of equilibration time on adsorption of zinc [Zn(II)] and nickel [Ni(II)] on pure and modified chitosan beads. The initial adsorption of Zn(II) was high on molybdenum (Mo)-impregnated chitosan beads (MoCB) during the initial 60 min. However, after 240 min, Zn(II) adsorption occurred more on single super phosphate chitosan beads (SSPCB), followed by monocalcium phosphate chitosan beads (MCPCB), untreated pure chitosan beads (UCB), and MoCB. Similarly, Ni(II) adsorption was greatest on MoCB during the initial 60 min. At the conclusion of the experiment (at 240 min), the greatest adsorption was occurred on MCPCB, followed by MoCB, UCB, and SSPCB. Chemical sorption and intra-particle diffusion were probably the dominant processes responsible for Zn(II) and Ni(II) sorption onto chitosan beads. The results demonstrated that modified chitosan beads were effective in adsorbing Zn and Ni and hence, could be used for the removal of these toxic metals from soil. PMID:27497960

  12. Kinetics and equilibrium of the sorption of bisphenol A by carbon nanotubes from wastewater.

    PubMed

    Bohdziewicz, J; Kamińska, G

    2013-01-01

    The aim of this study was to determine the sorption potential of carbon nanotubes (CNTs) to bisphenol A (BPA) contained in synthetic wastewater whose composition corresponds to biologically treated effluents. These nanotubes differed in their outer diameter, the number of graphene layers and the presence of modifying functional groups. Based on the nitrogen adsorption-desorption isotherms, mensuration of the specific surface area and pore size distribution was undertaken. The porous structure of the CNTs was bidispersive; the majority consisted of micropores, there was an average fraction of mesopores, and macropores did not occur. On the basis of common kinetics models (pseudo-first-order and pseudo-second-order models), a trial of modelling the kinetics of BPA sorption onto nanotubes was undertaken. The experimental data were well fitted only to the pseudo-second-order models. The kinetics study indicated that adsorption of BPA on CNTs proceeded very fast, with the majority of the adsorbate being adsorbed in the first few seconds. The sorption capacity of nanotubes to BPA was the highest for single-walled CNTs. A decrease in the sorption potential of the nanotubes for higher pH values occurred as a result of the deprotonation of the BPA and formation of bisphenolate anions, consequently leading to a decrease of π-π (hydrophobic) interaction and enhancing electrostatic repulsion. Overall, these results unequivocally confirm the ideal performance and potential of nanotubes for removal of micropollutants from synthetic wastewater. Replicating the conditions occurring in real wastewater allows us to expect a high sorption of BPA in real competitive sorption systems. PMID:24056428

  13. Kinetic research on the sorption of aqueous lead by synthetic carbonate hydroxyapatite.

    PubMed

    Xu, HuanYan; Yang, Lei; Wang, Peng; Liu, Yu; Peng, MingSheng

    2008-01-01

    The sorption of aqueous lead on carbonate-hydroxyapatite (CHAp) is a complicated non-homogeneous solid/water reaction, which from the kinetic point of view has two stages. In the first stage, the reaction rate is so fast and the kinetic pathway so intricate that further research is required. In the second stage, the reaction rate slows down and the reaction process follows that of a first-order kinetic equation. Experimental results show that the relationship between the reaction rate constant k(1) and temperature T agrees with the Arrhenius equation, and that the activation energy of sorption (E(a)) is 11.93 kJ/mol and the frequency factor (A) is 2.51/s. The reaction rate constant k(1) increases with the Pb(2+) initial concentration and decreasing pH, but with increasing CHAp dosage. X-ray diffraction (XRD), scanning electron microscopy with energy dispersion spectrum (SEM-EDS) and toxicity characteristic leaching procedure (TCLP) tests indicate that the main sorption mechanism is dissolution-precipitation, in conjunction with surface sorption. PMID:17360101

  14. Analysis of the importance of sorption kinetics to PCB fate modeling

    SciTech Connect

    Connolly, J.; Dean, M.

    1995-12-31

    A considerable amount of literature exists describing the importance of slow kinetics and resistantly bound fractions to the sorption process for hydrophobic organics such as PCBs. The frequently observed deviations of field measured partition coefficients from the presumed relationship between the organic carbon normalized partition coefficient (K{sub oc}) and octanol-water partition coefficient (K{sub ow}) may be evidence of slow sorption kinetics. Of note are the observations in Green Bay and New Bedford Harbor of increases in PCB partition coefficients along a gradient from high concentration to low concentration. These changes in partitioning were evaluated by incorporating a kinetic model derived from experiments with Hudson River sediment into a model of PCB fate in lower Green Bay. The kinetic model successfully described the observed changes in PCB partition coefficient. The results of this work support the conclusion that sorption kinetics are important to the transport and fate of PCBs. An implication of these results is that the resistant fraction of the sorbed PCBs increases with time. This may result in a decrease in bioavailability that could be significant to the use of models to protect future concentrations and ecological or human health risk.

  15. Kinetics of water vapor sorption on porous glass as a method of porometry

    NASA Astrophysics Data System (ADS)

    Kreisberg, V. A.; Rakcheev, V. P.

    2014-09-01

    Equilibrium low temperature nitrogen adsorption and a new method based on the kinetics of water vapor sorption at room temperature are used for a comparative study of pore morphology of high-silica porous glass. The values of the total pore volume, the specific surfaces, the effective mesopore diameters, and the fraction of each mode in the total mesopore volume are established using both techniques. It is found that the rate of water vapor sorption at constant pressure grows in inverse ratio to the diameter of cylindrical menisci in pores. The time dependence of the volume of adsorbed water is linear, while the characteristic time of filling for each pore mode varies directly with the square of the effective pore mode diameter. The proposed new kinetic porometry technique based on analyzing water vapor adsorption kinetics at room temperature is quite simple as it requires no complicated vacuum equipment and allows the simultaneous examination of large numbers of porous material samples.

  16. Kinetic desorption and sorption of U(VI) during reactive transport in a contaminated Hanford sediment.

    PubMed

    Qafoku, Nikolla P; Zachara, John M; Liu, Chongxuan; Gassman, Paul L; Qafoku, Odeta S; Smith, Steven C

    2005-05-01

    Column experiments were conducted to investigate U(VI) desorption and sorption kinetics in a sand-textured, U(VI)-contaminated (22.7 micromol kg(-1)) capillary fringe sediment from the U.S. Department of Energy (DOE) Hanford site. Saturated column experiments were performed under mildly alkaline 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 contaminant U(VI) desorption in columns where different flow rates were applied. Sorbed, contaminant U(VI) was partially labile (11.8%), and extended leaching times and water volumes were required for complete desorption of the labile fraction. Uranium-(VI) sorption was studied after the desorption of labile, contaminant U(VI) using different U(VI) concentrations in the leaching solution. Strong kinetic effects were observed for both U(VI) sorption and desorption, with half-life ranging from 8.5 to 48.5 h for sorption and from 39.3 to 150 h for desorption. Although U(VI) is semi-mobile in mildly alkaline, subsurface environments, we observed substantial U(VI) adsorption, 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 shortterm U(VI) sorption. Desorption was the slower process. We speculate that the kinetic behavior results from transport or chemical phenomena within the phyllosilicate-dominated fine fraction present in the sediment. 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. PMID:15926566

  17. THE AFFECTS OF HALIDE MODIFIERS ON THE SORPTION KINETICS OF THE LI-MG-N-H SYSTEM

    SciTech Connect

    Erdy, C.; Gray, J.; Lascola, R.; Anton, D.

    2010-12-16

    In this present work, the affects of different transition metal halides (TiCl{sub 3}, VCl{sub 3}, ScCl{sub 3} and NiCl{sub 2}) on the sorption properties of the 1:1 molar ratio of LiNH{sub 2} to MgH{sub 2} are investigated. The modified mixtures were found to contain LiNH{sub 2}, MgH{sub 2} and LiCl. TGA results showed that the hydrogen desorption temperature was reduced with the modifier addition in this order: TiCl{sub 3}>ScCl{sub 3}>VCl{sub 3}>NiCl{sub 2}. Ammonia release was not significantly reduced resulting in a weight loss greater than the theoretical hydrogen storage capacity of the material. The isothermal sorption kinetics of the modified systems showed little improvement after the first dehydrogenation cycle over the unmodified system but showed drastic improvement in rehydrogenation cycles. XRD and Raman spectroscopy identified the cycled material to be composed of LiH, MgH{sub 2}, Mg(NH{sub 2}){sub 2} and Mg{sub 3}N{sub 2}.

  18. THE EFFECTS OF HALIDE MODIFIERS ON THE SORPTION KINETICS OF THE LI-MG-N-H SYSTEM

    SciTech Connect

    Anton, D.; Gray, J.; Price, C.; Lascola, R.

    2011-07-20

    The effects of different transition metal halides (TiCl{sub 3}, VCl{sub 3}, ScCl{sub 3} and NiCl{sub 2}) on the sorption properties of the 1:1 molar ratio of LiNH{sub 2} to MgH{sub 2} are investigated. The modified mixtures were found to contain LiNH{sub 2}, MgH{sub 2} and LiCl. TGA results showed that the hydrogen desorption temperature was reduced with the modifier addition in this order: TiCl{sub 3} > ScCl{sub 3} > VCl{sub 3} > NiCL{sub 2}. Ammonia release was not significantly reduced resulting in a weight loss greater than the theoretical hydrogen storage capacity of the material. The isothermal sorption kinetics of the modified systems showed little improvement after the first dehydrogenation cycle over the unmodified system but showed drastic improvement in rehydrogenation cycles. X-ray diffraction and Raman spectroscopy identified the cycled material to be composed of LiH, MgH{sub 2}, Mg(NH{sub 2}){sub 2} and Mg{sub 3}N{sub 2}.

  19. Synthesis, characterization, and reversible hydrogen sorption study of sodium-doped fullerene

    NASA Astrophysics Data System (ADS)

    Knight, Douglas A.; Teprovich, Joseph A., Jr.; Summers, Andrew; Peters, Brent; Ward, Patrick A.; Compton, Robert N.; Zidan, Ragaiy

    2013-11-01

    Herein is presented a novel, straightforward route to the synthesis of an alkali metal-doped fullerene as well as a detailed account of its reversible and enhanced hydrogen sorption properties in comparison to pure C60. This work demonstrates that a reaction of sodium hydride with fullerene (C60) results in the formation of a sodium-doped fullerene capable of reversible hydrogen sorption via a chemisorption mechanism. This material not only demonstrated reversible hydrogen storage over several cycles, it also showed the ability to reabsorb over three times the amount of hydrogen (relative to the hydrogen content of NaH) under optimized conditions. The sodium-doped fullerene was hydrogenated on a pressure composition temperature (PCT) instrument at 275 ° C while under 100 bar of hydrogen pressure. The hydrogen desorption behavior of this sodium-doped fullerene hydride was observed over a temperature range up to 375 ° C on the PCT and up to 550 ° C on the thermogravimetric analysis (TGA). Powder x-ray diffraction verifies the identity of this material as being Na6C60. Characterization of this material by thermal decomposition analysis (e.g. PCT and TGA methods), as well as FT-IR and mass spectrometry, indicates that the hydrogen sorption activity of this material is due to the reversible formation of a hydrogenated fullerene (fullerane). However, the reversible formation of fullerane was found to be greatly enhanced by the presence of sodium. It was also demonstrated that the addition of a catalytic amount of titanium (via TiO2 or Ti(OBu)4) further enhances the hydrogen sorption process of the sodium-doped fullerene material.

  20. Synthesis, characterization, and reversible hydrogen sorption study of sodium-doped fullerene.

    PubMed

    Knight, Douglas A; Teprovich, Joseph A; Summers, Andrew; Peters, Brent; Ward, Patrick A; Compton, Robert N; Zidan, Ragaiy

    2013-11-15

    Herein is presented a novel, straightforward route to the synthesis of an alkali metal-doped fullerene as well as a detailed account of its reversible and enhanced hydrogen sorption properties in comparison to pure C60. This work demonstrates that a reaction of sodium hydride with fullerene (C60) results in the formation of a sodium-doped fullerene capable of reversible hydrogen sorption via a chemisorption mechanism. This material not only demonstrated reversible hydrogen storage over several cycles, it also showed the ability to reabsorb over three times the amount of hydrogen (relative to the hydrogen content of NaH) under optimized conditions. The sodium-doped fullerene was hydrogenated on a pressure composition temperature (PCT) instrument at 275 °C while under 100 bar of hydrogen pressure. The hydrogen desorption behavior of this sodium-doped fullerene hydride was observed over a temperature range up to 375 °C on the PCT and up to 550 °C on the thermogravimetric analysis (TGA). Powder x-ray diffraction verifies the identity of this material as being Na6C60. Characterization of this material by thermal decomposition analysis (e.g. PCT and TGA methods), as well as FT-IR and mass spectrometry, indicates that the hydrogen sorption activity of this material is due to the reversible formation of a hydrogenated fullerene (fullerane). However, the reversible formation of fullerane was found to be greatly enhanced by the presence of sodium. It was also demonstrated that the addition of a catalytic amount of titanium (via TiO2 or Ti(OBu)4) further enhances the hydrogen sorption process of the sodium-doped fullerene material. PMID:24129505

  1. Sorption kinetics of arsenic on laterite soil in aqueous medium.

    PubMed

    Maji, Sanjoy K; Pal, Anjali; Pal, Tarasankar; Adak, Asok

    2007-06-01

    The efficiency of a locally available laterite soil in removing both arsenite and arsenate from aqueous medium by adsorption was evaluated. It was observed that in batch experiment conducted at 0.5 mg/L initial concentration of arsenic, laterite soil could remove up to 98% of arsenite and 95% of arsenate under optimized conditions. The kinetic profiles under various conditions were developed. Both arsenite and arsenate removal followed pseudo--second order reaction kinetic model. Pore and film diffusion coefficients were determined from the half-time equation and film diffusion appeared to be the rate-limiting. This was further supported by multiple interruption tests. PMID:17558779

  2. Hydrogen-bond kinetics in liquid water

    NASA Astrophysics Data System (ADS)

    Luzar, Alenka; Chandler, David

    1996-01-01

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

  3. Relation of organic contaminant equilibrium sorption and kinetic uptake in plants

    USGS Publications Warehouse

    Li, H.; Sheng, G.; Chiou, C.T.; Xu, O.

    2005-01-01

    Plant uptake is one of the environmental processes that influence contaminant fate. Understanding the magnitude and rate of plant uptake is critical to assessing potential crop contamination and the development of phytoremediation technologies. We determined (1) the partition-dominated equilibrium sorption of lindane (LDN) and hexachlorobenzene (HCB) by roots and shoots of wheat seedlings, (2) the kinetic uptake of LDN and HCB by roots and shoots of wheat seedlings, (3) the kinetic uptake of HCB, tetrachloroethylene (PCE), and trichloroethylene (TCE) by roots and shoots of ryegrass seedlings, and (4) the lipid, carbohydrate, and water contents of the plants. Although the determined sorption and the plant composition together suggest the predominant role of plant lipids for the sorption of LDN and HCB, the predicted partition with lipids of LDN and HCB using the octanol-water partition coefficients is notably lower than the measured sorption, due presumably to underestimation of the plant lipid contents and to the fact that octanol is less effective as a partition medium than plant lipids. The equilibrium sorption or the estimated partition can be viewed as the kinetic uptake limits. The uptakes of LDN, PCE, and TCE from water at fixed concentrations increased with exposure time in approach to steady states. The uptake of HCB did not reach a plateau within the tested time because of its exceptionally high partition coefficient. In all of the cases, the observed uptakes were lower than their respective limits, due presumably to contaminant dissipation in and limited water transpiration by the plants. ?? 2005 American Chemical Society.

  4. Metal-anion sorption by chitosan beads: Equilibrium and kinetic studies

    SciTech Connect

    Guibal, E.; Milot, C.; Tobin, J.M.

    1998-04-01

    Chitosan is a well-known biopolymer, whose high nitrogen content confers remarkable ability for the sorption of metal ions from dilute effluents. However, its sorption performance in both equilibrium and kinetic terms is controlled by diffusion processes. Gel bead formation allows an expansion of the polymer network, which improves access to the internal sorption sites and enhances diffusion mechanisms. Molybdate and vanadate recovery using glutaraldehyde cross-linked chitosan beads reaches uptake capacities as high as 7--8 mmol/g, depending on the pH. The optimum pH (3--3.5) corresponded to the predominance range of hydrolyzed polynuclear metal forms and optimum electrostatic attraction. While for beads, particle size does not influence equilibrium, for flakes, increasing sorbent radius significantly decreases uptake capacities to 1.5 mmol/g. Sorption kinetics are mainly controlled by intraparticle diffusion for beads, while for flakes the controlling mechanisms are both external and intraparticle diffusion. The gel conditioning increases the intraparticle diffusivity by 3 orders of magnitude: intraparticle diffusivities range between 10{sup {minus}13} and 10{sup {minus}10} m{sup 2}/min, depending on the sorbent size and the conditioning.

  5. Feasibility study on high-temperature sorption of hydrogen sulfide by natural soils.

    PubMed

    Ko, Tzu-Hsing; Chu, Hsin; Tseng, Jeou-Jen

    2006-08-01

    In this study, seven natural soils were tested for the sorption of hydrogen sulfide from coal gasification gas at high temperature. Results indicate that the LP natural soil has the best performance and the highest sulfur sorption capacity. After extracting free iron oxides, most natural soils have no sorption efficiency. The free iron oxides, therefore, proved to be the major components that react with hydrogen sulfide to form iron sulfides. The sulfur sorption capacity, either determined by EA or breakthrough time, is very close to the theoretical value based on the stoichiometric calculation with the content of free iron oxides. Moreover, the presence of CO is a positive effect while H2 is a negative effect. This can be explained via the water-shift reaction. On the basis of the results of temperature-programmed sulfidation (TPS), the starting temperature for the sorption of hydrogen sulfide is between 623-673 K. From the analyses of temperature-programmed oxidation (TPO) and XPS, the iron polysulfides are the major products and approximately 90% regeneration efficiency can be theoretically achieved while the temperature is controlled higher than 813 K. In the regeneration tests, the results show that the LP natural soil can be regenerated and thus reused after the oxidation process. No significant degeneration occurs on the LP natural soil after five sorption/regeneration cycles. The sulfur sorption capacity of the tenth regenerated soil can be achieved at least 80% compared to the fresh one. The experimental analyzed SO2 concentration from the regeneration process is almost identical to the theoretical calculated equilibrium concentration of the process. Maghemite is the main product after the regeneration process. PMID:16527331

  6. Molecularly Imprinted Polymers: Thermodynamic and Kinetic Considerations on the Specific Sorption and Molecular Recognition

    PubMed Central

    Li, Songjun; Huang, Xing; Zheng, Mingxia; Li, Wuke; Tong, Kejun

    2008-01-01

    This article presents a work aiming at thermodynamically and kinetically interpreting the specific sorption and recognition by a molecularly imprinted polymer. Using Boc-L-Phe-OH as a template, the imprinted material was prepared. The result indicates that the prepared polymer can well discriminate the imprint species from its analogue (Boc-D-Phe-OH), so as to adsorb more for the former but less for the latter. Kinetic analysis indicates that this specific sorption, in nature, can be a result of a preferential promotion. The imprint within the polymer causes a larger adsorption rate for the template than for the analogue. Thermodynamic study also implies that the molecular induction from the specific imprint to the template is larger than to the analogue, which thus makes the polymer capable of preferentially alluring the template to bind.

  7. The kinetics of fluoride sorption by zeolite: Effects of cadmium, barium and manganese.

    PubMed

    Cai, Qianqian; Turner, Brett D; Sheng, Daichao; Sloan, Scott

    2015-01-01

    Industrial wastewaters often consist of a complex chemical cocktail with treatment of target contaminants complicated by adverse chemical reactions. The impact of metal ions (Cd(2+), Ba(2+) and Mn(2+)) on the kinetics of fluoride removal from solution by natural zeolite was investigated. In order to better understand the kinetics, the pseudo-second order (PSO), Hill (Hill 4 and Hill 5) and intra-particle diffusion (IPD) models were applied. Model fitting was compared using the Akaike Information Criterion (AIC) and the Schwarz Bayesian Information Criterion (BIC). The Hill models (Hill 4 and Hill 5) were found to be superior in describing the fluoride removal processes due to the sigmoidal nature of the kinetics. Results indicate that the presence of Mn (100 mg L(-1)) and Cd (100 mg L(-1)) respectively increases the rate of fluoride sorption by a factor of ~28.3 and ~10.9, the maximum sorption capacity is increased by ~2.2 and ~1.7. The presence of Ba (100 mg L(-1)) initially inhibited fluoride removal and very poor fits were obtained for all models. Fitting was best described with a biphasic sigmoidal model with the degree of inhibition decreasing with increasing temperature suggesting that at least two processes are involved with fluoride sorption onto natural zeolite in the presence of Ba. PMID:25909159

  8. The kinetics of fluoride sorption by zeolite: Effects of cadmium, barium and manganese

    NASA Astrophysics Data System (ADS)

    Cai, Qianqian; Turner, Brett D.; Sheng, Daichao; Sloan, Scott

    2015-06-01

    Industrial wastewaters often consist of a complex chemical cocktail with treatment of target contaminants complicated by adverse chemical reactions. The impact of metal ions (Cd2 +, Ba2 + and Mn2 +) on the kinetics of fluoride removal from solution by natural zeolite was investigated. In order to better understand the kinetics, the pseudo-second order (PSO), Hill (Hill 4 and Hill 5) and intra-particle diffusion (IPD) models were applied. Model fitting was compared using the Akaike Information Criterion (AIC) and the Schwarz Bayesian Information Criterion (BIC). The Hill models (Hill 4 and Hill 5) were found to be superior in describing the fluoride removal processes due to the sigmoidal nature of the kinetics. Results indicate that the presence of Mn (100 mg L- 1) and Cd (100 mg L- 1) respectively increases the rate of fluoride sorption by a factor of ~ 28.3 and ~ 10.9, the maximum sorption capacity is increased by ~ 2.2 and ~ 1.7. The presence of Ba (100 mg L- 1) initially inhibited fluoride removal and very poor fits were obtained for all models. Fitting was best described with a biphasic sigmoidal model with the degree of inhibition decreasing with increasing temperature suggesting that at least two processes are involved with fluoride sorption onto natural zeolite in the presence of Ba.

  9. Sorption of basic dyes onto granulated pillared clays: thermodynamic and kinetic studies.

    PubMed

    Cheknane, B; Zermane, F; Baudu, M; Bouras, O; Basly, J P

    2012-09-01

    Effect of the granulation process onto the thermodynamic and kinetic sorption parameters of two basic dyes (Basic Yellow 28-BY 28 and Basic Green 4-BG 4) was evaluated in the present work. The charge surface properties of the surfactant-modified aluminium-pillared clay (CTAB-Al-Mont-PILC) particles were not modified, and the isoelectric point remains constant after high shear wet granulation. The Gibbs free energy of both BY 28 and BG 4 sorption was negative and decreased with the granulation; the endothermic nature of the sorption process was confirmed by the positive values of ΔH°. Adsorption kinetics of the two dyes, studied at pH 6 and 150 mg L(-1), follow the pseudo-first order kinetic model with observed rate constants of 2.5-4.2×10(-2) min(-1). The intraparticle diffusion model, proposed by Weber and Morris, was applied, and the intraparticle plots revealed three distinct sections representing external mass transfer, intraparticle diffusion and adsorption/desorption equilibrium. Diffusion coefficients, calculated from the Boyd kinetic equation, increased with the granulation and the particle size. Pseudo-first order kinetic constants, intraparticle diffusion rate constants and diffusion coefficients were determined for two other initial concentrations (50 and 100 mg L(-1)) and include in a statistical study to evaluate the impact of granulation and initial concentration on the kinetic parameters. Kruskal-Wallis tests, Spearman's rank order correlation and factor analysis revealed a correlation between (i) the diffusion coefficients and granulation, and between (ii) the intraparticle diffusion rate constants and initial concentration. PMID:22721789

  10. Sorption kinetics of Cs and Sr in sediments of a Savannah River Site reservoir

    SciTech Connect

    Stephens, J.A.

    1997-07-01

    Laboratory measurements of the sorption and desorption of {sup 134}Cs and {sup 85}Sr to sediments were conducted. These sediments were sampled from the profundal zone of Par Pond at the Savannah River Site, Aiken, South Carolina. The isotopes {sup 134}Cs and {sup 85}Sr were used to trace the sorption properties of the main contaminants found in the reservoir which are {sup 137}Cs and {sup 90}Sr respectively. The sorption behavior of these two elements was studied using spiked sediment/water slurries of a known mass to volume ratio. The results reveal that Sr undergoes significant reversible sorption while a fraction of Cs irreversibly sorbs to the sediment. The calculated distribution coefficient Kd at equilibrium was (3 {+-} 0.6) x 10{sup 3} for {sup 134}Cs after 60 d and (1 {+-} 0.2) x 10{sup 3} for {sup 85}Sr after 7 d at pH {approx} 6 and slurry ratio of 1:1000 g/ml. The K{sub d} for {sup 134}Cs ranged from 2 x 10{sup 2} to 3 x 10{sup 4} depending on pH and conductivity. The {sup 85}Sr reached equilibrium in a few days, while {sup 134}Cs reached an apparent equilibrium in 1--2 months. The K{sub d} for {sup 134}Cs was a function of the slurry ratio, pH, conductivity, and contact time. These factors were interrelated since the sediments released ions to the slurry mixture which decreased the pH and increased the conductivity. A sorption isotherm measured for {sup 134}Cs was linear at water concentrations from 60 mBq/ml to 20 Bq/ml. A kinetic model was proposed to describe the basic sorption of {sup 134}Cs to Par Pond sediments under homogeneous laboratory conditions.

  11. Stable carbon and hydrogen isotope fractionation of dissolved organic groundwater pollutants by equilibrium sorption

    NASA Astrophysics Data System (ADS)

    Höhener, Patrick; Yu, Xianjing

    2012-03-01

    Linear free energy relationships (LFERs) were established which relate equilibrium vapor-liquid isotope effects to stable carbon and hydrogen isotope enrichment factors for equilibrium sorption to geosorbents. The LFERs were established for normal, cyclic or branched alkanes, monoaromatic hydrocarbons, and chloroethenes. These LFERs predict that isotopic light compounds sorb more strongly than their heavy counterparts. Defining fractionation as in classical literature by "heavy divided by light", carbon enrichment factors for equilibrium sorption were derived which ranged from - 0.13 ± 0.04‰ (benzene) to - 0.52 ± 0.19‰ (trichloroethene at 5-15 °C). Hydrogen enrichment factors for sorption of 14 different compounds were between - 2.4 and - 9.2‰. For perdeuterated hydrocarbons the predicted enrichment factors ranged from - 19 ± 5.4‰ (benzene) to - 64 ± 30‰ (cyclohexane). Equilibrium sorption experiments with a soil and activated carbon as sorbents were performed in the laboratory for perdeuterocyclohexane and perdeuterotoluene. The measured D/H enrichments agreed with the LFER prediction for both compounds and both sorbents within the uncertainty estimate of the prediction. The results of this work suggest that equilibrium sorption does create only very small isotope shifts for 13C in groundwater pollutants in aquifers. It is also suggested that deuterium shifts are expected to be higher, especially for strongly sorbing pollutants.

  12. Kinetic modeling of pH-dependent antimony (V) sorption and transport in iron oxide-coated sand.

    PubMed

    Cai, Yongbing; Li, Lulu; Zhang, Hua

    2015-11-01

    Understanding the mechanisms and kinetics controlling the retention and transport of antimony (Sb) is prerequisite for evaluating the risk of groundwater contamination by the toxic element. In this study, kinetic batch and saturated miscible displacement experiments were performed to investigate effects of protonation-deprotonation reactions on sorption-desorption and transport of Sb(V) in iron oxide-coated sand (IOCS). Results clearly demonstrated that Sb(V) sorption was highly nonlinear and time dependent, where both sorption capacity and kinetic rates decreased with increasing solution pH. Breakthrough curves (BTCs) obtained at different solution pH exhibited that mobility of Sb(V) were higher under neutral to alkaline condition than under acidic condition. Because of the nonlinear and non-equilibrium nature of Sb(V) retention and transport, multi-reaction models (MRM) with equilibrium and kinetic sorption expressions were utilized successfully to simulate the experiment data. Equilibrium distribution coefficient (Ke) and reversible kinetic retention parameters (k1 and k2) of both kinetic sorption and transport experiment showed marked decrease as pH increased from 4.0 to 7.5. Surface complexation is suggested as the dominant mechanism for the observed pH-dependent phenomena, which need to be incorporated into the kinetic models to accurately simulate the reactive transport of Sb(V) in vadose zone and aquifers. PMID:26291756

  13. Catalytic mechanism of transition-metal compounds on Mg hydrogen sorption reaction.

    PubMed

    Barkhordarian, Gagik; Klassen, Thomas; Bormann, Rüdiger

    2006-06-01

    The catalytic mechanisms of transition-metal compounds during the hydrogen sorption reaction of magnesium-based hydrides were investigated through relevant experiments. Catalytic activity was found to be influenced by four distinct physico-thermodynamic properties of the transition-metal compound: a high number of structural defects, a low stability of the compound, which however has to be high enough to avoid complete reduction of the transition metal under operating conditions, a high valence state of the transition-metal ion within the compound, and a high affinity of the transition-metal ion to hydrogen. On the basis of these results, further optimization of the selection of catalysts for improving sorption properties of magnesium-based hydrides is possible. In addition, utilization of transition-metal compounds as catalysts for other hydrogen storage materials is considered. PMID:16771356

  14. Kinetics of selenate sorption in soil as influenced by biotic and abiotic conditions: a stirred flow-through reactor study.

    PubMed

    Garcia-Sanchez, L; Loffredo, N; Mounier, S; Martin-Garin, A; Coppin, F

    2014-12-01

    This study (i) quantified the kinetics of selenate sorption and (ii) measured the influence of biotic processes in soil selenate stabilisation. Stirred flow-through reactor experiments were conducted on samples of a silty clay soil (pH = 8, Eh = 240-300 mV) from Bure (France) in both non-sterile and sterile conditions. Parameters of the proposed two-site sorption model (EK), adapted from van Genuchten and Wagenet (1989), were estimated by nonlinear regression. Fast selenate sorption on type-1 sites was moderate, with an equilibrium constant of 25.5 and 39.1 L/kg for non-sterile and sterile conditions. Rate-limited sorption on type-2 sites increased with time, and was predominant for longer periods of time in non-sterile conditions. At equilibrium, it would represent over 96% of the sorbed inventory, with mean sorption times of 17 h and 191 h for non-sterile and sterile conditions. Our results showed for Bure soil that (i) selenate sorption in flowing and mildly-oxidising conditions was strongly kinetically controlled, especially in non-sterile conditions, (ii) selenate desorption was much slower than sorption, which suggests its pseudo-irreversible stabilisation, and (iii) microbial activity increased the contribution of rate-limited sorption on type-2 sites, for which it increased sorption rate by a factor 7 but also facilitated its reversibility. This work stresses the limits of the Kd approach to represent selenate sorption in flowing conditions and supports an alternative formulation like the EK model, but also points out that biotic conditions are significant sources of variability for sorption parameters. PMID:25151638

  15. Sorption kinetics of Zn (II) ion by thermally treated rice husk

    NASA Astrophysics Data System (ADS)

    Ong, K. K.; Tarmizi, A. F. A.; Wan Yunus W. M., Z.; Safidin, K. M.; Fitrianto, A.; Hussin, A. G. A.; Azmi, F. M.

    2015-05-01

    Agricultural wastes such as orange peels, tea leave waste, rice husk and corn cobs have been widely studied as sorbents for heavy metal ion removal from various wastewaters. In order to understand their sorption mechanism, the adsorption kinetics is studied. This report describes the kinetics study of a thermally treated rice husk to adsorb Zn (II) ion from an aqueous solution. The adsorbent was obtained by heating the rice husk in a furnace at 500°C for two hours. Increase the contact period improved percentage of the removal of Zn (II) ion until an equilibrium was reached. The data obtained showed that the adsorption of Zn (II) ion by thermally treated rice husk obeyed pseudo-second order kinetics model, which is in agreement with chemisorption as the rate limiting mechanism.

  16. Kinetics of lead and copper removal from oil-field brine by potential sorption.

    PubMed

    Nourafkan, E; Asachi, M; Marandi, R

    2014-01-01

    The present study investigates the kinetics of lead and copper removal from oil-field brine by potential sorption. A population balance equation, coupled with a mass balance equation, was used in the estimation of kinetic parameters. Metal removal was performed by potential sorption of lead and copper through CaCO3 precipitates induced by the reaction of Na2CO3 and CaCl2. The oil-field brine was selected from an oil well in Gachsaran, Iran. The crystal size distribution of the solid phase was measured by dynamic laser scattering analyzer, and the liquor phase was analyzed using atomic adsorption. The morphology of calcium carbonate particles was illustrated using scanning electron microscopy and X-ray diffraction. The results showed that the presence of copper and lead decreases the average size distribution of calcium carbonate particles by influencing the kinetic parameters. Lead and copper concentrations were reduced from 2.911 to 0.127 ppm (95.63% removal) and 0.476 to 0.025 ppm (94.74% removal), respectively, in exchange for 12 g CaCO3 consumption per 100 ml oil-field brine. PMID:25521137

  17. Kinetics studies of uranium sorption by powdered corn cob in batch and fixed bed system

    PubMed Central

    Mahmoud, Mohamed A.

    2015-01-01

    Sorption of uranium (VI) from aqueous solution onto powdered corn cob has been carried out using batch and fixed-bed technique. The experimental results in batch technique were fitted well with pseudo second-order kinetics model. In the fixed bed technique, Thomas and Bohart–Adams models were evaluated by linear regression analysis for U(VI) uptake in different flow rates, bed heights and initial concentrations. The column experimental data were fitted well with Thomas mode (r2 = 0.999), but the Bohart–Adams model (r2 = 0.911), predicted poor performance of fixed-bed column. PMID:26843973

  18. Biodegradation kinetic constants and sorption coefficients of micropollutants in membrane bioreactors.

    PubMed

    Fernandez-Fontaina, Eduardo; Pinho, Ines; Carballa, Marta; Omil, Francisco; Lema, Juan M

    2013-04-01

    In order to elucidate the capability of biomass developed in membrane bioreactors (MBR) to degrade and sorb emerging micropollutants, biodegradation (kbiol) and sorption (ksor) kinetic constants as well as solid-liquid partition coefficients (Kd) of 13 selected pharmaceutical and personal care products (PPCPs) were determined with MBR heterotrophic biomass adding a pulse (100 ppb of each compound) and following the liquid and solid phase concentrations over time. The results obtained were compared to literature data referring to conventional activated sludge (CAS) systems. Two experiments were performed: one in the MBR itself and the second one in a batch reactor with the same type and concentration of biomass as in the MBR. Overall, both biodegradation and sorption coefficients were in the same range as previously reported by other studies in CAS systems, indicating that MBR biomass does not show better capabilities for the biological degradation and/or sorption of PPCPs compared to the biomass developed in CAS reactors. Therefore, the higher PPCPs removal efficiencies found in MBRs are explained by the high biomass concentrations obtained at the long sludge retention times at which this type of reactors are usually operated. PMID:22773131

  19. 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.

  20. Sorption and reaction kinetics of arsenate and arsenite from aqueous solution by waste cast iron

    NASA Astrophysics Data System (ADS)

    Kim, B. J.; Cho, k. H.; Wi, D. W.; Choi, N. C.; Park, C. Y.

    2012-04-01

    The Sorption and reaction kinetics of As(III) and As(V) from aqueous solution was investigated using waste cast iron, which is a byproduct of the iron casting process in foundries. Two types of waste cast iron were used in the experiment: grind precipitate dust (GPD) and cast iron shot (CIS). The X-ray diffraction analysis indicated the presence of Fe0 on GPD and CIS. Non-equilibrium batch experiments were performed under different concentrations of As(III) and As(V) and in the absence/presence of PO4-3 for prevention of sorption effect. Results showed that waste cast iron was effective in the removal of As(III) and As(V). The removal parameter pattern indicated that the two-stage reduction pattern type (consists of fast reduction type (sorption and reaction) and limited slow (reaction) type) was better than the first order reduction pattern at describing the experimental result. In the reduction of both As(III) and As(V), the reduction capacity of GPD was greater than CIS, mainly due to the fact that GPD had higher surface area and weight percent of Fe than CIS. The results of reduction parameter estimation revealed that In the removal of As(III) and As(V) by GPD and CIS case, both GPD and CIS were more effective at the removal of sorption and reaction than reaction under given experimental conditions. This study demonstrates that waste cast iron has potential as a reactive material to treat wastewater and groundwater containing arsenic.

  1. Sorption kinetics and equilibrium uptake for water vapor in soft-contact-lens hydrogels.

    PubMed

    Weinmüller, C; Langel, C; Fornasiero, F; Radke, C J; Prausnitz, J M

    2006-05-01

    A gravimetric-sorption technique was used to obtain kinetic and equilibrium adsorption/desorption data for water vapor in four different soft-contact-lens (SCL) polymers at 35 degrees C. The SCL materials are a conventional hydrogel (polymacon) with a low water content at saturation (<50 wt %); two conventional hydrogels (hilafilcon A and alphafilcon A) with a high water content at saturation (>50 wt %); and a siloxane hydrogel (balafilcon A). Absorption and desorption equilibrium isotherms (water activity versus water weight fraction) overlap at high water contents, whereas significant hysteresis is observed at low water contents. The hysteresis loop is likely due to trapping of water in the polymer during the desorption process because of a rubber-to-glass transition of the SCL-film surfaces. Sorption data were interpreted using Flory-Rehner theory. The positive Zimm and Lundberg cluster function suggests that water tends to cluster in these SCL materials, except at very low water content. For polymacon and hilafilcon A, Fickian diffusion is observed for all activities for both water sorption and desorption. However, for alphafilcon A and balafilcon A, non-Fickian features appear at intermediate/low activities, in particular during water desorption, suggesting coupling of the diffusion process with polymer-matrix relaxation. The diffusion coefficient increases significantly with water concentration for polymacon and hilafilcon A (from approximately 0.3 x 10(-8) to 4.0 x 10(-8) cm2/s) because of augmented mixture free volume induced by water sorption, whereas a more complex composition dependence is observed for alphafilcon A and balafilcon A probably as consequence of a combined effect of polymer relaxation, plasticization, and water clustering. PMID:16392136

  2. Sorption enhanced reaction process for production of hydrogen. Phase 1 final report

    SciTech Connect

    Mayorga, S.G.; Hufton, J.R.; Sircar, S.; Gaffney, T.R.

    1997-07-01

    Hydrogen is one of the most suitable energy sources from both technological and environmental perspectives for the next century, especially in the context of a sustainable global energy economy. The most common industrial process to produce high-purity (99.99+ mol%) hydrogen is to reform natural gas by a catalytic reaction with steam at a high temperature. Conventional steam-methane reforming (SMR) contributed to approximately 2.4 billion standard cubic feet per day (SCFD) of hydrogen production in the US. By 1998, the growth of SMR-produced hydrogen in the US is expected to reach 3.4 billion SCFD, with the increased demand attributed to hydrogen`s use in reformulated gasolines required by the Clean Air Act. The goal of this work is to develop an even more efficient process for reforming steam and methane to hydrogen product than the conventional SMR process. The application of Sorption Enhanced Reaction (SER) technology to SMR has the potential to markedly reduce the cost of hydrogen through lower capital and energy requirements. The development of a more cost-effective route to hydrogen production based on natural gas as the primary energy source will accelerate the transition to a more hydrogen-based economy in the future. The paper describes the process, which includes a sorbent for CO{sub 2} removal, and the various tasks involved in its development.

  3. Imidacloprid sorption kinetics, equilibria, and degradation in sandy soils of Florida.

    PubMed

    Leiva, Jorge A; Nkedi-Kizza, Peter; Morgan, Kelly T; Qureshi, Jawwad A

    2015-05-27

    Imidacloprid (IMD) is a neonicotinoid insecticide soil-drenched on sandy soils of southwest Florida for the control of Diaphorina citri Kuwayama or Asian citrus psyllid (ACP). The ACP vectors causal pathogens of a devastating citrus disease called citrus greening. Understanding the behavior of IMD in these soils and plants is critical to its performance against target pests. Samples from Immokalee fine sand (IFS) were used for sorption kinetics and equilibria experiments. IMD kinetics data were described by the one-site mass transfer (OSMT) model and reached equilibrium between 6 and 12 h. Batch equilibrium and degradation studies revealed that IMD was weakly sorbed (K(OC) = 163-230) and persistent, with a half-life of 1.0-2.6 years. Consequently, IMD has the potential to leach below the citrus root zone after the soil-drench applications. PMID:25938475

  4. 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.

  5. Synthesis and characterization of MnPS{sub 3} for hydrogen sorption

    SciTech Connect

    Ismail, N.; Temerk, Y.M.; El-Meligi, A.A.; Badr, M.A.; Madian, M.

    2010-05-15

    Single phase MnPS{sub 3} powder was prepared by solid state reaction between Mn, S and P carried out at 650 deg. C in evacuated silica tube. The structure, morphology and sorption characteristics of the prepared solid were investigated. The results revealed that the obtained MnPS{sub 3} compound was capable of adsorbing 3.5 wt% hydrogen at -193 deg. C and a pressure of 30 bar. Little amount of hydrogen (0.07 wt%) was adsorbed at room temperature. The hydrogen adsorption/desorption cycles at various temperatures did not result in irreversible chemical structural changes of the MnPS{sub 3} compound, but the microstructure after hydrogen cycling diminished and became finer. - Graphical abstract: Atomic building of MPS{sub 3}

  6. Pd nanoparticles embedded into a metal-organic framework: synthesis, structural characteristics, and hydrogen sorption properties.

    PubMed

    Zlotea, Claudia; Campesi, Renato; Cuevas, Fermin; Leroy, Eric; Dibandjo, Philippe; Volkringer, Christophe; Loiseau, Thierry; Férey, Gérard; Latroche, Michel

    2010-03-10

    The metal-organic framework MIL-100(Al) has been used as a host to synthesize Pd nanoparticles (around 2.0 nm) embedded within the pores of the MIL, showing one of the highest metal contents (10 wt %) without degradation of the porous host. Textural properties of MIL-100(Al) are strongly modified by Pd insertion, leading to significant changes in gas sorption properties. The loss of excess hydrogen storage at low temperature can be correlated with the decrease of the specific surface area and pore volume after Pd impregnation. At room temperature, the hydrogen uptake in the composite MIL-100(Al)/Pd is almost twice that of the pristine material. This can be only partially accounted by Pd hydride formation, and a "spillover" mechanism is expected to take place promoting the dissociation of molecular hydrogen at the surface of the metal nanoparticles and the diffusion of monatomic hydrogen into the porosity of the host metal-organic framework. PMID:20155921

  7. Modeling the sorption kinetic of metsulfuron-methyl on Andisols and Ultisols volcanic ash-derived soils: kinetics parameters and solute transport mechanisms.

    PubMed

    Cáceres, Lizethly; Escudey, Mauricio; Fuentes, Edwar; Báez, María E

    2010-07-15

    Metsulfuron-methyl sorption kinetic was studied in Andisol and Ultisol soils in view of their distinctive physical and chemical properties: acidic pH and variable surface charge. Different kinetic models were applied to the experimental results. The pseudo-second-order model fitted sorption kinetics data better than the pseudo-first-order model. The rate constant and the initial rate constant values obtained through this model demonstrated the different behavior of metsulfuron-methyl in both kinds of soils, both parameters being the highest for Andisol. The application of Elovich equation, intraparticle diffusion model and a two-site nonequilibrium model (TSNE) allowed to conclude that: (i) the high organic matter content is the governing factor for Andisols where mass transfer across the boundary layer, and in a lesser degree, intraparticle diffusion were the two processes controlling sorption kinetic and (ii) the mineral composition was more relevant in Ultisols where rate was controlled almost exclusively by intraparticle diffusion into macropores and micropores. The slower sorption rate on Ultisols, the mechanism involved and the lower sorption capacity of this kind of soils must be taken into account to assess leaching behavior of this herbicide. PMID:20399011

  8. Carbon and hydrogen isotope effects during sorption of organic contaminants on carbonaceous materials.

    PubMed

    Schüth, Christoph; Taubald, Heinrich; Bolaño, Nerea; Maciejczyk, Kirsten

    2003-07-01

    Stable carbon and hydrogen isotopes can be an efficient means to validate biodegradation of organic contaminants in groundwater since it results in an isotopic fractionation. A prerequisite in applying this method in the field is the proof that other processes decreasing the contaminant concentration are conservative with respect to isotope effects. In this paper we show for carbon isotopes of halogenated hydrocarbon compounds [trichloroethene (TCE), cis-dichloroethene (c-DCE), vinylchloride (VC)] and carbon and hydrogen isotopes of BTEX compounds (benzene, toluene, p-xylene) that no significant fractionation occurs during equilibrium sorption onto activated carbon, lignite coke and lignite. In general, effects were in the range of the reproducibility limit of the analytical instrument (0.5 per thousand for delta13C, and 8 per thousand for delta2H). This observation was made for fractions sorbed of less than 5% to more than 95%. Also for rate-limited sorption of TCE onto activated carbon, no significant fractionation in carbon isotopes could be observed. These findings support the assumption that for these classes of compounds, sorption processes in aquifer systems are conservative with respect to isotope effects. PMID:12814884

  9. Hydrogen sorption characteristics of nanostructured Pd–10Rh processed by cryomilling

    DOE PAGESBeta

    Yang, Nancy; Yee, Joshua K.; Zhang, Zhihui; Kurmanaeva, Lilia; Cappillino, Patrick; Stavila, Vitalie; Lavernia, Enrique J.; San Marchi, Chris

    2014-10-03

    Palladium and its alloys are model systems for studying solid-state storage of hydrogen. Mechanical milling is commonly used to process complex powder systems for solid-state hydrogen storage; however, milling can also be used to evolve nanostructured powder to modify hydrogen sorption characteristics. In the present study, cryomilling (mechanical attrition milling in a cryogenic liquid) is used to produce nanostructured palladium-rhodium alloy powder. Characterization of the cryomilled Pd-10Rh using electron microscopy, X-ray diffraction, and surface area analysis reveals that (i) particle morphology evolves from spherical to flattened disk-like particles; while the (ii) crystallite size decreases from several microns to less thanmore » 100 nm and (iii) dislocation density increases with increased cryomilling time. Hydrogen absorption and desorption isotherms as well as the time scales for absorption were measured for cryomilled Pd-10Rh, and correlated with observed microstructural changes induced by the cryomilling process. In short, as the microstructure of the Pd-10Rh alloy is refined by cryomilling: (i) the maximum hydrogen concentration in the α-phase increases, (ii) the pressure plateau becomes flatter, and (iii) the equilibrium hydrogen capacity at 760 Torr increases. In addition, the rate of hydrogen absorption was reduced by an order of magnitude compared to non-cryomilled (atomized) powder.« less

  10. Hydrogen sorption characteristics of nanostructured Pd–10Rh processed by cryomilling

    SciTech Connect

    Yang, Nancy; Yee, Joshua K.; Zhang, Zhihui; Kurmanaeva, Lilia; Cappillino, Patrick; Stavila, Vitalie; Lavernia, Enrique J.; San Marchi, Chris

    2014-10-03

    Palladium and its alloys are model systems for studying solid-state storage of hydrogen. Mechanical milling is commonly used to process complex powder systems for solid-state hydrogen storage; however, milling can also be used to evolve nanostructured powder to modify hydrogen sorption characteristics. In the present study, cryomilling (mechanical attrition milling in a cryogenic liquid) is used to produce nanostructured palladium-rhodium alloy powder. Characterization of the cryomilled Pd-10Rh using electron microscopy, X-ray diffraction, and surface area analysis reveals that (i) particle morphology evolves from spherical to flattened disk-like particles; while the (ii) crystallite size decreases from several microns to less than 100 nm and (iii) dislocation density increases with increased cryomilling time. Hydrogen absorption and desorption isotherms as well as the time scales for absorption were measured for cryomilled Pd-10Rh, and correlated with observed microstructural changes induced by the cryomilling process. In short, as the microstructure of the Pd-10Rh alloy is refined by cryomilling: (i) the maximum hydrogen concentration in the α-phase increases, (ii) the pressure plateau becomes flatter, and (iii) the equilibrium hydrogen capacity at 760 Torr increases. In addition, the rate of hydrogen absorption was reduced by an order of magnitude compared to non-cryomilled (atomized) powder.

  11. Sorption of methylene blue on treated agricultural adsorbents: equilibrium and kinetic studies

    NASA Astrophysics Data System (ADS)

    Tiwari, D. P.; Singh, S. K.; Sharma, Neetu

    2015-03-01

    Agricultural adsorbents are reported to have a remarkable performance for adsorption of dyes. In the present study, formaldehyde and sulphuric acid treated two agricultural adsorbents; potato peel and neem bark are used to adsorb methylene blue. On the whole, the acid-treated adsorbents are investigated to have high sorption efficiency compared to HCHO treated adsorbents. The percentage removal efficiency of H2SO4 treated potato peel (APP) increases considerably high from 75 to 100 % with increase in adsorbent dose, whereas the removal efficiency of H2SO4 treated neem bark (ANB) is found to be 98 % after adding the first dose only. The monolayer sorption behaviour of HCHO treated potato peel (PP) and APP is well defined by Langmuir, whereas the chemisorptions behaviour of HCHO treated neem bark (NB) and ANB is suggested by Temkin's isotherm model. The maximum adsorption capacity measured is highest in ANB followed by NB, PP and APP with the values of 1000, 90, 47.62 and 40.0 mg/g, respectively. The pseudo-second-order kinetic model fitted well with the observed data of all the four adsorbents. The results obtained reveal that NB and ANB both are good adsorbents compared to PP and APP.

  12. Quantum effects in the sorption kinetics of 4He by mesoporous materials

    NASA Astrophysics Data System (ADS)

    Dolbin, A. V.; Khlistyuck, M. V.; Esel'son, V. B.; Gavrilko, V. G.; Vinnikov, N. A.; Basnukaeva, R. M.; Danchuk, V. V.

    2016-02-01

    Sorption and desorption of 4He by a mesoporous silicate material MCM-41 was studied in the temperature range of 1.5-290 K. It was shown that for T = 25-290 K the thermal activation mechanism is dominant in the sorption kinetics of 4He atoms by an MCM-41 sample. Its activation energy was estimated as Ea ≈ 164.8 K. For T = 12-23 K, the diffusion of 4He atoms in the MCM-41 was practically independent of temperature, which typically occurs when the tunnelling mechanism of diffusion dominates over the thermally activated one. A change in the mobility of 4He atoms in MCM-41 channels was observed at T = 6-12 K, which may be indicative of the formation upon cooling (or decay upon heating) of a 4He monolayer and subsequent multilayers on the inner surfaces of the channels. Below 6 K, the diffusion coefficients of 4He are only weakly temperature dependent, which may be attributed to the behavior of quantum 4He liquid in the MCM-41 channels covered with several layers of 4He atoms.

  13. In-situ Hydrogen Sorption 2D-ACAR Facility for the Study of Metal Hydrides for Hydrogen Storage

    NASA Astrophysics Data System (ADS)

    Legerstee, W. J.; de Roode, J.; Anastasopol, A.; Falub, C. V.; Eijt, S. W. H.

    We developed a dedicated hydrogen sorption setup coupled to a positron 2D-ACAR (two-dimensional Angular Correlation of Annihilation Radiation) setup employing a 22Na-source, which will enable to collect 2D-ACAR momentum distributions in-situ as a function of temperature, hydrogen pressure and hydrogen content. In parallel, a dedicated glovebox was constructed for handling air-sensitive metal and metal hydride samples, with a special entrance for the 2D-ACAR sample insert. The 2D-ACAR setup was tested in first measurements on a Pd0.75Ag0.25 foil and on a ball-milled MgH2 powder in both the hydrogen loaded and desorbed states. The hydrogen loaded Pd0.75Ag0.25Hx sample was kept under a 1 bar hydrogen pressure to prevent partial desorption during measurements at room temperature. The collected 2D-ACAR distributions of Pd0.75Ag0.25 and Pd0.75Ag0.25Hx showed similar features as observed in previous studies. The broadening of the ACAR distributions observed for the Mg to MgH2 metal-insulator transition was compared in a quantitative manner to ab-initio calculations reported in the literature.

  14. Sorption kinetics of TNT and RDX in anaerobic freshwater and marine sediments: Batch studies.

    PubMed

    Ariyarathna, Thivanka; Vlahos, Penny; Tobias, Craig; Smith, Richard

    2016-01-01

    Examination of the partitioning of explosives onto sediment in marine environments is critical to predict the toxicological impacts of worldwide explosive-contaminated sites adjacent to estuaries, wetlands, and the coastal ocean. Marine sediments have been identified as sites of enhanced munitions removal, yet most studies addressing these interactions focus on soils and freshwater sediments. The present study measured the kinetics of 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) sorption onto 2 marine sediments of varying grain sizes (silt vs sand) and organic carbon (OC) content. Abiotic sediment sorption tests were performed at 23 °C, 15 °C, and 4 °C by spiking TNT and RDX solutions directly into anaerobic sediment slurries. Marine sediments showed significantly higher compound uptake rates (0.30-0.80 h(-1) ) than freshwater silt (0.0046-0.0065 h(-1) ) for both compounds, probably because of lower compound solubilities and a higher pH in marine systems. Equilibrium partition constants are on the same order of magnitude for marine silt (1.1-2.0 L kg(-1) sediment) and freshwater silt (1.4-3.1 L kg(-1) sediment) but lower for marine sand (0.72-0.92 L kg(-1) sediment). Total organic carbon content in marine sediments varied linearly with equilibrium partition constants for TNT and was moderately linear for RDX. Uptake rates and equilibrium constants of explosives are inversely correlated to temperature regardless of sediment type because of kinetic barriers associated with low temperatures. PMID:26178383

  15. Engineering and characterization of high surface area graphitic carbon nitrides for hydrogen sorption

    NASA Astrophysics Data System (ADS)

    Stalla, David; Seydel, Florian; Gillespie, Andrew; Lam, Thomas; Sweany, Mark; Lee, Mark; Pfeifer, Peter

    Theoretical calculations predict graphitic carbon nitride to produce a binding energy to hydrogen (6.4 kJ/mol) which is greater than that of pure graphene, making it attractive as a storage medium. However, the prohibitively small surface areas characteristic of g-CN materials dramatically limit H2 uptake. We discuss efforts to increase surface areas through physical/chemical exfoliation and templating. N2 sorption directly determines improvements to surface area, EF/TEM maps the thickness of aggregated planes, powder XRD indicates a novel, 2-phase structure, and XPS quantifies in-plane chemistry largely independent of the literature, which fails in a consensus regarding binding energy assignments.

  16. Hydrogen sorption behavior of CaAl1.5Li0.5

    NASA Astrophysics Data System (ADS)

    Bereznitsky, Matvey; Mogilyanski, Dmitry; Jacob, Isaac

    2016-04-01

    The hydrogen sorption properties of an alloy with nominal composition CaAl1.5Li0.5 have been investigated in a pursuit for hydrogen-absorbing Li-containing intermetallics. X-ray analysis of the original alloy indicated a coexistence of three closely related Laves phases. The maximum hydrogen capacity, recorded at about 6 MPa and 300 °C, was approximately 2.5 H atoms per formula unit (f.u.). Pressure-composition (p-c) isotherm measurements were taken in the temperature range between 350 and 450 °C up to pressures of 133 kPa. Thermodynamic parameters are derived for two plateau regions in the p-c isotherms. Analysis of these parameters and supporting evidence from X-ray patterns of hydrogenated and dehydrogenated samples suggest: (a) an initial irreversible disproportionation of the original alloy and (b) subsequent reversible hydrogenations, featuring reversible disproportionations of CaAl2 and LiAl intermetallic compounds. Attempts to form additional Li-containing intermetallics, namely CaAlLi, TiMn2- x Li x (x = 0.2, 0.3, 0.4, 0.6) and TiAl2- x Li x (x = 0.3, 0.5), and to hydrogenate them, are reported in brief.

  17. Interfacial thermodynamics and kinetics of sorption of diclofenac on prepared high performance flower-like MoS2.

    PubMed

    Zhang, Yalei; Yin, Zengfu; Dai, Chaomeng; Zhou, Xuefei; Chen, Wen

    2016-11-01

    Flower-like MoS2 with numerous wrinkled nanosheets was prepared via a facile hydrothermal method. The surface morphology and microstructure of the obtained materials were characterized using X-ray diffraction data (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Additionally, the compositions of the flower-like MoS2 were further revealed by an energy dispersion spectrometer (EDX) and X-ray photoelectron spectrometry (XPS). The obtained MoS2 was used as an adsorbent to remove diclofenac (DCF, C14H10Cl2NO2Na) from aqueous solutions and presented excellent performance for removing DCF. The sorption kinetics, isotherms and effect of solution pH on the sorption were evaluated in batch sorption experiments. The sorption characteristics of the interactions between DCF and MoS2 in water were analyzed using a pseudo-second-order model, an intraparticle diffusion model and Boyd model to determine the sorption rate-determining steps. It was concluded that the sorption of DCF on MoS2 was fitted better by the pseudo-second-order model and that external diffusion governed the sorption process of DCF onto the MoS2. The interfacial interaction free energies between DCF and MoS2 in the sorption process can be calculated based on the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO). The flower-like MoS2 presenting excellent performance for removing DCF, could be a better choice of treating DCF-containing wastewaters. PMID:27475708

  18. 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. PMID:27327628

  19. 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.

  20. Kinetics of sorption of Cu(II)-ethylenediaminetetraacetic acid chelated anions on cross-linked, polyaminated chitosan beads

    SciTech Connect

    Juang, R.S.; Ju, C.Y.

    1998-08-01

    Rates of sorption of Cu(II)-ethylenediaminetetraacetic acid (EDTA) chelated anions from aqueous solutions on cross-linked, poly(ethylenimine) (PEI)-modified chitosan beads were measured in a batch stirred vessel. All experiments were carried out in an equimolar solution of Cu(II) and EDTA (0.47--3.15 mol/m{sup 3}). It was shown that the rates of sorption increased with an increase in the initial concentration of Cu(II), pH, and temperature but decreased with an increase in the molecular weight of PEI introduced in the beads. The widely used homogeneous diffusion model based on Fick`s law and the shrinking core model cannot describe the sorption process. On the contrary, the kinetic data were well fit by the Elovich equation. The apparent activation energies evaluated (3.5--8.4 kcal/mol at pH 3) indicated the combined film and particle diffusion mechanism.

  1. Hydrogen production from glucose and sorbitol by sorption-enhanced steam reforming: challenges and promises.

    PubMed

    He, Li; Chen, De

    2012-03-12

    Concerning energy and environmental sustainability, it is appealing to produce hydrogen from sugars or sugar alcohols that are readily obtained from the hydrolysis of cellulosic biomass. Nevertheless, the conversion of such compounds for hydrogen production poses great technical challenges. In this paper, we report that hydrogen purity and yield can be significantly improved by integrating in situ CO(2) capture into the steam reforming reaction of the model compounds-glucose and sorbitol. The experimental assessment was conducted at a steam-to-carbon ratio of 1.8 for sorbitol and 6 for glucose from 450-625 °C. As predicted by thermodynamic analysis, combining CO(2) capture and reforming reactions at favorable operating conditions yielded very high purity hydrogen, for instance, 98.8 mol % from sorbitol and 99.9 mol % from glucose. However, there are trade-offs between hydrogen purity and yield in practice. The lower operating temperatures in the examined range helped to increase the hydrogen purity and reduce the CO content in the gas product, whereas a high hydrogen yield was more likely to be obtained at higher temperatures. Coupling CO(2) capture lowered the risk of coke formation during the steam reforming of glucose. Coke accumulated in the reactor for the sorption-enhanced steam reforming of glucose was mostly from the slow pyrolysis of glucose before it came into contact with the catalyst-acceptor bed. This problem may be solved by improving heat transfer or reconstructing the reactor, for instance, by using a fluidized-bed reactor. PMID:22378630

  2. Preparation, microstructure and hydrogen sorption properties of nanoporous carbon aerogels under ambient drying

    NASA Astrophysics Data System (ADS)

    Tian, H. Y.; Buckley, C. E.; Mulè, S.; Paskevicius, M.; Dhal, B. B.

    2008-11-01

    Organic aerogels are prepared by the sol-gel method from polymerization of resorcinol with furfural. These aerogels are further carbonized in nitrogen in order to obtain their corresponding carbon aerogels (CA); a sample which was carbonized at 900 °C was also activated in a carbon dioxide atmosphere at 900 °C. The chemical reaction mechanism and optimum synthesis conditions are investigated by means of Fourier transform infrared spectroscopy and thermoanalyses (thermogravimetric/differential thermal analyses) with a focus on the sol-gel process. The carbon aerogels were investigated with respect to their microstructures, using small angle x-ray scattering (SAXS), transmission electron microscopy (TEM) and nitrogen adsorption measurements at 77 K. SAXS studies showed that micropores with a radius of gyration of <0.35 ± 0.07 to 0.55 ± 0.05 nm were present, and TEM measurements and nitrogen adsorption showed that larger mesopores were also present. Hydrogen storage properties of the CA were also investigated. An activated sample with a Brunauer-Emmett-Teller surface area of 1539 ± 20 m2 g-1 displayed a reasonably high hydrogen uptake at 77 K with a maximum hydrogen sorption of 3.6 wt% at 2.5 MPa. These results suggest that CA are promising candidate hydrogen storage materials.

  3. 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.

  4. 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.

  5. Kinetics of hydrogen release from lunar soil

    NASA Astrophysics Data System (ADS)

    Bustin, Roberta

    1990-10-01

    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.

  6. Kinetics of cadmium, chromium, and lead sorption onto chemically modified sugarcane bagasse and wheat straw.

    PubMed

    Mahmood-ul-Hassan, M; Suthar, V; Rafique, E; Ahmad, R; Yasin, M

    2015-07-01

    In this study, cadmium (Cd), chromium (Cr), and lead (Pb) adsorption potential of unmodified and modified sugarcane bagasse and ground wheat straw was explored from aqueous solution through batch equilibrium technique. Both the materials were chemically modified by treating with sodium hydroxide (NaOH) alone and in combination with nitric acid (HNO3) and sulfuric acid (H2SO4). Two kinetic models, pseudo-first order and pseudo-second order were used to follow the adsorption process and reaction fallowed the later model. The Pb removal by both the materials was highest and followed by Cr and Cd. The chemical treatment invariably increased the adsorption capacity and NaOH treatment proved more effective than others. Langmuir maximum sorption capacity (q m) of Pb was utmost (12.8-23.3 mg/g of sugarcane bagasse, 14.5-22.4 mg/g of wheat straw) and of Cd was least (1.5-2.2 mg/g of sugarcane bagasse, 2.5-3.8 mg/g of wheat straw). The q m was in the order of Pb > Cr > Cd for all the three adsorbents. Results demonstrate that agricultural waste materials used in this study could be used to remediate the heavy metal-polluted water. PMID:26116198

  7. Application of multisection packing concept to sorption-enhanced steam methane reforming reaction for high-purity hydrogen production

    NASA Astrophysics Data System (ADS)

    Lee, Chan Hyun; Mun, Sungyong; Lee, Ki Bong

    2015-05-01

    Hydrogen has been gaining popularity as a new clean energy carrier, and bulk hydrogen production is achieved through the steam methane reforming (SMR) reaction. Since hydrogen produced via the SMR reaction contains large amounts of impurities such as unreacted reactants and byproducts, additional purification steps are needed to produce high-purity hydrogen. By applying the sorption-enhanced reaction (SER), in which catalytic reaction and CO2 byproduct removal are carried out simultaneously in a single reactor, high-purity hydrogen can be directly produced. Additionally, the thermodynamic limitation of conventional SMR reaction is circumvented, and the SMR reaction process becomes simplified. To improve the performance of the SER, a multisection packing concept was recently proposed. In this study, the multisection packing concept is experimentally demonstrated by applying it to a sorption-enhanced SMR (SE-SMR) reaction. The experimental results show that the SE-SMR reaction is significantly influenced by the reaction temperature, owing to the conflicting dependence of the reaction rate and the CO2 sorption uptake on the reaction temperature. Additionally, it is confirmed that more high-purity hydrogen (<10 ppm of CO) can be produced by applying the multisection packing concept to the SE-SMR reactions operated at sufficiently high temperatures where the SMR reaction is not limited by rate.

  8. Hydrogen pickup measurements in zirconium alloys: Relation to oxidation kinetics

    NASA Astrophysics Data System (ADS)

    Couet, Adrien; Motta, Arthur T.; Comstock, Robert J.

    2014-08-01

    The optimization of zirconium-based alloys used for nuclear fuel cladding aims to reduce hydrogen pickup during operation, and the associated cladding degradation. The present study focuses on precisely and accurately measuring hydrogen pickup fraction for a set of alloys to specifically investigate the effects of alloying elements, microstructure and corrosion kinetics on hydrogen uptake. To measure hydrogen concentrations in zirconium alloys two techniques have been used: a destructive technique, Vacuum Hot Extraction, and a non-destructive one, Cold Neutron Prompt Gamma Activation Analysis. The results of both techniques show that hydrogen pickup fraction varies significantly with exposure time and between alloys. A possible interpretation of the results is that hydrogen pickup results from the need to balance charge. That is, the pickup of hydrogen shows an inverse relationship to oxidation kinetics, indicating that, if transport of charged species is rate limiting, oxide transport properties such as oxide electronic conductivity play a key role in the hydrogen pickup mechanism. Alloying elements (either in solid solution or in precipitates) would therefore impact the hydrogen pickup fraction by affecting charge transport.

  9. HYGROSCOPIC MOISTURE SORPTION KINETICS MODELING OF CORN STOVER AND ITS FRACTIONS

    SciTech Connect

    Igathinathane, C.; Pordesimo, L. O.; Womac, A.R.; Sokhansanj, Shahabaddine

    2009-01-01

    Corn stover, a major crop-based lignocellulosic biomass feedstock, is required to be at an optimum moisture content for efficient bioconversion processes. Environmental conditions surrounding corn stover, as in storage facilities, affect its moisture due to hygroscopic sorption or desorption. The measurement and modeling of sorption characteristics of corn stover and its leaf, husk, and stalk fractions are useful from utilization and storage standpoints, hence investigated in this article. A benchtop low-temperature humidity chamber provided the test environments of 20 C, 30 C, and 40 C at a constant 95% relative humidity. Measured sorption characteristics with three replications for each fraction were obtained from instantaneous sample masses and initial moisture contents. Observed sorption characteristics were fitted using exponential, Page, and Peleg models. Corn stover fractions displayed a rapid initial moisture uptake followed by a slower sorption rates and eventually becoming almost asymptotic after 25 h. Sorption characteristics of all corn stover fractions were significantly different (P < 0.0001) but not the effect of temperature (P > 0.05) on these fractions. The initial 30 min of sorption was found to be critical due to peak rates of sorption from storage, handling, and processing standpoints. The Page and Peleg models had comparable performance fitting the sorption curves (R2 = 0.995), however the exponential model (R2 = 0.91) was not found suitable because of patterned residuals. The Arrhenius type relationship (P < 0.05; R2 = 0.80) explained the temperature variation of the fitted sorption model parameters. The Peleg model fitted constants, among the sorption models studied, had the best fit (R2 = 0.93) with the Arrhenius relationship. A developed method of mass proportion, involving individual corn stover fraction dry matter ratios, predicted the whole corn stover sorption characteristics from that of its individual fractions. Sorption

  10. Photosynthetic hydrogen and oxygen production - Kinetic studies

    NASA Astrophysics Data System (ADS)

    Greenbaum, E.

    1982-01-01

    The simultaneous photoproduction of hydrogen and oxygen was measured in a study of the steady-state turnover times of two biological systems, by driving them into the steady state with repetitive, single-turnover flash illumination. The systems were: (1) in vitro, isolated chloroplasts, ferredoxin and hydrogenase; and (2) the anaerobically-adapted green alga Chlamydomonas reinhardtii. It is found that the turnover times for production of both oxygen and hydrogen in photosynthetic water splitting are in milliseconds, and either equal to, or less than, the turnover time for carbon dioxide reduction in intact algal cells. There is therefore mutual compatibility between hydrogen and oxygen turnover times, and partial compatibility with the excitation rate of the photosynthetic reaction centers under solar irradiation conditions.

  11. Characterization of hot hydrogen-atom reactions by kinetic spectrography.

    NASA Technical Reports Server (NTRS)

    Tomalesky, R. E.; Sturm, J. E.

    1971-01-01

    The flash photolysis of hydrogen iodide in the presence of nitrous oxide, carbon dioxide, and water has been investigated by kinetic spectroscopy. Although the fraction of hydrogen iodide dissociated was very large, the only observable intermediate was imidogen. It was demonstrated that the rapid removal of imidogen and the apparent absence of hydroxyl radicals in each case is a result of the following two reactions, respectively: (1) NH + HI yields NH2 + I; and (2) OH + HI yields H2O + I.

  12. Kinetics of histidine sorption and desorption on Fumasep® FTCM cation-exchange membranes

    NASA Astrophysics Data System (ADS)

    Maigurova, N. I.; Eliseeva, T. V.; Lantsuzskaya, E. V.; Sholokhova, A. Yu.

    2015-05-01

    The sorption of the basic amino acid histidine by Fumasep® FTCM membranes in different ionic forms is investigated over a wide range of solution concentrations. It is established that sorption limited by the stage of external diffusion. The time required for equilibrium to be established in the membrane-amino acid solution system is found to grow from 4 to 9 h when the initial concentration of the solution is reduced. The reversibility of histidine sorption is demonstrated, and the conditions of effective desorption are determined.

  13. Sorption behavior of nonylphenol (NP) on sewage-irrigated soil: kinetic and thermodynamic studies.

    PubMed

    Liao, Xiaoping; Zhang, Caixiang; Yao, Linlin; Li, Jiale; Liu, Min; Xu, Liang; Evalde, Mulindankaka

    2014-03-01

    The reuse of wastewater for irrigation of agricultural land is a well established resources management practice but has the disadvantage of inputting various forms of contaminants into the terrestrial environment including nonylphenol (NP), a well known endocrine disrupting substance. To elucidate the environmental fate and transport of NP, the sorption behavior on sewage-irrigated soil was studied by batch experiment. It was found that sorption processes of NP on different sorbents (soil, humic acid (HA) and silica) could be expressed well using two compartment pseudo first-order model, where both surface and intra-particle diffusion were probable rate-controlling processes. Linear model could better express the sorption of NP on soil, black carbon (BC) and mineral (e.g., SiO2) except HA than Freundlich model. The large value of distribution coefficients of normalized organic carbon (Koc) on soils indicated that NP was limited to migrate to deep soil. The higher desorption partition coefficient of NP on soil showed enhanced hysteresis. According to the experimental data, the calculated thermodynamic parameters implied that the sorption reaction on sewage-irrigation was spontaneous, exothermic and entropy decreasing process. The amount of soil organic matter (SOM) dominated the sorption capacity, whereas the sorption behavior of NP on soil showed no significant correlation with ionic strength. PMID:24388903

  14. In situ X-ray Raman spectroscopy study of the hydrogen sorption properties of lithium borohydride nanocomposites.

    PubMed

    Miedema, Piter S; Ngene, Peter; van der Eerden, Ad M J; Sokaras, Dimosthenis; Weng, Tsu-Chien; Nordlund, Dennis; Au, Yuen S; de Groot, Frank M F

    2014-11-01

    Nanoconfined alkali metal borohydrides are promising materials for reversible hydrogen storage applications, but the characterization of hydrogen sorption in these materials is difficult. Here we show that with in situ X-ray Raman spectroscopy (XRS) we can track the relative amounts of intermediates and final products formed during de- and re-hydrogenation of nanoconfined lithium borohydride (LiBH4) and therefore we can possibly identify the de- and re-hydrogenation pathways. In the XRS of nanoconfined LiBH4 at different points in the de- and re-hydrogenation, we identified phases that lead to the conclusion that de- and re-hydrogenation pathways in nanoconfined LiBH4 are different from bulk LiBH4: intercalated lithium (LiCx), boron and lithium hydride were formed during de-hydrogenation, but as well Li2B12H12 was observed indicating that there is possibly some bulk LiBH4 present in the nanoconfined sample LiBH4-C as prepared. Surprisingly, XRS revealed that the de-hydrogenated products of the LiBH4-C nanocomposites can be partially rehydrogenated to about 90% of Li2B12H12 and 2-5% of LiBH4 at a mild condition of 1 bar H2 and 350 °C. This suggests that re-hydrogenation occurs via the formation of Li2B12H12. Our results show that XRS is an elegant technique that can be used for in and ex situ study of the hydrogen sorption properties of nanoconfined and bulk light-weight metal hydrides in energy storage applications. PMID:25231357

  15. Interaction between chitosan and uranyl ions. Role of physical and physicochemical parameters on the kinetics of sorption

    SciTech Connect

    Piron, E. |; Accominotti, M.; Domard, A.

    1997-03-19

    This work corresponds to the first part of our studies on the interactions between chitosan particles dispersed in water and uranyl ions. The measurements were obtained by ICP, and we considered the role of various physical and physicochemical parameters related to chitosan. We showed that the crystallinity, the particle dimensions, and the swelling in water of chitosan are parameters which are connected together and govern the kinetic laws of metal diffusion and sorption. The molecular mobility of the polymer chains is then essential parameter. 31 refs., 5 figs., 3 tabs.

  16. 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.

  17. 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. PMID:22565543

  18. Biosorption kinetics, thermodynamics and isosteric heat of sorption of Cu(II) onto Tamarindus indica seed powder.

    PubMed

    Chowdhury, Shamik; Saha, Papita Das

    2011-12-01

    Biosorption of Cu(II) by Tamarindus indica seed powder (TSP) was investigated as a function of temperature in a batch system. The Cu(II) biosorption potential of TSP increased with increasing temperature. The rate of the biosorption process followed pseudo second-order kinetics while the sorption equilibrium data well fitted to the Langmuir and Freundlich isotherm models. The maximum monolayer Cu(II) biosorption capacity increased from 82.97 mg g(-1) at 303 K to 133.24 mg g(-1) at 333 K. Thermodynamic study showed spontaneous and endothermic nature of the sorption process. Isosteric heat of sorption, determined using the Clausius-Clapeyron equation increased with increase in surface loading showing its strong dependence on surface coverage. The biosorbent was characterized by scanning electron microscopy (SEM), surface area and porosity analyzer, X-ray diffraction (XRD) spectrum and Fourier transform infrared (FTIR) spectroscopy. The results of FTIR analysis of unloaded and Cu(II)-loaded TSP revealed that -NH(2), -OH, -C=O and C-O functional groups on the biosorbent surface were involved in the biosorption process. The present study suggests that TSP can be used as a potential, alternative, low-cost biosorbent for removal of Cu(II) ions from aqueous media. PMID:21872453

  19. Chemisorption kinetics of hydrogen on evaporated iron films

    NASA Technical Reports Server (NTRS)

    Shanabarger, M. R.

    1975-01-01

    Measurements were made of the isothermal adsorption-desorption kinetics for H2 chemisorbed onto Fe films. The chemisorption process is observed to proceed via a precursor state of adsorbed molecular hydrogen similar to the H2-Ni system. The first measurements of the activation energy for desorption, and estimates of the values of the fast kinetic rates between the precursor and chemisorbed states are reported. Adsorption into the precursor state does not appear to be activated, but the process connecting the precursor state with the chemisorbed state will, under certain circumstances, be a rate limiting step for adsorption. The effects of contamination of the surface are evidenced in the measurements.

  20. The influence of nickel layer thickness on microhardness and hydrogen sorption rate of commercially pure titanium alloy

    NASA Astrophysics Data System (ADS)

    Kudiiarov, V. N.; Kashkarov, E. B.; Syrtanov, M. S.; Yugova, I. S.

    2016-02-01

    The influence of nickel coating thickness on microhardness and hydrogen sorption rate by commercially pure titanium alloy was established in this work. Coating deposition was carried out by magnetron sputtering method with prior ion cleaning of surface. It was shown that increase of sputtering time from 10 to 50 minutes leads to increase coating thickness from 56 to 3.78 μm. It was established that increase of nickel coating thickness leads to increase of microhardness at loads less than 0.5 kg. Microhardness values for all samples are not significantly different at loads 1 kg. Hydrogen content in titanium alloy with nickel layer deposited at 10 and 20 minutes exceeds concentration in initial samples on one order of magnitude. Further increasing of deposition time of nickel coating leads to decreasing of hydrogen concentration in samples due to coating delamination in process of hydrogenation.

  1. Determination of toluene hydrogenation kinetics with neutron diffraction.

    PubMed

    Falkowska, Marta; Chansai, Sarayute; Manyar, Haresh G; Gladden, Lynn F; Bowron, Daniel T; Youngs, Tristan G A; Hardacre, Christopher

    2016-06-29

    Total neutron scattering has been used to follow the hydrogenation of toluene-d8 to methylcyclohexane-d14 over 3 wt% platinum supported on highly ordered mesoporous silica (MCM-41) at 298 K and under 150 mbar D2 pressure. The detailed kinetic information so revealed indicates that liquid reorganisation inside pores is the slowest step of the whole process. Additionally, the results were compared with the reaction performed under 250 mbar D2 pressure as well as with toluene-h8 hydrogenation using D2 at 150 mbar. PMID:27052196

  2. Chemisorption kinetics of hydrogen on evaporated iron films

    NASA Technical Reports Server (NTRS)

    Shanabarger, M. R.

    1975-01-01

    An investigation is conducted of the kinetics of isothermal adsorption-desorption processes involving molecular hydrogen which is chemisorbed onto thin (20 to 50 A) polycrystalline Fe films at temperatures near 300 K. The results of the investigation indicate that chemisorption in the H2-Fe system occurs via a precursor state of molecularly adsorbed hydrogen. Contamination of the surface from unknown impurities in the gas phase is found to affect the number of available adsorption sites and to modify the prefactor for the absolute desorption rate constant for the precursor state.

  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. Stereoselective thymol hydrogenation. I. Kinetics of thymol hydrogenation on charcoal-supported platinum catalysts

    SciTech Connect

    Besson, M.; Bullivant, L.; Nicolaus, N.; Gallezot, P. )

    1993-03-01

    The kinetics of thymol hydrogenation on a well-characterized supported platinum catalyst have been investigated in cyclohexane at temperatures between 313 and 373 K and under 3 MPa of hydrogen pressure. The relative rate constants of the different reaction pathways (hydrogenation via menthone or isomenthone, and direct hydrogenation to the four menthol diastereoisomers) were determined from the changes in composition of the reaction medium during the reaction process. It has been shown that hydrogenation via the menthone intermediates is the major route, the formation of the cis isomer (isomenthone) being favored. The configuration of the menthols, produced from direct hydrogenation or from the ketone intermediates, is controlled by the geometry of adsorption of the precursors on the metal surface, so that neoisomenthol with all substituents in the cis position is by far the most abundant steroisomer produced. 21 refs., 11 figs., 2 tabs.

  5. Dissolution, sorption, and kinetics involved in systems containing explosives, water, and soil.

    PubMed

    Larson, Steven L; Martin, W Andy; Escalon, B Lynn; Thompson, Michelle

    2008-02-01

    Knowledge of explosives sorption and transformation processes is required to ensure that the proper fate and transport of such contaminants is understood at military ranges and ammunition production sites. Bioremediation of 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and related nitroaromatic compounds has met with mixed success, which is potentially due to the uncertainty of how energetic compounds are bound to different soil types. This study investigated the dissolution and sorption properties of TNT and RDX explosives associated with six different soil types. Understanding the associations that explosives have with a different soil type assists with the development of conceptual models used for the sequestration process, risk analysis guidelines, and site assessment tools. In three-way systems of crystalline explosives, soil, and water, the maximum explosive solubility was not achieved due to the sorption of the explosive onto the soil particles and observed production of transformation byproducts. Significantly different sorption effects were also observed between sterile (gamma-irradiated) and nonsterile (nonirradiated) soils with the introduction of crystalline TNT and RDX into soil-water systems. PMID:18323103

  6. 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

  7. 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.

  8. 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

  9. U(VI) sorption and reduction kinetics on the magnetite (111) surface

    SciTech Connect

    Singer, David M.; Chatman, Shawn ME; Ilton, Eugene S.; Rosso, Kevin M.; Banfield, Jillian F.; Waychunas, Glenn

    2012-04-03

    Sorption of contaminants onto mineral surfaces is an important process that can restrict their transport in the environment. In the current study, uranium (U) uptake on magnetite (111) was measured as a function of time and solution composition (pH, [CO3]T, [Ca]) under continuous batch-flow conditions. We observed, in real-time and in situ, adsorption and reduction of U(VI) and subsequent growth of UO2 nanoprecipitates using atomic force microscopy (AFM) and newly developed batch-flow U LIII-edge grazing-incidence x-ray absorption spectroscopy near-edge structure (GI-XANES) spectroscopy. U(VI) reduction occurred with and without CO3 present, and coincided with nucleation and growth of particles; maximum sorption loadings were 23 mol m-2 (pH 5) and 27 mol m-2 (pH 10). The U sorption loading was lower when Ca and CO3 were both present and during experiments in which no U(VI) reduction occurred; the maximum U sorption loading was 17 mol m-2 (pH 5 and 10). In situ batch-flow AFM data indicated that UO2 particles achieved a maximum height of 4-5 nm after about 8 hours of exposure, yet lateral growth as aggregates continued up to 300 nm. U uptake is therefore divided into three-stages; (1) initial adsorption of U(VI), (2) reduction of U(VI) to UO2 nanoprecipitates at surface-specific sites after 2-3 hours of exposure, and (3) completion of U(VI) reduction after 6-8 hours, with continuing slow adsorption of U(VI). U(VI) reduction also corresponded to detectable increases in Fe released to solution and surface topography changes, indicating that reduction is coupled to Fe(II) availability at or from the magnetite (111) surface. In addition to providing molecular-scale details about U sorption on magnetite, this work also presents novel advances for collecting surface sensitive molecular-scale information in real-time under batch-flow conditions.

  10. The role of sorption and biodegradation in the removal of acetaminophen, carbamazepine, caffeine, naproxen and sulfamethoxazole during soil contact: A kinetics study.

    PubMed

    Martínez-Hernández, Virtudes; Meffe, Raffaella; Herrera López, Sonia; de Bustamante, Irene

    2016-07-15

    In countries like Spain, where water is a limited resource, reusing effluents from wastewater treatment plants may imply the introduction of incompletely eliminated pollutants into the environment. Therefore, this work identified the role of sorption and biodegradation in attenuating pharmaceutical compounds (acetaminophen, carbamazepine, caffeine, naproxen and sulfamethoxazole) in natural soil. It also determined which sorption and removal ("sorption+biodegradation") kinetics models describe the behaviour of these substances in the water-soil system. Presence of potential transformation products (TPs) as a result of pharmaceuticals biodegradation was also studied. To this end, serial batch-type experiments were performed with a soil:water ratio of 1:4 and an initial pharmaceutical concentration of 100μgL(-1). Despite results are dependent on soil characteristics, they revealed that, for those substances with a higher affinity to the soil used (loamy sand), sorption seems to play a key role during the first 48h of contact with soil, and gives way to biodegradation afterwards. The sorption of the pharmaceuticals studied follows a pseudo second-order kinetics. Caffeine and sulfamethoxazole displayed the fastest initial sorption velocities (h=2055 and h=228μgkg(-1)h(-1), respectively). The removal kinetics experiments, satisfactorily simulated by the first-order kinetics model, indicated the presence of potential microbial adaptation to degradation. Indeed, half-lives decreased from 1.6- to 11.7-fold with respect to initial values. The microbial capacity to degrade sulfamethoxazole could be a matter of concern if bacteria have developed resistance to this antibiotic. Caffeine, acetaminophen and sulfamethoxazole were mitigated to a greater extent, whereas the removal of naproxen and carbamazepine was more limited. The appearance of epoxy-carbamazepine and N4-acetyl-sulfamethoxazole as possible TPs of carbamazepine and sulfamethoxazole, respectively, indicated that

  11. Optimized autonomous operations of a 20 K space hydrogen sorption cryocooler

    NASA Astrophysics Data System (ADS)

    Borders, J.; Morgante, G.; Prina, M.; Pearson, D.; Bhandari, P.

    2004-06-01

    A fully redundant hydrogen sorption cryocooler is being developed for the European Space Agency Planck mission, dedicated to the measurement of the temperature anisotropies of the cosmic microwave background radiation with unprecedented sensitivity and resolution [Advances in Cryogenic Engineering 45A (2000) 499]. In order to achieve this ambitious scientific task, this cooler is required to provide a stable temperature reference (˜20 K) and appropriate cooling (˜1 W) to the two instruments on-board, with a flight operational lifetime of 18 months. During mission operations, communication with the spacecraft will be possible in a restricted time-window, not longer than 2 h/day. This implies the need for an operations control structure with the required robustness to safely perform autonomous procedures. The cooler performance depends on many operating parameters (such as the temperatures of the pre-cooling stages and the warm radiator), therefore the operation control system needs the capability to adapt to variations of these boundary conditions, while maintaining safe operating procedures. An engineering bread board (EBB) cooler was assembled and tested to evaluate the behavior of the system under conditions simulating flight operations and the test data were used to refine and improve the operation control software. In order to minimize scientific data loss, the cooler is required to detect all possible failure modes and to autonomously react to them by taking the appropriate action in a rapid fashion. Various procedures and schemes both general and specific in nature were developed, tested and implemented to achieve these goals. In general, the robustness to malfunctions was increased by implementing an automatic classification of anomalies in different levels relative to the seriousness of the error. The response is therefore proportional to the failure level. Specifically, the start-up sequence duration was significantly reduced, allowing a much faster

  12. 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.

  13. Kinetic, equilibrium and thermodynamic studies on sorption of uranium and thorium from aqueous solutions by a selective impregnated resin containing carminic acid.

    PubMed

    Rahmani-Sani, Abolfazl; Hosseini-Bandegharaei, Ahmad; Hosseini, Seyyed-Hossein; Kharghani, Keivan; Zarei, Hossein; Rastegar, Ayoob

    2015-04-01

    In this work, the removal of uranium and thorium ions from aqueous solutions was studied by solid-liquid extraction using an advantageous extractant-impregnated resin (EIR) prepared by loading carminic acid (CA) onto Amberlite XAD-16 resin beads. Batch sorption experiments using CA/XAD-16 beads for the removal of U(VI) and Th(IV) ions were carried out as a function of several parameters, like equilibration time, metal ion concentration, etc. The equilibrium data obtained from the sorption experiments were adjusted to the Langmuir isotherm model and the calculated maximum sorption capacities in terms of monolayer sorption were in agreement with those obtained from the experiments. The experimental data on the sorption behavior of both metal ions onto the EIR beads fitted well in both Bangham and intra-particle diffusion kinetic models, indicating that the intra-particle diffusion is the rate-controlling step. The thermodynamic studies at different temperatures revealed the feasibility and the spontaneous nature of the sorption process for both uranium and thorium ions. PMID:25576783

  14. Initial hydrogen attack kinetics in a carbon steel

    NASA Astrophysics Data System (ADS)

    McKimpson, Marvin; Shewmon, Paul G.

    1981-05-01

    The kinetics of the initial stages of hydrogen attack in a commercial 0.3 pct C steel (grade A516) were investigated using an in situ dilatometer. The time, temperature and hydrogen pressure dependences of the rate of sample expansion were measured at hydrogen pressures from 1 to 20 MPa, and temperatures from 350 to 475 °C for sample strains of 10-6 to 10-3. Sample expansion began shortly after hydrogen exposure and proceeded at a nearly constant rate throughout the “incubation period” preceding rapid attack. At high temperatures and low pressures, this rate was proportional to PH 2 1.9±0.2 and had an apparent activation energy of 115 ± 9 kJ. At high pressures and low temperatures, the rate was proportional to PPH 2 1.0.62±0.07 and showed an apparent activation energy of 210 ± 13 kJ. This suggests that bubble growth during the incubation period occurs predominantly by grain boundary diffusion and is driven by near-equilibrium internal methane pressures. Sample expansion in the subsequent stages of accelerating growth probably is controlled by creep and methane generation.

  15. Removal of divalent heavy metals (Cd, Cu, Pb, and Zn) and arsenic(III) from aqueous solutions using scoria: kinetics and equilibria of sorption.

    PubMed

    Kwon, Jang-Soon; Yun, Seong-Taek; Lee, Jong-Hwa; Kim, Soon-Oh; Jo, Ho Young

    2010-02-15

    Kinetic and equilibrium sorption experiments were conducted on removal of divalent heavy metals (Pb(II), Cu(II), Zn(II), Cd(II)) and trivalent arsenic (As(III)) from aqueous solutions by scoria (a vesicular pyroclastic rock with basaltic composition) from Jeju Island, Korea, in order to examine its potential use as an efficient sorbent. The removal efficiencies of Pb, Cu, Zn, Cd, and As by the scoria (size=0.1-0.2mm, dose=60gL(-1)) were 94, 70, 63, 59, and 14%, respectively, after a reaction time of 24h under a sorbate concentration of 1mM and the solution pH of 5.0. A careful examination on ionic concentrations in sorption batches suggested that sorption behaviors of heavy metals onto scoria are mainly controlled by cation exchange. On the other hand, arsenic appeared to be sensitive to specific sorption onto hematite (a minor constituent of scoria). Equilibrium sorption tests indicated that the removal efficiency for heavy metals increases with increasing pH of aqueous solutions, which is resulted from precipitation as hydroxides. Similarly, multi-component systems containing heavy metals and arsenic showed that the arsenic removal increases with increasing pH of aqueous solutions, which can be attributed to coprecipitation with metal hydroxides. The empirically determined sorption kinetics were well fitted to a pseudo-second order model, while equilibrium sorption data for heavy metals and arsenic onto scoria were consistent with the Langmuir and Freundlich isotherms, respectively. Natural scoria studied in this work is an efficient sorbent for concurrent removal of divalent heavy metals and arsenic. PMID:19828237

  16. Kinetics, equilibrium, and mechanisms of sorption and desorption of 17α-ethinyl estradiol in two natural soils and their organic fractions.

    PubMed

    Li, Jianzhong; Fu, Jing; Xiang, Xi; Wu, Miaomiao; Liu, Xiang

    2013-05-01

    A study was conducted on the kinetics, equilibrium, and mechanisms of sorption and desorption of 17α-ethinyl estradiol (EE2) in six sorbents, which were two natural soils (Bulk1 and Bulk2) and their fractions obtained by alkaline extraction, namely, humic acids (HA1 and HA2), and mineral-bond humins (MHU1 and MHU2). These sorbents, characterized by total organic carbon (TOC), black carbon (BC), gas adsorption and Fourier transform infrared spectra, were shown to be porous solids containing aromatic (hard carbon) and aliphatic carbon (soft carbon). The two-compartment first-order model fitted the kinetics of sorption very well (R(2)>0.990). The fast and slow sorption rate constants ranged from 1.110 h(-1) and 0.026 h(-1) to 2.063 h(-1) and 0.067 h(-1), respectively. The slow sorption was attributed to the diffusion of EE2 in micropores rather than organic matter. The Freundlich model fitted the equilibrium of sorption and desorption very well. The nonlinearity of sorption took the order MHU>bulk soil>HA and was positively related to BC/TOC (p<0.01). The hysteresis in MHU2 with higher BC/TOC was stronger than that in Bulk2 with lower BC/TOC, but a contrary observation was found in MHU1 and Bulk1. This contradictory phenomenon could be attributed to the location difference of hard carbon which greatly affected the desorption process. These findings could give an insight into the sorption mechanisms and promote an accurate model for the transport, fate and risk assessment of EE2 in the environment. PMID:23542434

  17. Synthesis, Structure Determination, and Hydrogen Sorption Studies of New Metal-Organic Frameworks Using Triazole and Naphthalenedicarboxylic Acid

    SciTech Connect

    Park,H.; Britten, J.; Mueller, U.; Lee, J.; Li, J.; Parise, J.

    2007-01-01

    Two new metal-organic framework compounds were synthesized under solvothermal conditions using Zn{sup 2+} ion, 1,2,4-triazole (TRZ), and 1,4- and 2,6-naphthalenedicarboxylic acids (NDC): Zn{sub 4}(TRZ){sub 4}(1,4-NDC){sub 2}-2DMF-2H{sub 2}O (1) and Zn{sub 4}(TRZ){sub 4}(2,6-NDC){sub 2}-2DMF-4H{sub 2}O (2). Their crystal structures were characterized by single-crystal X-ray diffraction. Structure 1 crystallizes in the P2{sub 1}/n space group with a = 13.609(2) {angstrom}, b = 27.181(5){angstrom}, c = 13.617(3) {angstrom}, {beta} = 92.46(1){sup o}, V = 5032.4(16) {angstrom}{sup 3}, and Z = 4. Structure 2 crystallizes in orthorhombic Pna2{sub 2} space group with a = 30.978(6) {angstrom}, b = 12.620(3) {angstrom}, c = 13.339(3) {angstrom}, V = 5215(2) {angstrom}{sup 3}, and Z = 4. Both structures are analogues of the previously reported Zn{sub 4}(TRZ){sub 4}(1,4-BDC){sub 2}-16H{sub 2}O where the layers of Zn-triazole moieties are pillared by aromatic dicarboxylates to create 3-D open frameworks. Nitrogen sorption studies revealed that these structures have Brunaer-Emmett-Teller (BET) surface areas of 362.1-584.1 m{sup 2}/g. Hydrogen sorption experiments showed they can store 0.84-1.09 wt % H{sub 2} at 77 K and 1 atm. Although they do not contain large pores or surface areas, they possess the hydrogen sorption capacities comparable to those of highly porous metal-organic frameworks.

  18. Hydrogen recombination kinetics and nuclear thermal rocket performance prediction

    SciTech Connect

    Wetzel, K.K.; Solomon, W.C.

    1994-07-01

    The rate constants for the hydrogen three-body collisional recombination reaction with atomic and molecular hydrogen acting as third bodies have been determined by numerous investigators during the past 30 yr, but these rates exhibit significant scatter. The discrepancies in the rate constants determined by different investigators are as great as two orders of magnitude in the temperature range of interest for nuclear thermal rocket (NTR) operation, namely, 2000-3300 K. The impact of this scatter on our ability to predict the specific impulse (I(sub sp)) delivered by a 30-klbf NTR has been determined for chamber pressures and temperatures from, respectively, 20-1000 psia and 2700-3300 K. The variation in I(sub sp) produced by using the different rate constants is as great as 10%, or 100 s. This variation also obscures the influence of chamber pressure on I(sub sp); using fast kinetics, low pressures yield significantly improved performance, while using slow or nominal kinetics, the pressure dependence of I(sub sp) is negligible. Because the flow composition freezes at very small area ratios, optimization of the nozzle contour in the near-throat region maximizes recombination. Vibrational relaxation is found to produce negligible losses in I(sub sp). 36 refs.

  19. Hydrogen-rich gas production via CaO sorption-enhanced steam gasification of rice husk: a modelling study.

    PubMed

    Beheshti, Sayyed Mohsen; Ghassemi, Hojat; Shahsavan-Markadeh, Rasoul; Fremaux, Sylvain

    2015-01-01

    Gasification is a thermochemical process in which solid or liquid fuels are transformed into synthesis gas through partial oxidation. In this paper, a kinetic model of rice husk gasification has been developed, which is interesting for the applications of the syngas produced. It is a zero-dimensional, steady-state model based on global reaction kinetic, empirical correlation of pyrolysis and is capable of predicting hydrogen yield in the presence of sorbent CaO. The model can also be used as a useful tool to investigate the influence of process parameters including steam/biomass ratio, CaO/fuel ratio (CaO/Fuel), and gasification temperature on hydrogen efficiency, CO2 capture ratio (CCR), and average carbonation conversion (Save). Similar to hydrogen formation, CCR also increases with increasing CaO/Fuel, but an opposite trend is exhibited in Save. Model predictions were compared with available data from the literature, which showed fairly good agreement. PMID:25403373

  20. 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. PMID:25866206

  1. Description of gas/particle sorption kinetics with an intraparticle diffusion model: Desorption experiments

    USGS Publications Warehouse

    Rounds, S.A.; Tiffany, B.A.; Pankow, J.F.

    1993-01-01

    Aerosol particles from a highway tunnel were collected on a Teflon membrane filter (TMF) using standard techniques. Sorbed organic compounds were then desorbed for 28 days by passing clean nitrogen through the filter. Volatile n-alkanes and polycyclic aromatic hydrocarbons (PAHs) were liberated from the filter quickly; only a small fraction of the less volatile ra-alkanes and PAHs were desorbed. A nonlinear least-squares method was used to fit an intraparticle diffusion model to the experimental data. Two fitting parameters were used: the gas/particle partition coefficient (Kp and an effective intraparticle diffusion coefficient (Oeff). Optimized values of Kp are in agreement with previously reported values. The slope of a correlation between the fitted values of Deff and Kp agrees well with theory, but the absolute values of Deff are a factor of ???106 smaller than predicted for sorption-retarded, gaseous diffusion. Slow transport through an organic or solid phase within the particles or preferential flow through the bed of particulate matter on the filter might be the cause of these very small effective diffusion coefficients. ?? 1993 American Chemical Society.

  2. Sorption of the herbicides diquat and difenzoquat from aqueous medium by polymeric resins in the presence of sodium dodecylsulfate: Kinetic and mechanistic study.

    PubMed

    Vinhal, Jonas O; Lima, Claudio F; Cassella, Ricardo J

    2016-07-01

    The goal of this work was to propose a novel method for the solid-phase extraction of the herbicides diquat (DQT(2+)) and difenzoquat (DFQT(+)) from aqueous medium using polymeric Amberlite XAD-2 and XAD-4 resins in the presence of sodium dodecylsulfate (SDS). The addition of SDS to the medium was of fundamental importance in order to allow the formation of a negatively charged surface able to sorb the cationic solutes. Several factors that could influence the sorption process, such as SDS concentration in the medium, sorbent mass, pH, ionic strength, and initial concentration of the solutes were investigated. Kinetic studies were also performed to model the system and to identify the mechanisms that operate the sorption process of the herbicides. SDS concentration in the medium presented remarkable influence on the extraction efficiency, achieving maximum values when the ratios [SDS]/[herbicide] were approximately 90, for XAD-2, and 22 and 11 for DQT(2+) and DFQT(+), respectively, for XAD-4. The sorption process followed a pseudo second-order kinetic in all cases studied. It was also found that an intraparticle diffusion process controlled exclusively the sorption of the herbicides by the Amberlite XAD-2 and XAD-4 resins in the first 15 min, becoming less active with time. PMID:27070666

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

    PubMed

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

    2014-10-01

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

  4. 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.

  5. Sorption of Zn(II) in aqueous solutions by scoria.

    PubMed

    Kwon, Jang-Soon; Yun, Seong-Taek; Kim, Soon-Oh; Mayer, Bernhard; Hutcheon, Ian

    2005-09-01

    We conducted kinetic and equilibrium sorption experiments on removal of Zn(II) from aqueous solutions by scoria (a vesicular pyroclastic rock with basaltic composition) from Jeju Island, Korea, in order to examine its potential use as an efficient sorbent. The batch-type kinetic sorption tests under variable conditions indicated that the percentage of Zn(II) removal by scoria increases with decreasing initial Zn(II) concentration, particle size, and sorbate/sorbent ratio. However, the sorption capacity decreases with the decrease of the initial Zn(II) concentration and sorbate/sorbent ratio. Equilibrium sorption tests show that Jeju scoria has a larger capacity and affinity for Zn(II) sorption than commercial powdered activated carbon (PAC); at initial Zn(II) concentrations of more than 10mM, the sorption capacity of Jeju scoria is about 1.5 times higher than that of PAC. The acquired sorption data are better fitted to the Langmuir isotherm than the Freundlich isotherm. Careful examination of ionic concentrations in sorption batches suggests that the sorption behavior is mainly controlled by cation exchange and typically displays characteristics of 'cation sorption'. The Zn(II) removal capacity decreases when solution pH decreases because of the competition with hydrogen ions for sorption sites, while the Zn(II) removal capacity increases under higher pH conditions, likely due to hydroxide precipitation. At an initial Zn(II) concentration of 5.0mM, the removal increases from 70% to 96% with the increase of initial pH from 3.0 to 7.0. We recommend Jeju scoria as an economic and efficient sorbent for Zn(II) in contaminated water. PMID:16054911

  6. Sorption-desorption kinetics for powdered and non-powered coal

    SciTech Connect

    Romanov, V.; Soong, Y.

    2007-05-01

    Diffusion through macro- and meso-pores with the subsequent filling of open micropores is a relatively fast process and the manometric measurements with fifteen minute pressure stabilization steps provide a good estimate of excess (ad)sorption. This can be followed by a much slower processes of the penetrant diffusion into the macromolecular network, accompanied by its structural relaxation, with or without free volume changes. The “free volume” effect is a change of the sample’s excluded volume because of the penetrant molecules mixing within the formerly excluded volume of the network or because of contraction (either reversible or semi-permanent) due to external pressure. If the resulting swelling of the sample leads to the mixture’s volume equal to the sum of the initial volumes of the components, there is no apparent change to the void volume and no pressure relaxation is observed (b). On the other hand, if the external forces (either macroscopic pressure or microscopic molecular interaction forces) change the excluded volume of the network (its density), without exchange of the sorbent molecules between the sample and the free fluid phase, such change causes a corresponding change in the void volume, which constitutes a pure free volume effect (c). In this case, no post-decompression exodus of the sorbent out of the sample is observed. As a special case, we consider an incorporation of the penetrant molecules into the network without any change in the volume of the mixture (d), though mathematically this can be written as a superposition of the previous two cases

  7. Kinetics of hydrogen/deuterium exchanges in cometary ices

    NASA Astrophysics Data System (ADS)

    Faure, Mathilde; Quirico, Eric; Faure, Alexandre; Schmitt, Bernard; Theulé, Patrice; Marboeuf, Ulysse

    2015-11-01

    The D/H composition of volatile molecules composing cometary ices brings key constraints on the origin of comets, on the extent of their presolar heritage, as well as on the origin of atmospheres and hydrospheres of terrestrial planets. Nevertheless, the D/H composition may have been modified to various extents in the nucleus when a comet approaches the Sun and experiences deep physical and chemical modifications in its subsurface. We question here the evolution of the D/H ratio of organic species by proton exchanges with water ice. We experimentally studied the kinetics of D/H exchanges on the ice mixtures H2O:CD3OD, H2O:CD3ND2 and D2O:HCN. Our results show that fast exchanges occur on the -OH and -NH2 chemical groups, which are processed through hydrogen bonds exchanges with water and by the molecular mobility triggered by structural changes, such as glass transition or crystallization. D/H exchanges kinetic is best described by a second-order kinetic law with activation energies of 4300 ± 900 K and 3300 ± 100 K for H2O:CD3OD and H2O:CD3ND2 ice mixtures, respectively. The corresponding pre-exponential factors ln(A(s-1)) are 25 ± 7 and 20 ± 1, respectively. No exchange was observed in the case of HCN trapped in D2O ice. These results strongly suggest that upon thermal heating (1) -OH and -NH2 chemical groups of any organic molecules loose their primordial D/H composition and equilibrate with water ice, (2) HCN does not experience proton transfer and keeps a primordial D/H composition and (3) C-H chemical groups are not isotopically modified.

  8. Detailed and global chemical kinetics model for hydrogen

    SciTech Connect

    Marinov, N.M.; Westbrook, C.K.; Pitz, W.J.

    1995-03-01

    Detailed and global chemical kinetic computations for hydrogen-air mixtures have been performed to describe flame propagation, flame structure and ignition phenomena. Simulations of laminar flame speeds, flame compositions and shock tube ignition delay times have been successfully performed. Sensitivity analysis was applied to determine the governing rate-controlling reactions for the experimental data sets examined. In the flame propagation and structure studies, the reactions, OH + H{sub 2} = H{sub 2}0 + H, 0 + H{sub 2} = OH + H and 0 + OH = 0{sub 2} + H were the most important in flames. The shock tube ignition delay time study indicated the H + 0{sub 2} + M = H0{sub 2} + M (M = N{sub 2}, H{sub 2}) and 0 + OH = 0{sub 2} + H reactions controlled ignition. A global rate expression for a one-step overall reaction was developed and validated against experimental hydrogen-air laminar flame speed data. The global reaction expression was determined to be 1.8 {times} 10{sup 13} exp({minus}17614K/T)[H{sub 2}]{sup 1.0}[O{sub 2}]{sup 0.5} for the single step reaction H{sub 2} + 1/2O{sub 2} = H{sub 2}O.

  9. Effect of radiogenic helium on stainless steel 12Cr18Ni10Ti structural changes and hydrogen sorption

    SciTech Connect

    Denisov, E.; Kanashenko, S.; Causey, R.; Grishechkin, S.; Glugla, M.; Hassanein, A.; Kompaniets, T.; Kurdyumov, A.; Malkov, I.; Yukhimchuk, A.

    2008-07-15

    The tritium trick technique was used to build-up radiogenic helium inside stainless steel 12Cr18Ni10Ti (SS). A great quantity of defects with a mean diameter of 20 nm, most probably platelet-like bubbles with {sup 3}He atoms, was observed in {sup 3}He-containing samples. The mean density of these bubbles in SS samples containing {approx}75 appm of {sup 3}He is estimated to be 6x10{sup 20} m{sup -3}. Much larger helium bubbles were observed in SS after annealing the samples at T {>=}1170 K. Thermal release of radiogenic helium occurs at T and >1500 K The presence of {sup 3}He in structural materials causes the formation of an additional state for hydrogen sorption. (authors)

  10. 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. PMID:26638824

  11. Sorption Kinetics on Open Carbon Nanohorn Aggregates: The Effect of Molecular Diameter.

    PubMed

    Russell, Brice A; Khanal, Pravin; Calbi, Maria M; Yudasaka, Masako; Iijima, Sumio; Migone, Aldo D

    2016-01-01

    We present the results of a study of the kinetics of adsorption on aggregates of open carbon nanohorns using argon and CF₄ sorbates. We measured the equilibration times for each value of the sorbent loading along eight adsorption isotherms (four isotherms for each sorbate species). We found that: the equilibration times decrease as the sorbent loading (and the equilibrium pressure of the coexisting gas) increases, for a given temperature; and, that, for a given value of the sorbent loading, the equilibration times decrease with increasing temperature. When considering the effect of scaling of the temperatures by the respective critical temperatures we found that, at the same scaled temperature and at comparable loadings, the equilibration times for CF₄ were longer than those for argon. We discuss a possible explanation for this result. PMID:27110748

  12. Structural study of Ni- or Mg-based complexes incorporated within UiO-66-NH{sub 2} framework and their impact on hydrogen sorption properties

    SciTech Connect

    Žunkovič, E.; Mazaj, M.; Mali, G.; Rangus, M.; Devic, T.; Serre, C.; Logar, N. Zabukovec

    2015-05-15

    Nickel and magnesium acetylacetonate molecular complexes were post-synthetically incorporated into microporous zirconium-based MOF (UiO-66-NH{sub 2}) in order to introduce active open-metal sites for hydrogen sorption. Elemental analysis, nitrogen physisorption and DFT calculations revealed that 5 molecules of Ni(acac){sub 2} or 2 molecules of Mg(acac){sub 2} were incorporated into one unit cell of UiO-66-NH{sub 2}. {sup 1}H–{sup 13}C CPMAS and {sup 1}H MAS NMR spectroscopy showed that, although embedded within the pores, both Ni- and Mg-complexes interacted with the UiO-66-NH{sub 2} framework only through weak van der Waals bonds. Inclusion of metal complexes led to the decrease of hydrogen sorption capacities in Ni-modified as well as in Mg-modified samples in comparison with the parent UiO-66-NH{sub 2}. The isosteric hydrogen adsorption enthalpy slightly increased in the case of Ni-modified material, but not in the case of Mg-modified analogue. - Graphical abstract: A post-synthesis impregnation of Mg- and Ni-acetylacetonate complexes performed on zirconium-based MOF UiO-66-NH{sub 2} does influence the hydrogen sorption performance with respect to the parent matrix. The structural study revealed that Mg- and Ni-acetylacetonate molecules interact with zirconium-terephthalate framework only by weak interactions and they are not covalently bonded to aminoterephthalate ligand. Still, they remain confined into the pores even after hydrogen sorption experiments. - Highlights: • Mg- and Ni-acetylacetonate molecules embedded in the pores of UiO-66-NH{sub 2} by PSM. • Molecules of complexes interact with framework only by van der Waals interactions. • Type/structure of deposited metal-complex impact hydrogen enthalpy of adsorption.

  13. Kinetics of sorption and abiotic oxidation of arsenic(III) by aquifer materials

    NASA Astrophysics Data System (ADS)

    Amirbahman, Aria; Kent, Douglas B.; Curtis, Gary P.; Davis, James A.

    2006-02-01

    The fate of arsenic in groundwater depends largely on its interaction with mineral surfaces. We investigated the kinetics of As(III) oxidation by aquifer materials collected from the USGS research site at Cape Cod, MA, USA, by conducting laboratory experiments. Five different solid samples with similar specific surface areas (0.6-0.9 m 2 g -1) and reductively extractable iron contents (18-26 μmol m -2), but with varying total manganese contents (0.5-3.5 μmol m -2) were used. Both dissolved and adsorbed As(III) and As(V) concentrations were measured with time up to 250 h. The As(III) removal rate from solution increased with increasing solid manganese content, suggesting that manganese oxide is responsible for the oxidation of As(III). Under all conditions, dissolved As(V) concentrations were very low. A quantitative model was developed to simulate the extent and kinetics of arsenic transformation by aquifer materials. The model included: (1) reversible rate-limited adsorption of As(III) onto both oxidative and non-oxidative (adsorptive) sites, (2) irreversible rate-limited oxidation of As(III), and (3) equilibrium adsorption of As(V) onto adsorptive sites. Rate constants for these processes, as well as the total oxidative site densities were used as the fitting parameters. The total adsorptive site densities were estimated based on the measured specific surface area of each material. The best fit was provided by considering one fast and one slow site for each adsorptive and oxidative site. The fitting parameters were obtained using the kinetic data for the most reactive aquifer material at different initial As(III) concentrations. Using the same parameters to simulate As(III) and As(V) surface reactions, the model predictions were compared to observations for aquifer materials with different manganese contents. The model simulated the experimental data very well for all materials at all initial As(III) concentrations. The As(V) production rate was related to the

  14. Kinetics of sorption and abiotic oxidation of arsenic(III) by aquifer materials

    USGS Publications Warehouse

    Amirbahman, A.; Kent, D.B.; Curtis, G.P.; Davis, J.A.

    2006-01-01

    The fate of arsenic in groundwater depends largely on its interaction with mineral surfaces. We investigated the kinetics of As(III) oxidation by aquifer materials collected from the USGS research site at Cape Cod, MA, USA, by conducting laboratory experiments. Five different solid samples with similar specific surface areas (0.6-0.9 m2 g-1) and reductively extractable iron contents (18-26 ??mol m-2), but with varying total manganese contents (0.5-3.5 ??mol m-2) were used. Both dissolved and adsorbed As(III) and As(V) concentrations were measured with time up to 250 h. The As(III) removal rate from solution increased with increasing solid manganese content, suggesting that manganese oxide is responsible for the oxidation of As(III). Under all conditions, dissolved As(V) concentrations were very low. A quantitative model was developed to simulate the extent and kinetics of arsenic transformation by aquifer materials. The model included: (1) reversible rate-limited adsorption of As(III) onto both oxidative and non-oxidative (adsorptive) sites, (2) irreversible rate-limited oxidation of As(III), and (3) equilibrium adsorption of As(V) onto adsorptive sites. Rate constants for these processes, as well as the total oxidative site densities were used as the fitting parameters. The total adsorptive site densities were estimated based on the measured specific surface area of each material. The best fit was provided by considering one fast and one slow site for each adsorptive and oxidative site. The fitting parameters were obtained using the kinetic data for the most reactive aquifer material at different initial As(III) concentrations. Using the same parameters to simulate As(III) and As(V) surface reactions, the model predictions were compared to observations for aquifer materials with different manganese contents. The model simulated the experimental data very well for all materials at all initial As(III) concentrations. The As(V) production rate was related to the

  15. Characterization of the atrazine sorption process on Andisol and Ultisol volcanic ash-derived soils: kinetic parameters and the contribution of humic fractions.

    PubMed

    Báez, María E; Fuentes, Edwar; Espinoza, Jeannette

    2013-07-01

    Atrazine sorption was studied in six Andisol and Ultisol soils. Humic and fulvic acids and humin contributions were established. Sorption on soils was well described by the Freundlich model. Kf values ranged from 2.2-15.6 μg(1-1/n)mL(1/n)g⁻¹. The relevance of humic acid and humin was deduced from isotherm and kinetics experiments. KOC values varied between 221 and 679 mLg⁻¹ for these fractions. Fulvic acid presented low binding capacity. Sorption was controlled by instantaneous equilibrium followed by a time-dependent phase. The Elovich equation, intraparticle diffusion model, and a two-site nonequilibrium model allowed us to conclude that (i) there are two rate-limited phases in Andisols related to intrasorbent diffusion in organic matter and retarded intraparticle diffusion in the organo-mineral complex and that (ii) there is one rate-limited phase in Ultisols attributed to the mineral composition. The lower organic matter content of Ultisols and the slower sorption rate and mechanisms involved must be considered to assess the leaching behavior of atrazine. PMID:23711282

  16. 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

  17. Kinetics study of solid ammonia borane hydrogen release--modeling and experimental validation for chemical hydrogen storage.

    PubMed

    Choi, Young Joon; Rönnebro, Ewa C E; Rassat, Scot; Karkamkar, Abhi; Maupin, Gary; Holladay, Jamie; Simmons, Kevin; Brooks, Kriston

    2014-05-01

    Ammonia borane (AB), NH3BH3, is a promising material for chemical hydrogen storage with 19.6 wt% gravimetric hydrogen capacity of which maximum 16.2 wt% hydrogen can be released via an exothermic thermal decomposition 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 hydrogen release rate at 300 °C is twice as fast as at 160 °C. 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 faster release rate in that temperature range. 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. PMID:24647627

  18. Minimisation of the Hydrogenic Inventory of the ITER Neutral Beamline and Torus Cryo-Sorption Pumps

    SciTech Connect

    Wykes, M

    2005-07-15

    The tritium inventory of all the ITER torus cryopumps open to the vacuum vessel has an administrative limit of 120 g, including tritium bound to hydrocarbon compounds formed by combination of fuel gas with carbon plasma-facing components. The total hydrogenic inventory of each of the torus cryopumps has to be less than that resulting in a deflagration pressure of 0.2 MPa (the design pressure of the ITER vacuum vessel of which the torus and neutral beam cryopump pressure boundaries are a part) following a hydrogen-air ignition. Since the neutral beamline fuelling is with protium and deuterium only, these pumps do not significantly contribute to the 120 g tritium limit. The hydrogenic inventories of both the torus and neutral beam cryopumps add to the total for the vacuum vessel following an in-vessel ingress of coolant from a failed water-cooled component, wherein hydrogen is produced from steam reacting with hot metallic dust. There is therefore a large incentive to keep the peak inventories of both the torus and neutral beamline cryopumps as low as practicable. The paper describes the regeneration patterns of the torus and neutral beamline cryopumps that are used to attain this goal while achieving the required vacuum conditions commensurate with the reference ITER pulse scenarios.

  19. 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.

  20. Probing the hydrogen equilibrium and kinetics in zeolite imidazolate frameworks via molecular dynamics and quasi-elastic neutron scattering experiments

    NASA Astrophysics Data System (ADS)

    Pantatosaki, Evangelia; Jobic, Hervé; Kolokolov, Daniil I.; Karmakar, Shilpi; Biniwale, Rajesh; Papadopoulos, George K.

    2013-01-01

    The problem of simulating processes involving equilibria and dynamics of guest sorbates within zeolitic imidazolate frameworks (ZIF) by means of molecular dynamics (MD) computer experiments is of growing importance because of the promising role of ZIFs as molecular "traps" for clean energy applications. A key issue for validating such an atomistic modeling attempt is the possibility of comparing the MD results, with real experiments being able to capture analogous space and time scales to the ones pertained to the computer experiments. In the present study, this prerequisite is fulfilled through the quasi-elastic neutron scattering technique (QENS) for measuring self-diffusivity, by elaborating the incoherent scattering signal of hydrogen nuclei. QENS and MD experiments were performed in parallel to probe the hydrogen motion, for the first time in ZIF members. The predicted and measured dynamics behaviors show considerable concentration variation of the hydrogen self-diffusion coefficient in the two topologically different ZIF pore networks of this study, the ZIF-3 and ZIF-8. Modeling options such as the flexibility of the entire matrix versus a rigid framework version, the mobility of the imidazolate ligand, and the inclusion of quantum mechanical effects in the potential functions were examined in detail for the sorption thermodynamics and kinetics of hydrogen and also of deuterium, by employing MD combined with Widom averaging towards studying phase equilibria. The latter methodology ensures a rigorous and efficient way for post-processing the dynamics trajectory, thereby avoiding stochastic moves via Monte Carlo simulation, over the large number of configurational degrees of freedom a nonrigid framework encompasses.

  1. Probing the hydrogen equilibrium and kinetics in zeolite imidazolate frameworks via molecular dynamics and quasi-elastic neutron scattering experiments.

    PubMed

    Pantatosaki, Evangelia; Jobic, Hervé; Kolokolov, Daniil I; Karmakar, Shilpi; Biniwale, Rajesh; Papadopoulos, George K

    2013-01-21

    The problem of simulating processes involving equilibria and dynamics of guest sorbates within zeolitic imidazolate frameworks (ZIF) by means of molecular dynamics (MD) computer experiments is of growing importance because of the promising role of ZIFs as molecular "traps" for clean energy applications. A key issue for validating such an atomistic modeling attempt is the possibility of comparing the MD results, with real experiments being able to capture analogous space and time scales to the ones pertained to the computer experiments. In the present study, this prerequisite is fulfilled through the quasi-elastic neutron scattering technique (QENS) for measuring self-diffusivity, by elaborating the incoherent scattering signal of hydrogen nuclei. QENS and MD experiments were performed in parallel to probe the hydrogen motion, for the first time in ZIF members. The predicted and measured dynamics behaviors show considerable concentration variation of the hydrogen self-diffusion coefficient in the two topologically different ZIF pore networks of this study, the ZIF-3 and ZIF-8. Modeling options such as the flexibility of the entire matrix versus a rigid framework version, the mobility of the imidazolate ligand, and the inclusion of quantum mechanical effects in the potential functions were examined in detail for the sorption thermodynamics and kinetics of hydrogen and also of deuterium, by employing MD combined with Widom averaging towards studying phase equilibria. The latter methodology ensures a rigorous and efficient way for post-processing the dynamics trajectory, thereby avoiding stochastic moves via Monte Carlo simulation, over the large number of configurational degrees of freedom a nonrigid framework encompasses. PMID:23343292

  2. Reaction kinetics for the oxygen hydrogenation process on Pt(111) derived from temperature-programmed XPS

    NASA Astrophysics Data System (ADS)

    Näslund, Lars-Åke

    2013-12-01

    Oxygen hydrogenation under ultra high vacuum conditions at the platinum surface was explored using temperature-programmed X-ray photoelectron spectroscopy. Through modeling of the oxygen consumption, information on the reaction kinetics was obtained indicating that the reaction rate of the oxygen hydrogenation process depends on the hydrogen diffusion and on the lifetime of hydroxyl intermediates. The reaction rate is, however, enhanced when an autocatalytic process stabilizes the hydroxyl intermediates through hydrogen bonding to neighboring water molecules. The overall activation energy for the hydrogenation of atomic oxygen to form water was determined to be 0.20 eV with a frequency factor of only 103 s- 1.

  3. Sorption of water alkalinity and hardness from high-strength wastewater on bifunctional activated carbon: process optimization, kinetics and equilibrium studies.

    PubMed

    Amosa, Mutiu K

    2016-08-01

    Sorption optimization and mechanism of hardness and alkalinity on bifunctional empty fruit bunch-based powdered activation carbon (PAC) were studied. The PAC possessed both high surface area and ion-exchange properties, and it was utilized in the treatment of biotreated palm oil mill effluent. Batch adsorption experiments designed with Design Expert(®) were conducted in correlating the singular and interactive effects of the three adsorption parameters: PAC dosage, agitation speed and contact time. The sorption trends of the two contaminants were sequentially assessed through a full factorial design with three factor interaction models and a central composite design with polynomial models of quadratic order. Analysis of variance revealed the significant factors on each design response with very high R(2) values indicating good agreement between model and experimental values. The optimum operating conditions of the two contaminants differed due to their different regions of operating interests, thus necessitating the utility of desirability factor to get consolidated optimum operation conditions. The equilibrium data for alkalinity and hardness sorption were better represented by the Langmuir isotherm, while the pseudo-second-order kinetic model described the adsorption rates and behavior better. It was concluded that chemisorption contributed majorly to the adsorption process. PMID:26752149

  4. Kinetic Monte Carlo and density functional study of hydrogen enhanced dislocation glide in silicon

    NASA Astrophysics Data System (ADS)

    Scarle, S.; Ewels, C. P.

    2006-05-01

    We investigate Hydrogen Enhanced Dislocation Glide [HEDG], using n-fold way Kinetic Monte Carlo simulations of the interaction between hydrogen and 90° partial dislocations in silicon, and a range of new density functional calculations. We examine two different hydrogen arrival species, as well as hydrogen recombination at the dislocation. The Monte Carlo simulations use a line-wise description of the dislocation line parameterized using density functional calculations of migration and formation energies of various dislocation line defects and their complexes with hydrogen. From this we suggest that the rate of H2 expulsion from the dislocation core increases as we approach HEDG, but that if the concentration of the hydrogen species goes beyond that required for HEDG it then slows dislocation motion by choking the line with defects comprised of two hydrogen atoms in a reconstruction bond. A `dislocation engine' model is proposed whereby hydrogen enters the dislocation line, catalyses motion, and is expelled along the core as H2.

  5. 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.

  6. Graphene CVD growth on copper and nickel: role of hydrogen in kinetics and structure.

    PubMed

    Losurdo, Maria; Giangregorio, Maria Michela; Capezzuto, Pio; Bruno, Giovanni

    2011-12-14

    Understanding the chemical vapor deposition (CVD) kinetics of graphene growth is important for advancing graphene processing and achieving better control of graphene thickness and properties. In the perspective of improving large area graphene quality, we have investigated in real-time the CVD kinetics using CH(4)-H(2) precursors on both polycrystalline copper and nickel. We highlighted the role of hydrogen in differentiating the growth kinetics and thickness of graphene on copper and nickel. Specifically, the growth kinetics and mechanism is framed in the competitive dissociative chemisorption of H(2) and dehydrogenating chemisorption of CH(4), and in the competition of the in-diffusion of carbon and hydrogen, being hydrogen in-diffusion faster in copper than nickel, while carbon diffusion is faster in nickel than copper. It is shown that hydrogen acts as an inhibitor for the CH(4) dehydrogenation on copper, contributing to suppress deposition onto the copper substrate, and degrades quality of graphene. Additionally, the evidence of the role of hydrogen in forming C-H out of plane defects in CVD graphene on Cu is also provided. Conversely, resurfacing recombination of hydrogen aids CH(4) decomposition in the case of Ni. Understanding better and providing other elements to the kinetics of graphene growth is helpful to define the optimal CH(4)/H(2) ratio, which ultimately can contribute to improve graphene layer thickness uniformity even on polycrystalline substrates. PMID:22006173

  7. Sorption Kinetics Of Selected Heavy Metals Adsorption To Natural And Fe(III) Modified Zeolite Tuff Containing Clinoptilolite Mineral

    NASA Astrophysics Data System (ADS)

    Sirotiak, Maroš; Lipovský, Marek; Bartošová, Alica

    2015-06-01

    In the research described in this paper, studied was sorption capacity of natural and ferric modification of zeolite tuff containing mineral clinoptilolite from the Nižný Hrabovec deposit to remove potentially toxic metals (ionic forms of chromium, nickel, copper and aluminium) from their water solutions. We reported that the Fe (III) zeolite has an enhanced ability to sorption of Cu (II), and a slight improvement occurs in the case of Cr (VI) and Ni (II). On the other hand, the deterioration was observed in the case of Al (III) adsorption.

  8. Sorption kinetics of superabsorbent polymers (SAPs) in fresh Portland cement-based pastes visualized and quantified by neutron radiography and correlated to the progress of cement hydration

    SciTech Connect

    Schroefl, Christof; Mechtcherine, Viktor; Vontobel, Peter; Hovind, Jan; Lehmann, Eberhard

    2015-09-15

    Water sorption of two superabsorbent polymers in cement-based pastes has been characterized by neutron radiography. Cement pastes with W/C of 0.25 and 0.50 and one additionally containing silica fume (W/C = 0.42) were investigated. The SAPs differed in their inherent sorption kinetics in extracted cement pore solution (SAP 1: self-releasing; SAP 2: retentive). Desorption from SAP 1 started very early after paste preparation. Hence, its individual non-retentiveness governs its behavior only. SAP 2 released water into all matrices, but its kinetics were different. In the paste with the highest W/C, some moderate water release was recorded from the beginning. In the other two pastes, SAP 2 retained its stored liquid during the dormant period, i.e., up to the percolation threshold. Intense desorption then set in and continued throughout the acceleration period. These findings explain the pronouncedly higher efficiency of SAP 2 as internal curing admixture as compared to SAP 1.

  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. A Flexible Microporous Hydrogen-Bonded Organic Framework for Gas Sorption and Separation.

    PubMed

    Wang, Hailong; Li, Bin; Wu, Hui; Hu, Tong-Liang; Yao, Zizhu; Zhou, Wei; Xiang, Shengchang; Chen, Banglin

    2015-08-12

    A microporous three-dimensional hydrogen-bonded organic framework (HOF-5) has been constructed from a new organic linker 4,4',4″,4‴-tetra(2,4-diamino-1,3,5-triazin-6-yl)tetraphenylethene. Activated HOF-5a exhibits a stepwise N2 adsorption isotherm at 77 K, suggesting framework flexibility. The structure of activated HOF-5a has been established by powder X-ray diffraction studies, indicating a significant framework contraction from as-synthesized HOF-5 to activated HOF-5a of ∼21% by volume. HOF-5a shows moderately high porosity with a Brunauer-Emmett-Teller (BET) surface area of 1101 m(2)/g, and takes up a large amount of acetylene and carbon dioxide under ambient conditions. Powder neutron diffraction studies and theoretical calculations reveal that suitable pore sizes, curvatures, and functional sites collectively enable HOF-5a to encapsulate a high density of carbon dioxide molecules packed in a pseudo-one-dimensional array along the pore channel. PMID:26214340

  11. Theoretical evidence of the difference in kinetics of water sorption and desorption in Nafion® membrane and experimental validation

    NASA Astrophysics Data System (ADS)

    Didierjean, S.; Perrin, J. C.; Xu, F.; Maranzana, G.; Klein, M.; Mainka, J.; Lottin, O.

    2015-12-01

    Water transport during sorption and desorption in Nafion® 117 samples is studied by means of dynamic model and experiments as a response of relative humidity step. The model takes into account a transfer resistance at the interface between the membrane and the surrounding medium, and considers that the water content of the membrane remains uniform at all times during sorption and desorption, which was confirmed using NMR imaging. Thus, its main hypothesis is that the membrane is in equilibrium with the humid gas located at the interface whose relative humidity is different than in the bulk. The calculated time-variations in the water content of a membrane sample (in acid form) during sorption and desorption show that desorption is faster than sorption due to the variations in the slope of the water uptake isotherm. The theoretical results and the experimental data show a good agreement which allows the determination of the mass transfer coefficient. The influence of diffusion and thermal effects are also discussed.

  12. Effects of soil organic matter on the kinetics and mechanisms of Pb(II) sorption and desorption in soil

    SciTech Connect

    Strawn, D.G.; Sparks, D.L.

    2000-02-01

    To improve predictions of the toxicity and threat from Pb contaminated soil, it is critical that time-dependent sorption and desorption behavior be understood. In this paper, the sorption and desorption behavior of Pb in a Matapeake silt loam soil (Typic Hapludult) were studied by stirred-flow and batch experiments. In addition, the authors studied the effects of soil organic matter (SOM) on sorption and desorption behavior by treating the soil with sodium hypochlorite to remove the SOM fraction, and using a soil with six times as much SOM (St. Johns loamy sand [Typic Haplaquods]) as the Matapeake soil. Lead sorption consisted of a fast initial reaction in which all of the Pb added to the stirred-flow chamber was sorbed. Following this initial fast reaction, sorption continued and appears to be rate limited. The total amount of Pb sorbed was 102, 44, and 27 mmol kg{sup {minus}1} for the St. Johns soil and the untreated and treated Matapeake soils, respectively. Desorption experiments were conducted on the soils with the background electrolyte as the eluent in the stirred-flow chamber. In the St. Johns soil only, 32% of the total sorbed Pb was desorbed, while 47 and 76% of the sorbed Pb was released from the untreated and treated Matapeake soil, respectively. The correlation between SOM in the soils, and the percentage Pb desorbed from the soils suggests that SOM plays an important role in slow desorption reactions of Pb from soil materials. Aging experiments in which sorbed Pb was incubated for 1, 10, and 32 d showed that sorption incubation time had no effect on Pb desorption behavior. Analysis of the treated and untreated Matapeake soils by x-ray absorption fine structure (XAFS) spectroscopy revealed that the local atomic structure of sorbed Pb is distinctly different in the two samples. In the soil treated to remove SOM, the data were well represented by theoretical models using O, Si, and Pb backscattering atoms. In the untreated soil, the XAFS data were best

  13. [Sorption Characteristics of Phenanthrene and 1, 1-Dichloroethene onto Reed Straw Biochar in Aquatic Solutions].

    PubMed

    Wu, Qing-wen; Meng, Liang; Zhang, Zhi-hao; Luo, Qi-shi; Yang, Jie

    2016-02-15

    The purpose of this study was to investigate the sorption characteristics of phenanthrene (PHE) and 1, 1-dichloroethene (1, 1-DCE) onto reed straw biochar at 500 degrees C in aquatic solutions. The sorption mechanisms and effects of solution pH and biochar mass on sorption intensity were discussed. The results showed that the time required to reach sorption equilibrium was 60 min and 480 min for PHE and 1, 1-DCE, respectively, with maximum removal rates of 81, 87% and 90.18%. The sorption kinetics of both PHE and 1, 1-DCE fitted the pseudo-second-order model well, but the pseudo-second-order reaction rate of PHE was higher than that of 1, 1-DCE. Furthermore, the sorption processes were controlled by both membrane diffusion and intra-particle diffusion, and the latter was found to be the rate-controlling step. Sorption isotherms of the two organic pollutants fitted well with the Freundlich equation, and the sorption affinity of 1, 1-DCE onto biochar was greater than that of PHE. The total sorption mechanism of biochar was the combination of partition and adsorption, and dominated by adsorption. The adsorption capacity of 1, 1-DCE was greater than that of PHE, but its partition capacity was much smaller, indicating that pollutants' molecular volume and relative polarity would mainly affect the total sorption. Analysis of Fourier transform infrared spectroscopy (FTIR) demonstrated that oxygen- and hydrogen-containing functional groups and pi--pi interaction were important for PHE and 1, 1-DCE sorption onto biochar. The solution pH value had no significant effect on the sorption intensity of PHE and 1, 1-DCE, however, with biochar mass increasing from 5 mg to 50 mg, the equilibrium sorption amount of PHE and 1, 1-DCE decreased by 6.78 times and 2.18 times, and the removal rate increased by 20.21% and 15.78%, respectively. PMID:27363160

  14. Kinetic and Prediction of Hydrogen Outgassing from Lithium Hydride

    SciTech Connect

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

    2006-08-31

    In most industrial or device applications, LiH is placed in either an initially dry or a vacuum environment with other materials that may release moisture slowly over many months, years, or even decades. In such instances, the rate of hydrogen outgassing from the reaction of LiH with H{sub 2}O can be reasonably approximated by the rate at which H{sub 2}O is released from the moisture containing materials. In a vacuum or dry environment, LiOH decomposes slowly with time into Li{sub 2}O even at room temperature according to: 2LiOH(s) {yields} Li{sub 2}O(s) + H{sub 2}O(g) (1). The kinetics of the decomposition of LiOH depends on the dryness/vacuum level and temperature. It was discovered by different workers that vacuum thermal decomposition of bulk LiOH powder (grain sizes on the order of tens to hundreds of micrometers) into Li{sub 2}O follows a reaction front moving from the surface inward. Due to stress at the LiOH/vacuum interface and defective and missing crystalline bonding at surface sites, lattice vibrations at the surfaces/interfaces of most materials are at frequencies different than those in the bulk, a phenomenon observed in most solids. The chemical reactivity and electronic properties at surfaces and interfaces of materials are also different than those in the bulk. It is, therefore, expected that the amount of energy required to break bonds at the LiOH/vacuum interface is not as large as in the bulk. In addition, in an environment where there is a moisture sink or in the case of a continuously pumped vacuum chamber, H{sub 2}O vapor is continuously removed and LiOH decomposes into Li{sub 2}O from the LiOH/vacuum interface (where it is thermally less stable) inward according to reaction (1) in an effort to maintain the equilibrium H{sub 2}O vapor pressure at the sample/vacuum interface. In a closed system containing both LiH and LiOH, the H{sub 2}O released from the decomposition of LiOH reacts with LiH to form hydrogen gas according to the following

  15. Hydrogen Reduction Kinetics of Magnetite Concentrate Particles Relevant to a Novel Flash Ironmaking Process

    NASA Astrophysics Data System (ADS)

    Wang, Haitao; Sohn, H. Y.

    2013-02-01

    A novel ironmaking technology is under development at the University of Utah. The purpose of this research was to determine comprehensive kinetics of the flash reduction reaction of magnetite concentrate particles by hydrogen. Experiments were carried out in the temperature range of 1423 K to 1673 K (1150 °C to 1400 °C) with the other experimental variables being hydrogen partial pressure and particle size. The nucleation and growth kinetics expression was found to describe the reduction rate of fine concentrate particles and the reduction kinetics had a 1/2-order dependence on hydrogen partial pressure and an activation energy of 463 kJ/mol. Unexpectedly, large concentrate particles reacted faster at 1423 K and 1473 K (1150 °C and 1200 °C), but the effect of particle size was negligible when the reduction temperature was above 1573 K (1300 °C). A complete reaction rate expression incorporating all these factors was formulated.

  16. A study of spin isomer conversion kinetics in supercritical fluid hydrogen for cyrogenic fuel storage technologies

    NASA Astrophysics Data System (ADS)

    Matthews, Manyalibo J.; Petitpas, Guillaume; Aceves, Salvador M.

    2011-08-01

    A detailed kinetic study of para-ortho hydrogen conversion under supercritical conditions using rotational Raman scattering is presented. Isochoric measurements of initially low ortho concentrations over temperatures 32 < T < 280 K and densities 0.014 < ρ < 0.060 g/cm3 were used to derive kinetic rate constants k(ρ, T) by solving an autocatalytic kinetic rate equation. At low ortho concentrations and T < 100 K, k is found to be ˜2× higher than previous results based on thermal conductivity measurements, decreasing weakly with temperature, similar to Wigner's original paramagnetic theory. Accurate modeling of k(ρ, T) is critical in predicting cryogenic hydrogen fuel tank dormancy performance for hydrogen-power vehicles.

  17. Mechanisms and kinetics of coal hydrogenation. Quarterly progress report, October-December 1979

    SciTech Connect

    Gary, J. H.; Baldwin, R. M.; Bain, R. L.

    1980-02-01

    Colorado School of Mines is conducting coal hydrogenation research with the following objectives and scope of work: (1) Comparison of the rates of coal hydrogenation in continuous flow stirred tank and tube flow reactors using pure hydrogen, catalyzed CO-STEAM, and syngas processing conditions; (2) Investigation of the influence of coal rank on the rate of hydrogenation of coal to preasphaltene, asphaltenes, and oil in batch reactors; (3) Batch evaluation of the effect of operating conditions (temperature and pressure) on the rate of hydrogenation of coal-derived preasphaltanes and asphaltenes; (4) Determination of the effect of selected disposable catalysts on the rate of batch hydrogenation of preasphaltenes and asphaltenes and selected bituminous coals. Testing and evaluation of promising catalyst systems in the contunuous processing unit; (5) Formulation of a unified kinetic/mechanistic model for coal liquefaction taking into account petrography of the feed coal and hydrocarbon lumps in the product oil.

  18. Hydrogenation kinetics in oxidized boron-doped silicon irradiated by keV electrons

    NASA Astrophysics Data System (ADS)

    Lin, Wallace Wan-Li; Sah, Chih-Tang

    1988-08-01

    Hydrogenation kinetics of boron acceptors in oxidized silicon during and after repeated 8-keV electron irradiation (225-2700-μC/cm2 stresses and 10-168-h interirradiation anneals) at room temperature are reported. Hydrogenation proceeds rapidly during irradiation but continues for many hours after the 8-keV electron beam is removed. Postoxidation process dependencies show that postoxidation and postmetallization annealing processes reduce the hydrogenation effect during the 8-keV electron irradiation, while exposure of the oxide to water prior to aluminum electrode deposition enhances it. The data can be interpreted by our two-reaction model consisting of the hydrogen capture reaction by the boron acceptor and the hydrogen recombination reaction to form hydrogen molecule.

  19. Sorption kinetics and equilibrium of the herbicide diuron to carbon nanotubes or soot in absence and presence of algae.

    PubMed

    Schwab, Fabienne; Camenzuli, Louise; Knauer, Katja; Nowack, Bernd; Magrez, Arnaud; Sigg, Laura; Bucheli, Thomas D

    2014-09-01

    Carbon nanotubes (CNT) are strong sorbents for organic micropollutants, but changing environmental conditions may alter the distribution and bioavailability of the sorbed substances. Therefore, we investigated the effect of green algae (Chlorella vulgaris) on sorption of a model pollutant (diuron, synonyms: 3-(3,4-Dichlorophenyl)-1,1-dimethylurea, DCMU) to CNT (multi-walled purified, industrial grade, pristine, and oxidized; reference material: Diesel soot). In absence of algae, diuron sorption to CNT was fast, strong, and nonlinear (Freundlich coefficients: 10(5.79)-10(6.24) μg/kgCNT·(μg/L)(-n) and 0.62-0.70 for KF and n, respectively). Adding algae to equilibrated diuron-CNT mixtures led to 15-20% (median) diuron re-dissolution. The relatively high amorphous carbon content slowed down ad-/desorption to/from the high energy sorption sites for both industrial grade CNT and soot. The results suggest that diuron binds readily, but - particularly in presence of algae - partially reversibly to CNT, which is of relevance for environmental exposure and risk assessment. PMID:24949853

  20. 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.

  1. 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.

  2. Kinetics of fatigue cracks in iron in electrolytic hydrogen impregnation

    SciTech Connect

    Pokhmurskii, V.I.; Bilyi, L.M.

    1985-05-01

    Fatigue failure of metals is localized in the zone of plastic deformation at the tip of the developing crack. Crack development depends to a large extent upon the parameters of the deformed volume, the loading conditions, and features of the material microstructure. It may be assumed that the medium, especially a hydrogen-impregnating medium, leads to a change in the zone of plastic deformation and thereby influences the rate of fatigue crack growth. This work is devoted to a study of cyclic crack resistance and determination of the zone of plastic deformation of failure specimens of Armco iron under conditions of the action of a hydrogen-impregnating medium.

  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. 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.

  5. 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.

  6. 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.

  7. Sorption kinetic study of selenite and selenate onto a high and low pressure aged iron oxide nanomaterial

    PubMed Central

    Gonzalez, Christina M.; Hernandez, Jeffrey; Peralta-Videa, Jose R.; Botez, Cristian E.; Parsons, Jason G.; Gardea-Torresdey, Jorge L.

    2015-01-01

    The sorption of selenite (SeO32−) and selenate (SeO42−) onto Fe3O4 nanomaterials produced by non microwave-assisted or microwave-assisted synthetic techniques was investigated through use of the batch technique. The phase of both synthetic nanomaterials was determined to be magnetite by X-ray diffraction. The average grain sizes of non microwave-assisted and microwave-assisted synthetic Fe3O4 were determined to be 27 and 25 nm, respectively through use of the Scherrer's equation. Sorption of selenite was pH independent in the pH range of 2-6, while sorption of selenate decreased at pH 5 and 6. The addition of Cl− had no significant effect on selenite or selenate binding, while the addition of NO3− only affected selenate binding to the microwave assisted Fe3O4. A decrease of selenate binding to both synthetic particles was observed after the addition of SO42− while selenite binding was not affected. The addition of PO43− beginning at concentrations of 0.1 ppm had the most prominent effect on the binding of both selenite and selenate. The capacities of binding, determined through the use of Langmuir isotherm, were found to be 1923 and 1428 mg Se/kg of non microwave-assisted Fe3O4 and 2380 and 2369 mg Se/kg of microwave-assisted Fe3O4 for selenite and selenate, respectively. PMID:21907486

  8. 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)

  9. 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.

  10. Mechanisms and kinetics of coal hydrogenation. Quarterly progress report, April-June

    SciTech Connect

    Baldwin, R.M.; Furlong, M.W.

    1981-07-01

    Colorado School of Mines is engaged in an experimental program for the Department of Energy to develop comprehensive models for the effects of coal composition upon the kinetics and mechanisms of coal hydrogenation, for the effects of mineral matter additives (disposable catalysts) upon kinetics and mechanisms of coal hydrogenation, and for the kinetics and mechanisms of the hydrogenation of coal derived products such as preasphaltenes and asphaltenes. The continuous flow coal processing unit was modified to alleviate problems with non-representative sampling during the course of operation. A synthetic recycle oil solvent was prepared to allay any doubts regarding the distribution of reacted solvent components in the product samples. Data from the coal reactivity study was fitted by true second-order reversible kinetics expressions. The forward rate constants were correlated with H/C ratio, mean-max reflectance, and fraction reactive macerals of the parent coals. Kinetic reactivities were also shown to correlate with the percentage of volatile carbon in the parent coals. Intrinsic THF solubilities of the parent coals were measured experimentally and the resulting values incorporated in the evaluation of second-order rate constants. The reactivities were not significantly affected by this modification. Reproductibility tests were initiated in the disposable catalysts study. Agreement between these data and those from the initial phase of this study were fair. Further tests will be made to verify these results.

  11. Characterization of electron kinetics regime with electron energy probability functions in inductively coupled hydrogen plasmas

    NASA Astrophysics Data System (ADS)

    Kim, June Young; Cho, Won-Hwi; Dang, Jeong-Jeung; Chung, Kyoung-Jae; Hwang, Y. S.

    2016-02-01

    Electron kinetics regime is characterized with the evolution of electron energy probability functions (EEPFs) in inductively coupled hydrogen plasmas. Measurements on EEPFs are carried out with a radio-frequency-compensated single Langmuir probe at the center of a planar-type hydrogen plasma driven by 13.56 MHz wave frequency. Measured EEPFs deviate considerably from the Maxwellian distribution only at relatively high pressures (15-40 mTorr), and the effective electron temperature steeply decreases as the gas pressure increases. Such evolution of the EEPF shapes with pressures is discussed in the consideration of the electron energy relaxation length and various characteristic frequencies. It is found that the EEPFs show locally depleted electron energy distribution where the electron-molecule vibrational collision frequency exceeds the electron-electron collision frequency at the local kinetics regime, while the measured EEPF is not dependent on the vibrational collision frequency at the non-local kinetics regime. Variation of the EEPF shape with distance from the heating region at the local kinetics regime is also well explained in the context of the energy relaxation length and electron-molecule collision frequencies. This study indicates that the control of electron energy distribution should be carried out in the consideration of electron kinetic regime depending on the energy relaxation length for various hydrogen plasma sources.

  12. 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.

  13. Kinetics of hydrogen attack of 2 1/4 Cr-1 Mo steel

    SciTech Connect

    Parthasarathy, T.A.

    1983-01-01

    The effect of welding on the kinetics of hydrogen attack of 2 1/4 Cr-1 Mo quenched and tempered steel was studied using a highly sensitive capacitance dilatometer, in the temperature range of 490 C to 590 C and hydrogen pressures of 10 to 23 MPa. The strain rate of the weld metal was an order of magnitude greater than that of the base metal at 500 C and 20.3 MPa of hydrogen, but it was the same as that of the base metal at 570 C. The base metal exhibited an activation energy of 256 +/- 5 KJ/mol and a methane pressure dependence of 1.76 +/- 0.4. The weld metal had an activation energy of 313 +/- 36 KJ/mol and a methane pressure dependence of 6.6 +/- 1.5. The bubbles in the base metal formed preferentially at the grain boundaries, but those in the weld metal showed no such preference. The effects of tempering on the hydrogen attack kinetics was studied by measuring strain rates and carbon activities of 2 1/4 Cr-1 Mo steel samples tempered to different extents. Both carbon activity and the hydrogen attack strain rate decreased monotonically with tempering. Tempering for up to 500 hrs at 700 C does not decrease carbon activity below 0.05 and appreciable strain rates were measured at 550 C and 20.3 MPa. Bubble growth mechanism maps were drawn for both carbon and low alloy steels, and the maps give the predicted mechanisms controlling bubble growth at various temperatures and hydrogen pressures. Commercial 2 1/4 Cr-1 Mo Q and T steel was found to suffer hydrogen attack by grain boundary diffusion up to about 25 MPa hydrogen. The weld metal however was found to suffer hydrogen attack by the growth of bubbles by power-law creep of the matrix.

  14. 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.

  15. Diffusion of hydrogen within idealized grains of bcc Fe: A kinetic Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Du, Yaojun A.; Rogal, Jutta; Drautz, Ralf

    2012-11-01

    Structural defects in materials such as vacancies, grain boundaries, and dislocations may trap hydrogen and a local accumulation of hydrogen at these defects can lead to the degradation of the materials properties. An important aspect in obtaining insight into hydrogen-induced embrittlement on the atomistic level is to understand the diffusion of hydrogen in these materials. In our study we employ kinetic Monte Carlo (kMC) simulations to investigate hydrogen diffusion in bcc iron within different microstructures. All input data to the kMC model, such as available sites, solution energies, and diffusion barriers, are obtained from first-principles calculations. We find that hydrogen mainly diffuses within the interface region with an overall diffusivity that is lower than in pure bcc Fe bulk. The concentration dependence of the diffusion coefficient is strongly nonlinear and the diffusion coefficient may even decrease with an increasing hydrogen concentration. To describe the macroscopic diffusion coefficient we derive an analytic expression as a function of hydrogen concentrations and temperatures which is in excellent agreement with our numerical results for idealized microstructures.

  16. Mechanisms and kinetics of coal hydrogenation. Quarterly progress report, October-December 1980

    SciTech Connect

    Gary, J H; Baldwin, R M; Bain, R L; Furlong, M W

    1981-01-01

    Colorado School of Mines is engaged in an experimental program to develop comprehensive models for the effects of coal composition upon the kinetics and mechanisms of coal hydrogenation, for the effects of mineral matter additives (disposable catalysts) upon kinetics and mechanisms of coal hydrogenation, and for the kinetics and mechanisms of the hydrogenation of coal-derived products such as preasphaltenes and asphaltenes. Safety modifications to the CSM continuous processing unit were completed to shield the control room from the gas and liquid-solid product sampling systems. A mass balance analysis of sample validity was begun. All but two of sixteen coals in the suite of coal reactivity study coals have been run. Computer modelling of proposed reaction networks was started. Initial efforts at coal property versus reactivity correlations were begun. Feed material preparation for the asphaltene hydrogenation study was completed, and preliminary testing of the reactor system was begun. The experimental portion of the disposable catalyst study screening program was completed. Conclusions are pending statistical analyses of the data.

  17. Influence of hydrogen chemisorption kinetics on the interpretation of hydrogen transport through iron membranes

    NASA Technical Reports Server (NTRS)

    Shanabarger, M. R.; Taslami, A.; Nelson, H. G.

    1981-01-01

    The influence of a specific surface reaction on the transport of gas-phase hydrogen through iron membranes has been investigated on the basis of model calculations. The surface reaction involves an adsorbed molecular hydrogen precursor between the gas phase and the dissociated chemisorbed state. The calculations demonstrate that the surface reaction for the H2/Fe system makes significant contributions to the time delay associated with the transient hydrogen transport through iron membranes, even under conditions where the steady-state hydrogen transport is independent of the surface reaction. These contributions to the time delay are interpreted in terms of an effective diffusivity, which is a function of the pressure on the entrance side and the thickness of the membrane.

  18. Kinetics of the reaction of nitric oxide with hydrogen

    NASA Technical Reports Server (NTRS)

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

    1975-01-01

    The reaction of nitric oxide with hydrogen has been studied in the temperature range 2400-4500 K using a shock-tube technique. 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 decomposition of nitric oxide behind the shock was found to be modeled well by a fifteen-reaction system. A principal result of the study was the determination of the rate constant k1 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 k1 were obtained for each test through comparisons of measured and numerically predicted NO profiles. The data are fit closely by the expression k1 = 1.34 times 10 to the fourteenth power exp(-49 200/RT) cu cm/mole-sec. These data appear to be the first available for this rate constant.

  19. 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. PMID:18490114

  20. Kinetics and mechanisms of hydrogen sulfide adsorption by biochars.

    PubMed

    Shang, Guofeng; Shen, Guoqing; Liu, Liang; Chen, Qin; Xu, Zhiwei

    2013-04-01

    Three different biochars as cost-effective substitutes for activated carbon (AC) were tested for their hydrogen sulfide (H2S) adsorption ability. The biochars were produced from camphor (SC), bamboo (SB), and rice hull (SR) at 400°C by oxygen-limited pyrolysis. The surface area (SA), pH, and Fourier transform infrared spectras of the biochars and AC were compared. The maximum removal rates and the saturation constants were obtained using the Michaelis-Menten-type equation. The three biochars were found to be alkaline, and the SAs of the biochars were much smaller than that of the AC. The H2S breakthrough capacity was related to the local pH within the pore system of the biochar. The order observed in terms of both biochar and AC adsorption capacity was SR>SB>SC>AC. SR efficiently removed H2S within the inlet concentration range of 10-50 μL/L. Biochars derived from agricultural/forestry wastes are a promising H2S adsorbent with distinctive properties. PMID:23455220

  1. Kinetics and capacities of phosphorus sorption to tertiary stage wastewater alum solids, and process implications for achieving low-level phosphorus effluents.

    PubMed

    Maher, Chris; Neethling, J B; Murthy, Sudhir; Pagilla, Krishna

    2015-11-15

    The role of adsorption and/or complexation in removal of reactive or unreactive effluent phosphorus by already formed chemical precipitates or complexes has been investigated. Potential operational efficiency gains resulting from age of chemically precipitated tertiary alum sludge and the recycle of sludge to the process stream was undertaken at the Iowa Hill Water Reclamation Facility which employs the DensaDeg(®) process (IDI, Richmond, VA) for tertiary chemical P removal to achieve a filtered final effluent total phosphorus concentration of <30 μg/L. The effect of sludge solids age was found to be insignificant over the solids retention time (SRT) of 2-8 days, indicating that the solids were unaffected by the aging effects of decreasing porosity and surface acidity. The bulk of solids inventory was retained in the clarifier blanket, providing no advantage in P removal from increased solids inventory at higher SRTs. When solids recycle was redirected from the traditional location of the flocculation reactor to a point just prior to chemical addition in the chemical mixing reactor, lower effluent soluble P concentrations at lower molar doses of aluminum were achieved. At laboratory scale, the "spent" or "waste" chemical alum sludge from P removal showed high capacity and rapid kinetics for P sorption from real wastewater effluents. Saturation concentrations were in the range of 8-29 mg soluble reactive P/g solids. Higher saturation concentrations were found at higher temperatures. Alum sludge produced without a coagulant aid polymer had a much higher capacity for P sorption than polymer containing alum sludge. The adsorption reaction reached equilibrium in less than 10 min with 50% or greater removal within the first minute. PMID:26331896

  2. Thermodynamics, Kinetics, and Activation energy Studies of the sorption of chromium(III) and chromium(VI) to a Mn3O4 nanomaterial

    PubMed Central

    Cantu, Yvette; Remes, Abril; Reyna, Alejandra; Martinez, Denise; Villarreal, Jahaziel; Ramos, Hilda; Trevino, Samantha; Tamez, C.; Martinez, A.; Eubanks, T.; Parsons, J. G.

    2014-01-01

    In this study, a manganese oxide, Mn3O4 was used to remove chromium(III) and chromium(VI) from aqueous solutions. The Mn3O4 nanomaterial was synthesized through a precipitation method, and was characterized using XRD, which confirmed the material had a crystal structure similar to hausmannite. In addition, using Scherrer’s equation it was determined that the nanomaterial had an average grain size of 19.5 ± 1.10 nm. A study of the effects of pH on the binding of chromium(III) and chromium(VI) showed that the optimum binding pH was 4 and 3 respectively. Batch isotherm studies were performed to determine the binding capacity of chromium(III), which was determined to be 18.7 mg/g, 41.7 mg/g, and 54.4 mg/g respectively for 4°C, 21°C, and 45°C. Chromium(VI) on the other hand had lower binding capacities of 2.5 mg/g, 4.3 mg/g, and 5.8 mg/g for 4°C, 21°C, 45°C, respectively. Thermodynamic studies performed indicated the sorption process was for the most part controlled by physisorption. The ΔG for the sorption of chromium(III) and Chromium(VI) ranged from −0.9 to −13 kJ/mol, indicating a spontaneous reaction was occurring. The enthalpy indicated a endothermic reaction was occurring during the binding and show ΔH values of 70.6 and 19.1 kJ.mol for chromium(III) and Chromium(VI), respectively. In addition, ΔS for the reaction had positive values of 267 and 73 J/mol for chromium(III) and chromium(VI) which indicate a spontaneous reaction. In addition, the sorption process was found to follow pseudo second order kinetic and the activation energy studies indicated the binding process occurred through chemisorption. PMID:25097453

  3. Time-dependent gas phase kinetics in a hydrogen diluted silane plasma

    NASA Astrophysics Data System (ADS)

    Nunomura, S.; Yoshida, I.; Kondo, M.

    2009-02-01

    The gas phase kinetics in a high-pressure hydrogen diluted silane plasma has been studied at time scales of 10-2-6×102 s. The time-resolved gas phase composition shows the following kinetics at different time scales: silane decomposition and polysilane generation in ≲2×10-1 s, nanoparticle formation and plasma density reduction in 10-1-100 s, polysilane accumulation in 100-102 s, and silane depletion and electrode heating in ≳101 s. Disilane radicals are implied to be the dominant film precursors in addition to silyl radicals.

  4. Time-dependent gas phase kinetics in a hydrogen diluted silane plasma

    SciTech Connect

    Nunomura, S.; Kondo, M.; Yoshida, I.

    2009-02-16

    The gas phase kinetics in a high-pressure hydrogen diluted silane plasma has been studied at time scales of 10{sup -2}-6x10{sup 2} s. The time-resolved gas phase composition shows the following kinetics at different time scales: silane decomposition and polysilane generation in < or approx. 2x10{sup -1} s, nanoparticle formation and plasma density reduction in 10{sup -1}-10{sup 0} s, polysilane accumulation in 10{sup 0}-10{sup 2} s, and silane depletion and electrode heating in > or approx. 10{sup 1} s. Disilane radicals are implied to be the dominant film precursors in addition to silyl radicals.

  5. 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.

  6. 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

    2014-11-01

    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. PMID:25244324

  7. SEDIMENT-ASSOCIATED REACTIONS OF AROMATIC AMINES: 1. ELUCIDATION OF SORPTION MECHANISMS

    EPA Science Inventory

    Sorption of aromatic amines to sediments and soils can occur by both reversible physical processes and irreversible chemical processes. To elucidate the significance of these sorption pathways, the sorption kinetics of aniline and pyridine were studied in resaturated pond sedimen...

  8. 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. PMID:22750091

  9. 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.

  10. 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.

  11. 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.

  12. 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). PMID:19520509

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

    PubMed

    Harris, Steve H; Smith, Richard L; Suflita, Joseph M

    2007-05-01

    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. PMID:17439588

  14. 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.

  15. 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.

  16. Mechanism and kinetics of the vapor-phase hydrogenation of acetone and dehydrogenation of 2-propanol on a platinum catalyst

    SciTech Connect

    Golodets, G.I.; Pavlenko, N.V.; Tripol'skii, A.I.

    1986-09-01

    A study was carried out on the mechanism and kinetics of the vapor-phase hydrogenation of acetone and the dehydrogenation of 2-propanol on a Pt/ A1/sub 2/O/sub 3/ catalyst. A general kinetic equation was obtained describing both the forward and reverse reactions.

  17. Kinetic Monte Carlo simulation on influence of vacancy on hydrogen diffusivity in tungsten

    NASA Astrophysics Data System (ADS)

    Oda, Takuji; Zhu, Deqiong; Watanabe, Yoshiyuki

    2015-12-01

    Kinetic Mote Carlo (KMC) simulations are performed to quantify the influence of trap in hydrogen diffusivity in tungsten. As a typical trap, mono-vacancy is considered in the simulation. Experimental results reported by Frauenfelder are nicely reproduced when hydrogen concentration and trap concentration expected in the experiment are employed in the simulation. The effective diffusivity of hydrogen is evidently decreased by traps even at high temperatures like 1300 K. These results suggest that only high-temperature experimental data, which are not significantly affected by traps, should be fitted to, in order to derive the true hydrogen diffusivity from experiments. Therefore, we recommend D = 1.58 ×10-7exp(- 0.25 eV / kT) m2 s-1 as the equation for hydrogen diffusion coefficient in tungsten, which was obtained by fitting only to experimental data at 1500-2400 K by Heinola and Ahlgren, rather than the most cited equation D = 4.1 ×10-7exp(- 0.39 eV / kT) m2 s-1, which was obtained by fitting to all experimental data at 1100-2400 K including some data that should be affected by traps.

  18. 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.

  19. Sorption enhanced reaction process for direct production of fuel-cell grade hydrogen by low temperature catalytic steam-methane reforming

    NASA Astrophysics Data System (ADS)

    Beaver, Michael G.; Caram, Hugo S.; Sircar, Shivaji

    New experimental data are reported to demonstrate that a sorption enhanced reaction (SER) concept can be used to directly produce fuel-cell grade H 2 (<20 ppm CO) by carrying out the catalytic, endothermic, steam-methane reforming (SMR) reaction (CH 4 + 2H 2O ↔ CO 2 + 4H 2) in presence of a CO 2 selective chemisorbent such as K 2CO 3 promoted hydrotalcite at reaction temperatures of 520 and 550 °C, which are substantially lower than the conventional SMR reaction temperatures of 700-800 °C. The H 2 productivity of the sorption enhanced reactor can be large, and the conversion of CH 4 to H 2 can be very high circumventing the thermodynamic limitations of the SMR reaction due to the application of the Le Chetalier's principle in the SER concept. Mathematical simulations of a cyclic two-step SER concept showed that the H 2 productivity of the process (moles of essentially pure H 2 produced per kg of catalyst-chemisorbent admixture in the reactor per cycle) is much higher at a reaction temperature of 590 °C than that at 550 or 520 °C. On the other hand, the conversion of feed CH 4 to high purity H 2 product is relatively high (>99+%) at all three temperatures. The conversion is much higher than that in a conventional catalyst-alone reactor at these temperatures, and it increases only moderately (<1%) as the reaction temperature is increased from 520 to 590 °C. These results are caused by complex interactions of four phenomena. They are (a) favorable thermodynamic equilibrium of the highly endothermic SMR reaction at the higher reaction temperature, (b) faster kinetics of SMR reaction at higher temperatures, (c) favorable removal of CO 2 from the reaction zone at lower temperatures, and (d) higher cyclic working capacity for CO 2 chemisorption at higher temperature.

  20. Charged particle dynamics and molecular kinetics in the hydrogen postdischarge plasma

    SciTech Connect

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

    2006-11-15

    The afterglow of a parallel plate radio frequency discharge in hydrogen is studied by numerical modelling to compare ion dynamics and chemical effects on the behavior of negative ions. While the ion dynamics requires a kinetic description of space dependent plasma relaxation (at least 1D), chemical effects require a vibrational kinetics of hydrogen molecules. Since previous models did not include both features it has not been possible until now to realize both effects in a single simulation. We apply an updated version of the 1D Bari model which includes a 1.5D (1Dr2Dv) Particle in Cell/Monte Carlo (PIC/MC) multispecies module coupled to the space and time dependent master equation for H{sub 2}(X{sup 1}{sigma}{sub g}{sup +},v=0,...,14) vibrational level population. Negative ion fronts are described in hydrogen for the first time and their impact on the plasma limiting surfaces produces a negative ion current evolution compatible with experimental findings. In the same conditions, the attachment rate overshoot is found to contribute about 7% to the average ion density in the plasma.

  1. Time-Resolved Pulsed Hydrogen/Deuterium Exchange Mass Spectrometry Probes Gaseous Proteins Structural Kinetics

    NASA Astrophysics Data System (ADS)

    Rajabi, Khadijeh

    2015-01-01

    A pulsed hydrogen/deuterium exchange (HDX) method has been developed for rapid monitoring of the exchange kinetics of protein ions with D2O a few milliseconds after electrospray ionization (ESI). The stepwise gradual evolution of HDX of multiply charged protein ions was monitored using the pulsed HDX mass spectrometry technique. Upon introducing a very short pulse of D2O (in the μs to ms time scale) into the linear ion trap (LIT) of a time-of-flight (TOF) mass spectrometer, bimodal distributions were detected for the ions of cytochrome c and ubiquitin. Mechanistic details of HDX reactions for ubiquitin and cytochrome c in the gas phase were uncovered and the structural transitions were followed by analyzing the kinetics of HDX.

  2. Time-resolved pulsed hydrogen/deuterium exchange mass spectrometry probes gaseous proteins structural kinetics.

    PubMed

    Rajabi, Khadijeh

    2015-01-01

    A pulsed hydrogen/deuterium exchange (HDX) method has been developed for rapid monitoring of the exchange kinetics of protein ions with D2O a few milliseconds after electrospray ionization (ESI). The stepwise gradual evolution of HDX of multiply charged protein ions was monitored using the pulsed HDX mass spectrometry technique. Upon introducing a very short pulse of D2O (in the μs to ms time scale) into the linear ion trap (LIT) of a time-of-flight (TOF) mass spectrometer, bimodal distributions were detected for the ions of cytochrome c and ubiquitin. Mechanistic details of HDX reactions for ubiquitin and cytochrome c in the gas phase were uncovered and the structural transitions were followed by analyzing the kinetics of HDX. PMID:25318698

  3. Hydrogen Reduction Kinetics of Hematite Concentrate Particles Relevant to a Novel Flash Ironmaking Process

    NASA Astrophysics Data System (ADS)

    Chen, Feng; Mohassab, Yousef; Jiang, Tao; Sohn, Hong Yong

    2015-04-01

    As an integral part of developing a novel ironmaking process, the hydrogen reduction kinetics of hematite concentrate particles (average particle size 21 µm) were measured in the temperature range from 1423 K to 1623 K (1150 °C to 1350 °C). The novel ironmaking process aims at producing iron from iron oxide concentrates in a flash reactor using gaseous fuels and reductants, which will help reduce energy consumption and minimize greenhouse gas emissions. More than 90 pct reduction of hematite concentrate particles could be obtained by hydrogen at a temperature of 1573 K (1300 °C) and 3 seconds of residence time, indicating that hematite concentrate is suitable for the flash reduction process under development largely aimed at the use of magnetite concentrates. The nucleation and growth rate equation with the Avrami parameter, n, of 1.0 well described the kinetics of hematite reduction. The reduction rate has a 1st-order dependence on the partial pressure of hydrogen. The activation energy of the reaction was 214 kJ/mol, indicating strong temperature dependence. The following complete rate equation was developed that can satisfactorily predict the kinetics of hematite concentrate particles and is suitable for the design of a flash reactor: {{{d}}X}/{{{d}t}} = 4.41 × 107 × {{e}}^{{ - 214{,}000/RT}} × ( {p{{H}}2 - {p{{H}}2 {{O}}}/K} ) × (1 - X), where X is fractional reduction degree, R is 8.314 J/mol K, T is in K, p is in atm, and t is in seconds.

  4. 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.

  5. 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

  6. Diffusion-limited Kinetic Pathway for Hydrogen Release from LiNH2/LiH

    NASA Astrophysics Data System (ADS)

    Rolih, Biljana; Ozolins, Vidvuds

    2011-03-01

    From experimental work on decomposition of hydrogen storage materials it has been suggested that bulk diffusion of metal species is the bottleneck for hydrogen release. In this work we study the underlying mechanism for diffusion reactions in the dehydrogenation of Li NH2 . Using first-principle, density functional theory methods we have calculated concentration gradients and diffusivities of neutral and charged defects in Li NH2 and Li 2 NH phases. The overall activation energy is obtained from these calculations. The calculated activation energies are found to agree well with experimental work on the kinetics of Li NH2 decomposition, suggesting that diffusion of metal species is a possible method for dehydrogenation of Lithium Amide.

  7. Ab Initio Kinetics of Hydrogen Abstraction from Methyl Acetate by Hydrogen, Methyl, Oxygen, Hydroxyl, and Hydroperoxy Radicals.

    PubMed

    Tan, Ting; Yang, Xueliang; Krauter, Caroline M; Ju, Yiguang; Carter, Emily A

    2015-06-18

    The kinetics of hydrogen abstraction by five radicals (H, O((3)P), OH, CH3, and HO2) from methyl acetate (MA) is investigated theoretically in order to gain further understanding of certain aspects of the combustion chemistry of biodiesels, such as the effect of the ester moiety. We employ ab initio quantum chemistry methods, coupled cluster singles and doubles with perturbative triples correction (CCSD(T)) and multireference averaged coupled pair functional theory (MRACPF2), to predict chemically accurate reaction energetics. Overall, MRACPF2 predicts slightly higher barrier heights than CCSD(T) for MA + H/CH3/O/OH, but slightly lower barrier heights for hydrogen abstraction by HO2. Based on the obtained reaction energies, we also report high-pressure-limit rate constants using transition state theory (TST) in conjunction with the separable-hindered-rotor approximation, the variable reaction coordinate TST, and the multi-structure all-structure approach. The fitted modified Arrhenius expressions are provided over a temperature range of 250 to 2000 K. The predictions are in good agreement with available experimental results. Abstractions from both of the methyl groups in MA are expected to contribute to consumption of the fuel as they exhibit similar rate coefficients. The reactions involving the OH radical are predicted to have the highest rates among the five abstracting radicals, while those initiated by HO2 are expected to be the lowest. PMID:25974050

  8. Ab initio reaction kinetics of hydrogen abstraction from methyl formate by hydrogen, methyl, oxygen, hydroxyl, and hydroperoxy radicals.

    PubMed

    Tan, Ting; Pavone, Michele; Krisiloff, David B; Carter, Emily A

    2012-08-23

    Combustion of renewable biofuels, including energy-dense biodiesel, is expected to contribute significantly toward meeting future energy demands in the transportation sector. Elucidating detailed reaction mechanisms will be crucial to understanding biodiesel combustion, and hydrogen abstraction reactions are expected to dominate biodiesel combustion during ignition. In this work, we investigate hydrogen abstraction by the radicals H·, CH(3)·, O·, HO(2)·, and OH· from methyl formate, the simplest surrogate for complex biodiesels. We evaluate the H abstraction barrier heights and reaction enthalpies, using multireference correlated wave function methods including size-extensivity corrections and extrapolation to the complete basis set limit. The barrier heights predicted for abstraction by H·, CH(3)·, and O· are in excellent agreement with derived experimental values, with errors ≤1 kcal/mol. We also predict the reaction energetics for forming reactant complexes, transition states, and product complexes for reactions involving HO(2)· and OH·. High-pressure-limit rate constants are computed using transition state theory within the separable-hindered-rotor approximation for torsions and the harmonic oscillator approximation for other vibrational modes. The predicted rate constants differ significantly from those appearing in the latest combustion kinetics models of these reactions. PMID:22830521

  9. Passive Measurement of Hydrogen Ground State Rotational and Vibrational Temperatures in Kinetic Plasmas

    SciTech Connect

    D.R. Farley, D.P. Ludberg and S.A. Cohen

    2010-09-21

    A dipole-quadrupole electron-impact excitation model, consistent with molecular symmetry rules, is presented to fit ro-vibronic spectra of the hydrogen Fulcher-α Q-branch line emissions for passively measuring the rotational temperature of hydrogen neutral molecules in kinetic plasmas with the coronal equilibrium approximation. A quasi-rotational temperature and quadrupole contribution factor are adjustable parameters in the model. Quadrupole excitation is possible due to a violation of the 1st Born approximation for low to medium energy electrons (up to several hundred eV). The Born-Oppenheimer and Franck-Condon approximations are implicitly shown to hold. A quadrupole contribution of 10% is shown to fit experimental data at several temperatures from different experiments with electron energies from several to 100 eV. A convenient chart is produced to graphically determine the vibrational temperature of the hydrogen molecules from diagonal band intensities, if the ground state distribution is Boltzmann. Hydrogen vibrational modes are long-lived, surviving up to thousands of wall collisions, consistent with multiple other molecular dynamics computational results. The importance of inter-molecular collisions during a plasma pulse are also discussed.

  10. Isosteric heat of hydrogen adsorption on MOFs: comparison between adsorption calorimetry, sorption isosteric method, and analytical models

    NASA Astrophysics Data System (ADS)

    Kloutse, A. F.; Zacharia, R.; Cossement, D.; Chahine, R.; Balderas-Xicohténcatl, R.; Oh, H.; Streppel, B.; Schlichtenmayer, M.; Hirscher, M.

    2015-12-01

    Isosteric heat of adsorption is an important parameter required to describe the thermal performance of adsorptive storage systems. It is most frequently calculated from adsorption isotherms measured over wide ranges of pressure and temperature, using the so-called adsorption isosteric method. Direct quantitative estimation of isosteric heats on the other hand is possible using the coupled calorimetric-volumetric method, which involves simultaneous measurement of heat and adsorption. In this work, we compare the isosteric heats of hydrogen adsorption on microporous materials measured by both methods. Furthermore, the experimental data are compared with the isosteric heats obtained using the modified Dubinin-Astakhov, Tóth, and Unilan adsorption analytical models to establish the reliability and limitations of simpler methods and assumptions. To this end, we measure the hydrogen isosteric heats on five prototypical metal-organic frameworks: MOF-5, Cu-BTC, Fe-BTC, MIL-53, and MOF-177 using both experimental methods. For all MOFs, we find a very good agreement between the isosteric heats measured using the calorimetric and isosteric methods throughout the range of loading studied. Models' prediction on the other hand deviates from both experiments depending on the MOF studied and the range of loading. Under low-loadings of less than 5 mol kg-1, the isosteric heat of hydrogen adsorption decreases in the order Cu-BTC > MIL-53 > MOF-5 > Fe-BTC > MOF-177. The order of isosteric heats is coherent with the strength of hydrogen interaction revealed from previous thermal desorption spectroscopy measurements.

  11. Kinetics of hydrogen desorption in surface-limited thin-film growth of SiGe alloys

    SciTech Connect

    Sharp, J.W. ); Eres, G. )

    1993-05-31

    The kinetics of hydrogen desorption in surface-limited thin-film growth of SiGe alloys from binary mixtures of disilane and digermane was investigated by surface differential reflectance. The hydrogen desorption process from the alloy surface was found to consist of two components. Both components are thermally activated, but the activation energies appear to equal neither the hydrogen desorption energy from pure silicon nor that from pure germanium surfaces. We suggest that the two components represent Ge- and Si-mediated hydrogen desorption, with the former being more rapid than the latter.

  12. 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.

  13. Hydrogen absorption by Zr-1Nb alloy with TiNx film deposited by filtered cathodic vacuum arc

    NASA Astrophysics Data System (ADS)

    Kashkarov, E. B.; Nikitenkov, N. N.; Syrtanov, M. S.; Babihina, M. N.

    2016-02-01

    coating for Zr-2.5Nb alloy from hydrogenation. Dense TiNx films were prepared by filtered cathodic vacuum arc (CVA). Hydrogen absorption rate was calculated from the kinetic curves of hydrogen sorption at elevated temperature of the sample (T = 673 K) and pressure (P = 2 atm). Results revealed that TiNx films significantly reduced hydrogen absorption rate of Zr-2.5Nb.

  14. 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

  15. Surface properties of the Ni-silica gel catalyst precursors for the vegetable oil hydrogenation process: N2 sorption and XPS studies

    NASA Astrophysics Data System (ADS)

    Nikolova, D.; Krstić, J.; Spasov, L.; Simeonov, D.; Lončarević, D.; Stefanov, Pl.; Jovanović, D.

    2011-12-01

    The effect of the type of the silica gel pore structure on the surface properties of the Ni-silica gel catalyst precursors for the vegetable oil hydrogenation process has been examined applying N2 sorption and X-ray photoelectron spectroscopy techniques. The nickel catalyst precursors with identical composition (SiO2/Ni = 1.0) has been synthesized by precipitation of Ni(NO3)2 · 6H2O solution with Na2CO3 solution on the three types of silica gel with different pore structures. It is shown that the usage of the silica gel supports with different texture as source of SiO2 causes different location of Ni-species into the support pores and on the external surface area. The XPS data confirm the formation of surface species with different strength of interaction and different dispersion. These surface characteristics of the precursors will predetermine the formation of the active nickel metallic phase as well as the mass transfer of the reactants and products to and from the catalytic sites.

  16. COSOLVENT EFFECTS ON SORPTION ISOTHERM LINEARITY

    EPA Science Inventory

    Sorption-desorption hysteresis, slow desorption kinetics, and other nonideal phenomena have been attributed to the differing sorptive characteristics of the natural organic polymers associated with soils and sediments. In this study, aqueous and mixed solvent systems were used t...

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

    SciTech Connect

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

    2008-11-15

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

  18. Intermetallic compounds LaNi/sub 5/- /SUB x/ Cu /SUB x/ and their hydrides in the sorption of hydrogen and the hydrogenation of olefins

    SciTech Connect

    Konenko, I.R.; Fedorovskaya, E.A.; Slinkin, A.A.; Starodubtseva, E.V.; Stepanov, Y.P.

    1985-09-01

    This paper studies the sorptive and catalytic properties of the intermetallic compounds (IMC) LaNi /SUB 5-x/ Cu /SUB x/ and also of their hydrides in the hydrogenation of propylene. The existence of an inverse dependence between the bond strength in the IMC-H system and the rate of formation of the alpha-phase of the hydrides was established. It was shown that the observed extremal dependence of the specific catalytic activity of the hydrides on composition is determined by the optimum value of the bond energy of the hydrogen in the IMC matrix. It was found that the rate of hydrogenation of an olefin on IMC hydrides follows a rate equation zero-order in hydrogen and first-order in olefin. In the case of the same IMC, on the contrary, the rate is first-order in H/sub 2/ and zero-order in C/sub 3/H/sub 6/. It is proposed that the sorptive and catalytic properties of the catalysts show the effect of the structure on the surface active center - a cluster.

  19. Hydrogen electrosorption into Pd-Cd nanostructures.

    PubMed

    Adams, Brian D; Ostrom, Cassandra K; Chen, Aicheng

    2010-05-18

    Hydrogen-absorbing materials are crucial for both the purification and storage of hydrogen. Pd and Pd-based alloys have been studied extensively for their use as both hydrogen dissociation catalysts and hydrogen selective membrane materials. It is known that incorporating metal atoms of different sizes into the Pd lattice has a major impact on the hydrogen absorption process. In this paper, hydrogen electrosorption into nanostructured Pd-Cd alloys has been studied for different compositions of Cd that varied from 0 to 15 at. %. The low cost of Cd makes it an attractive material to combine with Pd for hydrogen sorption. A combination of chronoamperometry and cyclic voltammetric experiments was used to determine the ratio of the H/(Pd + Cd) and the kinetics of hydrogen sorption into these Pd-Cd alloys at different potentials. It was found that the maximum H/(Pd + Cd) value was 0.66 for pure Pd, and this decreased with increasing the amount of Cd. Also, the alpha (solid solution) to beta phase (metal hydride) hydrogen transition was determined to be the slowest step in the absorption process and was practically eliminated when an optimum amount of Cd atoms was doped (i.e., Pd-Cd(15%)). With increasing the amount of Cd, more hydrogen was absorbed into the Pd-Cd nanostructures at the higher potentials (the alpha phase region). The faster kinetics, along with the decrease in the phase transition of hydrogen sorption into the Pd-Cd nanostructures when compared to pure Pd, makes the Pd-Cd nanostructures attractive for use as a hydrogen dissociation catalytic capping layer for other metal hydrides or as a hydrogen selective membrane. PMID:20099788

  20. Kinetic Analysis of Competitive Electrocatalytic Pathways: New Insights into Hydrogen Production with Nickel Electrocatalysts.

    PubMed

    Wiedner, Eric S; Brown, Houston J S; Helm, Monte L

    2016-01-20

    The hydrogen production electrocatalyst Ni(P(Ph)2N(Ph)2)2(2+) (1) is capable of traversing multiple electrocatalytic pathways. When using dimethylformamidium, DMF(H)(+), the mechanism of H2 formation by 1 changes from an ECEC to an EECC mechanism as the potential approaches the Ni(I/0) couple. Two electrochemical methods, current-potential analysis and foot-of-the-wave analysis (FOWA), were performed on 1 to measure detailed kinetics of the competing ECEC and EECC pathways. A sensitivity analysis was performed on the methods using digital simulations to understand their strengths and limitations. Chemical rate constants were significantly underestimated when not accounting for electron-transfer kinetics, even when electron transfer was fast enough to afford a reversible noncatalytic wave. The EECC pathway of 1 was faster than the ECEC pathway under all conditions studied. Buffered DMF:DMF(H)(+) mixtures afforded an increase in the catalytic rate constant (k(obs)) of the EECC pathway, but k(obs) for the ECEC pathway did not change when using buffered acid. Further kinetic analysis of the ECEC path revealed that base increases the rate of isomerization from exo-protonated Ni(0) isomers to the catalytically active endo-isomers, but decreases the rate of protonation of Ni(I). FOWA did not provide accurate rate constants, but FOWA was used to estimate the reduction potential of the previously undetected exo-protonated Ni(I) intermediate. Comparison of catalytic Tafel plots for 1 under different conditions reveals substantial inaccuracies in the turnover frequency at zero overpotential when the kinetic and thermodynamic effects of the conjugate base are not accounted for properly. PMID:26692398

  1. 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.

  2. 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

  3. Hybrid electrodynamics and kinetics simulation for electromagnetic wave propagation in weakly ionized hydrogen plasmas

    NASA Astrophysics Data System (ADS)

    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.

  4. Hydrogen micro-kinetics in titanium under mechanical stress studied by ion beam analysis

    NASA Astrophysics Data System (ADS)

    Wang, T. S.; Lv, H. Y.; Grambole, D.; Yang, Z.; Peng, H. B.; Han, Y. C.

    2009-04-01

    Hydrogen (H) is continuously produced by the large dose fast neutron irradiation on fusion reactor material. The concentration, diffusion and evolution of H in the structure material may cause H-embrittlement. Ion beam analysis is one of the most useful methods for studying the micro-kinetics of H in solids. In this work, the H-distribution in titanium (Ti) has been studied by resonance nuclear reaction analysis (resonance-NRA) and micro-elastic recoil detection analysis (micro-ERDA). The evolution of H-depth-profile in titanium samples has been studied versus the change of normal stress. Evident H diffusion has been observed, while a normal stress is changed in the range of 107-963 MPa. The H diffusion is related to the concentration of H in samples.

  5. Effect of grain boundary trapping kinetics on diffusion in polycrystalline materials: hydrogen transport in Ni

    NASA Astrophysics Data System (ADS)

    Ilin, Dmitrii N.; Kutsenko, Anton A.; Tanguy, Dome; Olive, Jean-Marc

    2016-03-01

    Due to experimental limitations, the solute distribution in polycrystalline materials is difficult to obtain directly, especially in the vicinity of grain boundaries. Using a newly developed computational method which mixes continuum diffusion equations and atomic scale jump rates, we study the interstitial diffusion in solids containing interfaces taking into account trapping kinetics. The model is applied to hydrogen diffusion in Ni in elementary configurations: fast intergranular diffusion with no segregation (in agreement with Fisher’s model), slow intergranular diffusion with trapping, diffusion through a triple junction and solute redistribution due to stress gradients across the interface. It is shown that the classical diffusion modes can be captured and a new diffusion regime with the effect of grain boundary trapping is revealed.

  6. Dynamic Kinetic Resolution Approach for the Asymmetric Synthesis of Tetrahydrobenzodiazepines Using Transfer Hydrogenation by Chiral Phosphoric Acid.

    PubMed

    Horiguchi, Kosaku; Yamamoto, Eri; Saito, Kodai; Yamanaka, Masahiro; Akiyama, Takahiko

    2016-06-01

    Asymmetric synthesis of tetrahydrobenzodiazepines was achieved by transfer hydrogenation of dihydrobenzodiazepines with benzothiazoline having a hydrogen-bonding donor substituent by means of a newly synthesized chiral phosphoric acid. This method was applicable to various racemic dihydrobenzodiazepines to give the corresponding products in good yields with excellent diastereoselectivities and enantioselectivities taking advantage of the dynamic kinetic resolution. Furthermore, the effect of bulky substituent at 3,3'-position on the catalyst and hydrogen-bonding donor substituent on benzothiazoline was fully elucidated by the theoretical study. PMID:27150449

  7. Flow-tube kinetics study of the reaction between ground-state hydrogen atoms and nitromethane

    SciTech Connect

    Ko, Taeho; Flaherty, W.F.; Fontijn, A. )

    1991-09-05

    The kinetics of the H + CH{sub 3}NO{sub 2} reaction have been studied by using a discharge-flow resonance-fluorescence technique. H atoms are produced from microwave discharges through NH{sub 3}Ar mixtures. The data in the 360-570 K range are well fitted by the empirical expression k(T) = 7.8 {times} 10{sup {minus}12} exp(-1878K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. Precision of the data varies from {plus minus} 6 to {plus minus} 11%, and the resulting accuracy is estimated to be better than {+-} 20%, where both figures represent 2{sigma} statistical confidence intervals. Results of some experiments where h{sub 2} was discharged indicate that the channel leading to OH and CH{sub 3}NO is significant for the reaction. A comparison of the kinetics of several reactions where a methyl-group hydrogen is abstracted by H atoms indicates that such a channel is not important in the present work but could become significant at elevated temperatures. To confirm the accuracy achieved with the present apparatus, measurements on the H + C{sub 6}H{sub 6} reaction have been made in the 410-530 K range and are compared to results from other studies.

  8. Influence of Hydrogen Bonding on the Kinetic Stability of Vapor Deposited Triazine Glasses

    NASA Astrophysics Data System (ADS)

    Laventure, Audrey; Gujral, Ankit; Lebel, Olivier; Pellerin, Christian; Ediger, Mark D.

    Physical vapor deposition (PVD) can produce glasses with enhanced kinetic stability, high density and anisotropy. However, the influence of hydrogen bonding on these properties has not been fully explored. We vapor deposit a series of triazine derivatives containing functional groups with different H-bonding capability, i.e. NHMe (H-bond donor), OMe (H-bond acceptor) and Et (none) using a wide range of substrate temperatures, from 0.60 to 1.05Tg. PVD glasses of the NHMe derivative have inferior kinetic stability compared to its OMe and Et analogues. This behavior can be rationalized by the higher average number of bonded NH per molecule found in PVD glasses of the NHMe derivative, as quantified by infrared spectroscopy (IR). Despite this difference in H-bonding, IR and wide angle X-ray scattering reveal that all three compounds show a tendency to orient parallel to the substrate at low substrate temperatures. Our results support the hypothesis that strong intermolecular interactions, such as H-bonds, can hinder mobility of the molecules at the interface and thus limit their possibility to sample the potential energy landscape to produce stable glasses.

  9. Kinetic modeling of E-to-H mode transition in inductively coupled hydrogen plasmas

    NASA Astrophysics Data System (ADS)

    Nishida, K.; Mattei, S.; Mochizuki, S.; Lettry, J.; Hatayama, A.

    2016-06-01

    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.

  10. 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.