WorldWideScience

Sample records for surface exchange kinetics

  1. Surface defect chemistry and oxygen exchange kinetics in La2-xCaxNiO4+δ

    Science.gov (United States)

    Tropin, E. S.; Ananyev, M. V.; Farlenkov, A. S.; Khodimchuk, A. V.; Berenov, A. V.; Fetisov, A. V.; Eremin, V. A.; Kolchugin, A. A.

    2018-06-01

    Surface oxygen exchange kinetics and diffusion in La2-xCaxNiO4+δ (x = 0; 0.1; 0.3) have been studied by the isotope exchange method with gas phase equilibration in the temperature range of 600-800 °C and oxygen pressure range 0.13-2.5 kPa. Despite an enhanced electrical conductivity of La2-xCaxNiO4+δ theirs oxygen surface exchange (k*) and oxygen tracer diffusion (D*) coefficients were significantly lower in comparison with La2NiO4+δ. The rates of the elementary stages of oxygen exchange have been calculated. Upon Ca doping the change of the rate-determining stage was observed. The surface of the oxides was found to be inhomogeneous towards oxygen exchange process according to the recently developed model. The reasons of such inhomogeneity are discussed as well as Ca influence on the surface defect chemistry and oxygen surface exchange and diffusivity.

  2. Oxygen exchange at gas/oxide interfaces: how the apparent activation energy of the surface exchange coefficient depends on the kinetic regime.

    Science.gov (United States)

    Fielitz, Peter; Borchardt, Günter

    2016-08-10

    In the dedicated literature the oxygen surface exchange coefficient KO and the equilibrium oxygen exchange rate [Fraktur R] are considered to be directly proportional to each other regardless of the experimental circumstances. Recent experimental observations, however, contradict the consequences of this assumption. Most surprising is the finding that the apparent activation energy of KO depends dramatically on the kinetic regime in which it has been determined, i.e. surface exchange controlled vs. mixed or diffusion controlled. This work demonstrates how the diffusion boundary condition at the gas/solid interface inevitably entails a correlation between the oxygen surface exchange coefficient KO and the oxygen self-diffusion coefficient DO in the bulk ("on top" of the correlation between KO and [Fraktur R] for the pure surface exchange regime). The model can thus quantitatively explain the range of apparent activation energies measured in the different regimes: in the surface exchange regime the apparent activation energy only contains the contribution of the equilibrium exchange rate, whereas in the mixed or in the diffusion controlled regime the contribution of the oxygen self-diffusivity has also to be taken into account, which may yield significantly higher apparent activation energies and simultaneously quantifies the correlation KO ∝ DO(1/2) observed for a large number of oxides in the mixed or diffusion controlled regime, respectively.

  3. Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes

    Directory of Open Access Journals (Sweden)

    Nicola H. Perry

    2016-10-01

    Full Text Available Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic, and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I2CNER, Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance.

  4. Kinetics of the homogeneous exchange of alpha-lactalbumin adsorbed on titanium oxide surface.

    Science.gov (United States)

    Bentaleb, A; Haïkel, Y; Voegel, J C; Schaaf, P

    1998-06-05

    The homogeneous exchange process whereby alpha-lactalbumine molecules adsorbed on hydrophilic titanium oxide particles are replaced by alpha-lactalbumine molecules in solution has been investigated by means of a 125I radio-labeling technique, alpha-lactalbumine is a compact and highly negatively charged protein, making this study complementary to previous work devoted to the general understanding of the exchange mechanisms of adsorbed proteins on solid surfaces. The isotherm of alpha-lactalbumine exhibits bimodal adsorption shape, and the exchange process whereby adsorbed proteins are replaced by new incoming ones from the bulk solution has been studied at both the upper and the lower plateau of the isotherm. In the upper plateau the exchange process was found to be of first order with respect to the bulk molecules, and the release rate constant was equal to 0.914 L. mol-1.s-1. This behavior is identical to what has been observed with other proteinic systems. In the lower plateau domain, in contrast, the protein release process is independent of the concentration of proteins in the bulk, but the release rates are higher than the pure desorption rates. This constitutes, to our knowledge, a behavior that never before has been observed and that remains to be explained.

  5. Measuring oxygen surface exchange kinetics on mixed-conducting composites by electrical conductivity relaxation

    NARCIS (Netherlands)

    Hu, Bobing; Wang, Yunlong; Zhu, Zhuoying; Xia, Changrong; Bouwmeester, Henricus J.M.

    2015-01-01

    The oxygen release kinetics of mixed-conducting Sr2Fe1.5Mo0.5O6 d–Sm0.2Ce0.8O2 d (SFM–SDC) dualphase composites has been investigated, at 750 C, as a function of the SDC phase volume fraction using electrical conductivity relaxation (ECR) under reducing atmospheres, extending our previous work on

  6. Time-dependent photoluminescence spectroscopy as a tool to measure the ligand exchange kinetics on a quantum dot surface

    NARCIS (Netherlands)

    Koole, R.; Schapotschnikow, P.Z.; de Mello Donega, C.; Vlugt, T.J.H.; Meijerink, A.

    2008-01-01

    The exchange kinetics of native ligands that passivate CdSe quantum dots (hexadecylamine (HDA), trioctylphosphine oxide (TOPO), and trioctylphosphine (TOP)) by thiols is followed in situ. This is realized by measuring, in real-time, the decrease in emission intensity of the QDs upon addition of

  7. Oxygen surface exchange kinetics measurement by simultaneous optical transmission relaxation and impedance spectroscopy: Sr(Ti,Fe)O3-x thin film case study.

    Science.gov (United States)

    Perry, Nicola H; Kim, Jae Jin; Tuller, Harry L

    2018-01-01

    We compare approaches to measure oxygen surface exchange kinetics, by simultaneous optical transmission relaxation (OTR) and AC-impedance spectroscopy (AC-IS), on the same mixed conducting SrTi 0.65 Fe 0.35 O 3-x film. Surface exchange coefficients were evaluated as a function of oxygen activity in the film, controlled by gas partial pressure and/or DC bias applied across the ionically conducting yttria-stabilized zirconia substrate. Changes in measured light transmission through the film over time (relaxations) resulted from optical absorption changes in the film corresponding to changes in its oxygen and oxidized Fe (~Fe 4+ ) concentrations; such relaxation profiles were successfully described by the equation for surface exchange-limited kinetics appropriate for the film geometry. The k chem values obtained by OTR were significantly lower than the AC-IS derived k chem values and k q values multiplied by the thermodynamic factor (bulk or thin film), suggesting a possible enhancement in k by the metal current collectors (Pt, Au). Long-term degradation in k chem and k q values obtained by AC-IS was also attributed to deterioration of the porous Pt current collector, while no significant degradation was observed in the optically derived k chem values. The results suggest that, while the current collector might influence measurements by AC-IS, the OTR method offers a continuous, in situ , and contact-free method to measure oxygen exchange kinetics at the native surfaces of thin films.

  8. Oxygen surface exchange kinetics measurement by simultaneous optical transmission relaxation and impedance spectroscopy: Sr(Ti,Fe)O3-x thin film case study

    Science.gov (United States)

    Perry, Nicola H.; Kim, Jae Jin; Tuller, Harry L.

    2018-01-01

    Abstract We compare approaches to measure oxygen surface exchange kinetics, by simultaneous optical transmission relaxation (OTR) and AC-impedance spectroscopy (AC-IS), on the same mixed conducting SrTi0.65Fe0.35O3-x film. Surface exchange coefficients were evaluated as a function of oxygen activity in the film, controlled by gas partial pressure and/or DC bias applied across the ionically conducting yttria-stabilized zirconia substrate. Changes in measured light transmission through the film over time (relaxations) resulted from optical absorption changes in the film corresponding to changes in its oxygen and oxidized Fe (~Fe4+) concentrations; such relaxation profiles were successfully described by the equation for surface exchange-limited kinetics appropriate for the film geometry. The kchem values obtained by OTR were significantly lower than the AC-IS derived kchem values and kq values multiplied by the thermodynamic factor (bulk or thin film), suggesting a possible enhancement in k by the metal current collectors (Pt, Au). Long-term degradation in kchem and kq values obtained by AC-IS was also attributed to deterioration of the porous Pt current collector, while no significant degradation was observed in the optically derived kchem values. The results suggest that, while the current collector might influence measurements by AC-IS, the OTR method offers a continuous, in situ, and contact-free method to measure oxygen exchange kinetics at the native surfaces of thin films. PMID:29511391

  9. Kinetics from Replica Exchange Molecular Dynamics Simulations.

    Science.gov (United States)

    Stelzl, Lukas S; Hummer, Gerhard

    2017-08-08

    Transitions between metastable states govern many fundamental processes in physics, chemistry and biology, from nucleation events in phase transitions to the folding of proteins. The free energy surfaces underlying these processes can be obtained from simulations using enhanced sampling methods. However, their altered dynamics makes kinetic and mechanistic information difficult or impossible to extract. Here, we show that, with replica exchange molecular dynamics (REMD), one can not only sample equilibrium properties but also extract kinetic information. For systems that strictly obey first-order kinetics, the procedure to extract rates is rigorous. For actual molecular systems whose long-time dynamics are captured by kinetic rate models, accurate rate coefficients can be determined from the statistics of the transitions between the metastable states at each replica temperature. We demonstrate the practical applicability of the procedure by constructing master equation (Markov state) models of peptide and RNA folding from REMD simulations.

  10. Study on Modification of NaX Zeolites: The Cobalt (II-Exchange Kinetics and Surface Property Changes under Thermal Treatment

    Directory of Open Access Journals (Sweden)

    Hoai-Lam Tran

    2016-01-01

    Full Text Available The cobalt (II ion-exchange process followed the Freundlich and Langmuir adsorption models as well as the pseudo-second-order kinetic model. The cobalt-exchanged contents increased when the initial Co(NO32 solution concentration increased up to 0.14 mol L−1 at the optimal pH of 6.05. The N2 adsorption isotherms are mixed types I/II isotherms and H3 type hysteresis. Both the micropore and mesopore adsorptions occurred during the adsorption process. The modification, which is both the cobalt (II exchange and thermal treatment, significantly improved the surface properties of NaX zeolites. Accordingly, the optimal temperature range is 500 to 600°C for a thermal treatment. This is consistent with the results of XRD analysis.

  11. Effects of pressure, temperature and atomic exchanges on phase separation dynamics in Au/Ni(111) surface alloy: Kinetic Monte Carlo study

    Energy Technology Data Exchange (ETDEWEB)

    Zvejnieks, G. [Institute for Solid State Physics, University of Latvia, Kengaraga 8, LV-1063 Riga (Latvia); Ibenskas, A., E-mail: ibenskas@pfi.lt [Center for Physical Sciences and Technology, Semiconductor Physics Institute, Gostauto 11, LT-01108 Vilnius (Lithuania); Tornau, E.E. [Center for Physical Sciences and Technology, Semiconductor Physics Institute, Gostauto 11, LT-01108 Vilnius (Lithuania)

    2015-11-15

    Instability of the Au/Ni(111) surface alloy is studied in different CO gas pressure, p, and temperature limits using kinetic Monte Carlo simulations. We analyze the reaction front dynamics and formation of Au clusters using the model which takes into account surface adatom pair and three-body interactions, CO adsorption and desorption, catalytic carbonyl formation reaction, Au and Ni adatom diffusion and their concerted exchange. Variation of interaction parameters allows us to identify three possible reaction front propagation limits with different pressure dependencies: (i) slow channel-like flow in agreement with experimental data [1] (step flow rate, R, increases with p), (ii) intermediate regime (weak p–dependence), and (iii) fast homogeneous flow (R decreases with p). We find that only Au–Ni exchange, contrary to both Ni–CO and Au–CO exchanges, significantly reduces the number of screened Ni atoms inside the Au clusters and stimulates the occurrence of Ni-free Au clusters. The size of Au islands depends on both pressure and temperature. At a fixed temperature it decreases with pressure due to an increased step flow rate. In the high temperature limit, despite the step flow rate exponential increase with temperature, the cluster size increases due to an enhanced Au mobility. - Highlights: • Kinetic Monte Carlo study of Au–Ni surface alloy instability to CO pressure and temperature. • Three reaction front propagation regimes. • In channel-like regime, the step flow rate increases with CO pressure as in experiment. • Ni-free Au islands are obtained when Au-Ni adatom exchange mechanism is considered. • The size of Au islands decreases with pressure and increases with temperature.

  12. Effects of pressure, temperature and atomic exchanges on phase separation dynamics in Au/Ni(111) surface alloy: Kinetic Monte Carlo study

    International Nuclear Information System (INIS)

    Zvejnieks, G.; Ibenskas, A.; Tornau, E.E.

    2015-01-01

    Instability of the Au/Ni(111) surface alloy is studied in different CO gas pressure, p, and temperature limits using kinetic Monte Carlo simulations. We analyze the reaction front dynamics and formation of Au clusters using the model which takes into account surface adatom pair and three-body interactions, CO adsorption and desorption, catalytic carbonyl formation reaction, Au and Ni adatom diffusion and their concerted exchange. Variation of interaction parameters allows us to identify three possible reaction front propagation limits with different pressure dependencies: (i) slow channel-like flow in agreement with experimental data [1] (step flow rate, R, increases with p), (ii) intermediate regime (weak p–dependence), and (iii) fast homogeneous flow (R decreases with p). We find that only Au–Ni exchange, contrary to both Ni–CO and Au–CO exchanges, significantly reduces the number of screened Ni atoms inside the Au clusters and stimulates the occurrence of Ni-free Au clusters. The size of Au islands depends on both pressure and temperature. At a fixed temperature it decreases with pressure due to an increased step flow rate. In the high temperature limit, despite the step flow rate exponential increase with temperature, the cluster size increases due to an enhanced Au mobility. - Highlights: • Kinetic Monte Carlo study of Au–Ni surface alloy instability to CO pressure and temperature. • Three reaction front propagation regimes. • In channel-like regime, the step flow rate increases with CO pressure as in experiment. • Ni-free Au islands are obtained when Au-Ni adatom exchange mechanism is considered. • The size of Au islands decreases with pressure and increases with temperature

  13. Kinetic equation of heterogeneous catalytic isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

    Trokhimets, A I [AN Belorusskoj SSR, Minsk. Inst. Fiziko-Organicheskoj Khimii

    1979-12-01

    A kinetic equation is derived for the bimolecular isotope exchange reaction between AXsub(n)sup(*) and BXsub(m)sup(o), all atoms of element X in each molecule being equivalent. The equation can be generalized for homogeneous and heterogeneous catalytic isotope exchange.

  14. Calmodulin-lanthanide ion exchange kinetics

    International Nuclear Information System (INIS)

    Buccigross, J.; O'Donnell, C.; Nelson, D.

    1985-01-01

    A flow dialysis apparatus suitable for the study of high affinity metal binding proteins has been utilized to study calmodulin-metal exchange kinetics. Calmodulin labeled with Eu-155 and Gd-153 was dialyzed against buffer containing various competing metal ions. The rate of metal exchange was monitored by a gamma-ray scintillation detector. The kinetics of exchange are first order, and the rates fall into two categories: Ca (II) and CD (II) in one, and the lanthanides Eu (III), Gd (III), and La (III) in the other

  15. The Balescu kinetic equation with exchange interaction

    International Nuclear Information System (INIS)

    Belyi, V V; Kukharenko, Yu A

    2009-01-01

    Starting with the quantum BBGKY hierarchy for the distribution functions, we have obtained the quantum kinetic equation including the dynamical screening of the interaction potential, which exactly takes into account the exchange scattering in the plasma. The collision integral is expressed in terms of the Green function of the linearized Hartree–Fock equation. The potential energy takes into account the polarization and exchange interaction too

  16. Exercise: Kinetic considerations for gas exchange.

    Science.gov (United States)

    Rossiter, Harry B

    2011-01-01

    The activities of daily living typically occur at metabolic rates below the maximum rate of aerobic energy production. Such activity is characteristic of the nonsteady state, where energy demands, and consequential physiological responses, are in constant flux. The dynamics of the integrated physiological processes during these activities determine the degree to which exercise can be supported through rates of O₂ utilization and CO₂ clearance appropriate for their demands and, as such, provide a physiological framework for the notion of exercise intensity. The rate at which O₂ exchange responds to meet the changing energy demands of exercise--its kinetics--is dependent on the ability of the pulmonary, circulatory, and muscle bioenergetic systems to respond appropriately. Slow response kinetics in pulmonary O₂ uptake predispose toward a greater necessity for substrate-level energy supply, processes that are limited in their capacity, challenge system homeostasis and hence contribute to exercise intolerance. This review provides a physiological systems perspective of pulmonary gas exchange kinetics: from an integrative view on the control of muscle oxygen consumption kinetics to the dissociation of cellular respiration from its pulmonary expression by the circulatory dynamics and the gas capacitance of the lungs, blood, and tissues. The intensity dependence of gas exchange kinetics is discussed in relation to constant, intermittent, and ramped work rate changes. The influence of heterogeneity in the kinetic matching of O₂ delivery to utilization is presented in reference to exercise tolerance in endurance-trained athletes, the elderly, and patients with chronic heart or lung disease. © 2011 American Physiological Society.

  17. Effects of apolipoproteins on the kinetics of cholesterol exchange

    International Nuclear Information System (INIS)

    Letizia, J.Y.; Phillips, M.C.

    1991-01-01

    The effects of apolipoproteins on the kinetics of cholesterol exchange have been investigated by monitoring the transfer of [ 14 C]cholesterol from donor phospholipid/cholesterol complexes containing human apolipoproteins A, B, or C. Negatively charged discoidal and vesicular particles containing purified apolipoproteins complexed with lipid and a trace of [ 14 C]cholesterol were incubated with a 10-fold excess of neutral, acceptor, small unilamellar vesicles. The donor and acceptor particles were separated by chromatogrphy of DEAE-Sepharose, and the rate of movement of labeled cholesterol was analyzed as a first-order exchange process. The kinetics of exchange of cholesterol from both vesicular and discoidal complexes that contain apoproteins are consistent with an aqueous diffusion mechanism, as has been established previously for PC/cholesterol SUV. Apolipoproteins A-I, A-II, reduced and carboxymethylated A-11, and B-100 present in SUV at the same lipid/protein (w/w) ratio all enhance the rate of cholesterol exchange to about the same degree. Cholesterol molecules exchange more rapidly from discoidal complexes. Generally, as the diameter of apoprotein/phospholipid/cholesterol discs decreases, t 1/2 for cholesterol exchange decreases. Since small bilayer discs have a relatively high ratio of boundary to face surface area, cholesterol molecules desorb more rapidly than from larger discs. The modulation of lipid packing by the apoprotein molecules present at the surface of lipoprotein particles affects the rate of cholesterol exchange from such particles

  18. Surface- vs Diffusion-Limited Mechanisms of Anion Exchange in CsPbBr3 Nanocrystal Cubes Revealed through Kinetic Studies.

    Science.gov (United States)

    Koscher, Brent A; Bronstein, Noah D; Olshansky, Jacob H; Bekenstein, Yehonadav; Alivisatos, A Paul

    2016-09-21

    Ion-exchange transformations allow access to nanocrystalline materials with compositions that are inaccessible via direct synthetic routes. However, additional mechanistic insight into the processes that govern these reactions is needed. We present evidence for the presence of two distinct mechanisms of exchange during anion exchange in CsPbX3 nanocrystals (NCs), ranging in size from 6.5 to 11.5 nm, for transformations from CsPbBr3 to CsPbCl3 or CsPbI3. These NCs exhibit bright luminescence throughout the exchange, allowing their optical properties to be observed in real time, in situ. The iodine exchange presents surface-reaction-limited exchanges allowing all anionic sites within the NC to appear chemically identical, whereas the chlorine exchange presents diffusion-limited exchanges proceeding through a more complicated exchange mechanism. Our results represent the first steps toward developing a microkinetic description of the anion exchange, with implications not only for understanding the lead halide perovskites but also for nanoscale ion exchange in general.

  19. Determination of kinetic parameters of heterogeneous isotopic exchange reaction

    International Nuclear Information System (INIS)

    Huang, Ting-Chia; Tsai, Fuan-Nan

    1977-01-01

    A mathematical model has been proposed for a heterogeneous isotopic exchange reaction which involves film diffusion, surface chemical reaction and intraparticle diffusion. The exchange equation to predict the exchange fraction as a function of time for the spherical particles immersed in a solution of finite volume has been derived. The relations between the exchange fraction and dimensionless time are plotted with xi(=ak sub(f)/KD sub(e)), xi 1 (=K 1 a 2 /D sub(e)) and final fractional uptake as parameters. From the values of the kinetic parameters xi and xi 1 , the relative importance of each limiting step is discussed. Experimental results of the isotopic exchange reaction of calcium ion in both system CaCO 3 (s)/Ca 2+ (aq) and system calcium type resin Dowex 50W-X8/Ca 2+ (aq) are coincident with the theoretical equation proposed in this study. (auth.)

  20. Kinetics and Mechanisms of Oxygen Surface Exchange on La0.6Sr0.4FeO3-delta Thin Films

    OpenAIRE

    Mosleh, Majid; Søgaard, Martin; Hendriksen, Peter Vang

    2009-01-01

    The thermodynamic properties as well as oxygen exchange kinetics were examined on mixed ionic and electronic conducting (La0.6Sr0.4)0.99FeO3− (LSF64) thin films deposited on MgO single crystals. It is found that thin films and bulk material have the same oxygen stoichiometry for a given temperature and oxygen partial pressure [i.e., the incorporation reaction has the same reaction enthalpy (H0=−105 KJ/mol) and entropy (S0=−75.5 J/mol/K) as found for bulk material]. The thin film shows smaller...

  1. Ion exchange kinetics of alkaline earths on Zr(IV) arsenosilicate cation exchanger

    International Nuclear Information System (INIS)

    Varshney, K.G.; Agrawal, S.; Varshney, K.

    1984-01-01

    A new approach based on the Nernst-Planck equations was applied to study the ion exchange kinetics for the exchange reactions of Mg(II), Ca(II), Sr(II) and Ba(II) with H + -ions at various temperatures on the zirconium(IV) arsenosilicate phase. Under the conditions of particle diffusion, the rate of exchange was found to be independent of the metal ion concentration at and above 0.1 M in aqueous medium. Energy and entropy of activation were determined and found to vary linearly with the ionic radii and mobilities of alkaline earths, a unique feature observed for an inorganic ion exchanger. The results are useful for predicting the ion exchange processes occurring on the surface of an inorganic material of the type studied. (author)

  2. Radiative heat exchange between surfaces

    International Nuclear Information System (INIS)

    Yener, Y.; Yuncu, H.

    1987-01-01

    The geometrical features of radiative heat exchange between surfaces are discussed first by developing various radiation shape factor relations. The governing equations for enclosures with diffusely emitting and diffusely reflecting surfaces, as well as the equations for enclosures with gray surfaces having specular component of reflectivity are introduced next. Finally, a simplified model for enclosures with isothermal surfaces under the assumption of uniform radiosity over the surfaces is discussed, and various working relations for different conditions are presented

  3. Ligand Exchange Kinetics of Environmentally Relevant Metals

    Energy Technology Data Exchange (ETDEWEB)

    Panasci, Adele Frances [Univ. of California, Davis, CA (United States)

    2014-07-15

    The interactions of ground water with minerals and contaminants are of broad interest for geochemists but are not well understood. Experiments on the molecular scale can determine reaction parameters (i.e. rates of ligand exchange, activation entropy, activation entropy, and activation volume) that can be used in computations to gain insight into reactions that occur in natural groundwaters. Experiments to determine the rate of isotopic ligand exchange for three environmentally relevant metals, rhodium (Rh), iron (Fe), and neptunium (Np), are described. Many environmental transformations of metals (e.g. reduction) in soil occur at trivalent centers, Fe(III) in particular. Contaminant ions absorb to mineral surfaces via ligand exchange, and the reversal of this reaction can be dangerous, releasing contaminants into the environment. Ferric iron is difficult to study spectroscopically because most of its complexes are paramagnetic and are generally reactive toward ligand exchange; therefore, Rh(III), which is diamagnetic and less reactive, was used to study substitution reactions that are analogous to those that occur on mineral oxide surfaces. Studies on both Np(V) and Np(VI) are important in their own right, as 237Np is a radioactive transuranic element with a half-life of 2 million years.

  4. Logarithmic Exchange Kinetics in Monodisperse Copolymeric Micelles

    Science.gov (United States)

    García Daza, Fabián A.; Bonet Avalos, Josep; Mackie, Allan D.

    2017-06-01

    Experimental measurements of the relaxation kinetics of copolymeric surfactant exchange for micellar systems unexpectedly show a peculiar logarithmic decay. Several authors use polydispersity as an explanation for this behavior. However, in coarse-grained simulations that preserve microscopic details of the surfactants, we find evidence of the same logarithmic behavior. Since we use a strictly monodisperse distribution of chain lengths such a relaxation process cannot be attributed to polydispersity, but has to be caused by an inherent physical process characteristic of this type of system. This is supported by the fact that the decay is specifically logarithmic and not a power law with an exponent inherited from the particular polydispersity distribution of the sample. We suggest that the degeneracy of the energy states of the hydrophobic block in the core, which is broken on leaving the micelle, can qualitatively explain the broad distribution of energy barriers, which gives rise to the observed nonexponential relaxation.

  5. Oxygen tracer diffusion and surface exchange kinetics in Ba0.5Sr0.5Co0.8Fe0.2O3-δ

    NARCIS (Netherlands)

    Berenov, A.; Atkinson, A.; Kilner, J.; Ananyev, M.; Eremin, V.; Porotnikova, N.; Farlenkov, A.; Kurumchin, E.; Bouwmeester, Henricus J.M.; Bucher, E.; Sitte, W.

    2014-01-01

    The oxygen tracer diffusion coefficient, Db⁎, and the oxygen tracer surface exchange coefficient, k, were measured in Ba0.5Sr0.5Co0.8Fe0.2O3 − δ (BSCF5582) over the temperature range of 310–800 °C and the oxygen partial pressure range of 1.3 × 10−3–0.21 bar. Several measurement techniques were used:

  6. Kinetics and Mechanisms of Oxygen Surface Exchange on La0.6Sr0.4FeO3-delta Thin Films

    DEFF Research Database (Denmark)

    Mosleh, Majid; Søgaard, Martin; Hendriksen, Peter Vang

    2009-01-01

    and oxygen partial pressure [i.e., the incorporation reaction has the same reaction enthalpy (H0=−105 KJ/mol) and entropy (S0=−75.5 J/mol/K) as found for bulk material]. The thin film shows smaller apparent electrical conductivity than reported for bulk. This is due to imperfections in the film, which...... is not totally dense and contains closed porosity. Electrical conductivity relaxation was used to determine the surface exchange coefficient and its dependence on the temperature and oxygen partial pressure. Relaxation curves showed a good fit to a simple exponential decay. The vacancy surface exchange...... coefficient (kV) determined from Kchem shows a slope (log kV vs log PO2) between 0.51 and 0.85. It is further found that kV is proportional to the product of the oxygen partial pressure and the vacancy concentration (kVPO2). Different reaction mechanisms that can account for the observed PO2 and -dependence...

  7. Groundwater–Surface Water Exchange

    DEFF Research Database (Denmark)

    Karan, Sachin

    The exchange of groundwater-surface water has been invetigated in the western part of Denmark. Holtum AA provides the framework for all the performed investigations. Several methods are used, primarily eld based measurements ombined with numerical models to achieve insight to the governing...... processes of interaction between groundwater and surface water. By using heat as a tracer it has been possible to use temperature directly as calibrationtargets in a groundwater and heat transport model. Thus, it is possible to use heat investigate the change in groundwater discharge in dynamic conditions...... by using simple temperature devices along a stream to delineate the areas of interest in regard to GW{SW exchange. Thus, at several locations in a stream a temperature data logger was placed in the water column and right at the streambed-water interface. By looking at the correlation of streambed...

  8. Study of kinetics, equilibrium and isotope exchange in ion exchange systems Pt. 6

    International Nuclear Information System (INIS)

    Plicka, J.; Stamberg, K.; Cabicar, J.; Gosman, A.

    1986-01-01

    The description of kinetics of ion exchange in ternary system was based upon three Nernst-Planck equations, each of them describing the particle diffusion flux of a given counterion as an independent process. For experimental verification, the strongly acidic cation exchanger OSTION KS 08 the shallow-bed technique, and 0.2 mol x dm -3 aqueous nitrate solutions were chosen. The kinetics of ion exchange in the system of cations Na + - Mg 2+ - UO 2 2+ was studied. The values of diffusion coefficients obtained by evaluating of kinetics of isotope exchange and binary ion exchange were used for calculation. The comparison of calculated exchange rate curves with the experimental ones was made. It was found that the exchanging counterions were affected by each other. (author)

  9. Control of DNA strand displacement kinetics using toehold exchange.

    Science.gov (United States)

    Zhang, David Yu; Winfree, Erik

    2009-12-02

    DNA is increasingly being used as the engineering material of choice for the construction of nanoscale circuits, structures, and motors. Many of these enzyme-free constructions function by DNA strand displacement reactions. The kinetics of strand displacement can be modulated by toeholds, short single-stranded segments of DNA that colocalize reactant DNA molecules. Recently, the toehold exchange process was introduced as a method for designing fast and reversible strand displacement reactions. Here, we characterize the kinetics of DNA toehold exchange and model it as a three-step process. This model is simple and quantitatively predicts the kinetics of 85 different strand displacement reactions from the DNA sequences. Furthermore, we use toehold exchange to construct a simple catalytic reaction. This work improves the understanding of the kinetics of nucleic acid reactions and will be useful in the rational design of dynamic DNA and RNA circuits and nanodevices.

  10. Kinetics of isotopic exchanges by using radioactive indicators

    International Nuclear Information System (INIS)

    May, S.

    1958-12-01

    After having noticed that iodine 131 under the form of sodium iodide has always been used as radioactive indicator in the CEA atomic pile located in Chatillon, this research report recalls the counting technique and some historical aspects of the notion of isotopic exchange and qualitative works, and presents some generalities on isotopic exchanges (reactions and calculation of rate constants of order 1 and 2, calculation of activation energy, spectro-photometric studies, Walden inversion, alkaline hydrolysis, influence of solvent on exchange kinetics, influence of the nature of the mineral halide). The author then addresses exchanges in aliphatic series (exchange with sodium iodide and with molecular iodine), exchanges in olefin series, exchanges in alicyclic series, and exchanges in aromatic series

  11. Kinetics of hydrogen isotope exchange reactions

    International Nuclear Information System (INIS)

    Gold, V.; McAdam, M.E.

    1975-01-01

    Under the influence of tritium β-radiation, 1,4-dioxan undergoes hydrogen exchange with the solvent water. The inhibition of the reaction by known electron scavengers (Ag + , Cu 2+ , Ni 2+ , Co 2+ , Zn 2+ , H 3 + O) and also by species with high reactivity towards hydroxyl radicals but negligible reactivity towards solvated electrons (N 3 - , Br - , SCN - ) has been examined in detail. γ-irradiation similarly induces hydrogen exchange. The action of scavengers is interpreted as requiring the involvement of two separately scavengeable primary radiolysis products in the sequence of reactions leading to exchange. The presence of electron scavengers, even at high concentration, does not totally inhibit the exchange, and a secondary exchange route, involving a low vacancy state of inhibitor cations, is considered responsible for the 'unscavengeable' portion of the reaction, by providing an alternative exchange route. Analogies are drawn between the exchange reaction and other radiation-induced reactions that are thought to involve spur processes. Some implication of radiation-chemical studies in water-alcohol mixtures are indicated. (author)

  12. Kinetics of the high temperature oxygen exchange reaction on 238PuO2 powder

    International Nuclear Information System (INIS)

    Whiting, Christofer E.; Du, Miting; Felker, L. Kevin; Wham, Robert M.; Barklay, Chadwick D.; Kramer, Daniel P.

    2015-01-01

    Oxygen exchange reactions performed on PuO 2 suggest the reaction is influenced by at least three mechanisms: an internal chemical reaction, surface mobility of active species/defects, and surface exchange of gaseous oxygen with lattice oxygen. Activation energies for the surface mobility and internal chemical reaction are presented. Determining which mechanism is dominant appears to be a complex function including at least specific surface area and temperature. Thermal exposure may also impact the oxygen exchange reaction by causing reductions in the specific surface area of PuO 2 . Previous CeO 2 surrogate studies exhibit similar behavior, confirming that CeO 2 is a good qualitative surrogate for PuO 2 , in regards to the oxygen exchange reaction. Comparison of results presented here with previous work on the PuO 2 oxygen exchange reaction allows complexities in the previous work to be explained. These explanations allowed new conclusions to be drawn, many of which confirm the conclusions presented here. - Highlights: • PuO 2 Oxygen exchange kinetics can be influenced by at least 3 different mechanisms. • An internal chemical reaction controls the rate at high temperature and large SSA. • Surface mobility and surface exchange influence rate at lower temperatures and SSA. • Exchange temperatures may alter SSA and make data difficult to interpret.

  13. Adsorption behaviour and kinetics of exchange of Zn2+ and Eu3+ ions on a composite ion exchanger

    International Nuclear Information System (INIS)

    Morcos, T.N.

    2007-01-01

    Equilibria and kinetics of exchange of both Zn2+ and Eu3+ ions on a composite ion-exchanger, cobalt hexacyanocobaltate (III) (CoHCC) incorporated in polyacrylonitrile (PAN), has been studied. The apparent capacity of CoHCC-PAN for Zn2+ and Eu3+ was determined and found to be 0.353 and 0.69 meq/g, respectively. The higher capacity for Eu3+ ions than that for Zn2+ ions is due to the higher electrostatic interaction strength of the higher charge ion with the surface. Freundlich and Langmiur adsorption isotherms were used to investigate solute (Zn2+ or Eu3+) exchange phenomenon at the liquid/solid interface. The results indicated that both Langmuir and Freundlich isotherms fit well for both Zn2+ and Eu3+. Sorption data have been also treated with the Dubinin-Radushkevich equation. The kinetics of Zn2+ or Eu3+ sorption on the composite seems to show that the reaction was proceed via two steps. The first one was fast and probably due to adsorption followed by a slow exchange reaction. In view of the data obtained on the effect of particle size and metal ion concentrations on the rate of exchange reaction, it is concluded that the mechanism for both ions was chemical control. Generally, it seems that there are two exchange sites chemically equivalent but present in pores of different sizes which lead to different degrees of dehydration of the ions sorbed on the two sites

  14. Study of kinetics, equilibrium and isotope exchange in ion exchange systems Pt. 4

    International Nuclear Information System (INIS)

    Stamberg, K.; Plicka, J.; Calibar, J.; Gosman, A.

    1985-01-01

    The kinetics of ion exchange in the Nasup(+)-Mgsup(2+)-strongly acidic cation exchanger system in a batch stirred reactor was studied. The samples of exchangers OSTION KS (containing DVB in the range of 1.5 - 12%) and AMBERLITE IR 120 for experimental work were used; the concentration of the aqueous nitrate solution was always 0.2M. The Nernst-Planck equation for description of diffusion of ions in a particle was used. The values of diffusion coefficients of magnesium ions in the exchangers and their dependence on the content of DVB were obtained by evaluating the experimental data and using the self-diffusion coefficients of sodium. (author)

  15. Disordering kinetics in surface overlayers

    International Nuclear Information System (INIS)

    Jesina, A.; Tringides, M.C.

    1993-01-01

    The disordering kinetics of the O/W(110)-p(2x1)+p(2x2) overlayer, prepared initially in a well-ordered state, are studied with low-energy electron diffraction profile analysis. The decay of the peak intensity, used as a measure of the growing disorder, cannot be fitted to a power law as in the case of ordering processes. The full width at half maximum of the time-dependent structure factor S(q,t) is constant with time, which suggests that the average size remains constant. Diffusion activation energy extracted for the temperature dependence of the disordering is 1.0±0.05 eV, which is different from the value of 0.6 eV measured in ordering processes. The difference can be explained by the adsorbate-adsorbate interactions, which contribute differently to the diffusion barrier, in the two experiments

  16. Kinetic theory of oxygen isotopic exchange between minerals and water

    Science.gov (United States)

    Criss, R.E.; Gregory, R.T.; Taylor, H.P.

    1987-01-01

    Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in "closed" and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on ??-?? plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (??), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated. ?? 1987.

  17. Equilibrium amide hydrogen exchange and protein folding kinetics

    International Nuclear Information System (INIS)

    Bai Yawen

    1999-01-01

    The classical Linderstrom-Lang hydrogen exchange (HX) model is extended to describe the relationship between the HX behaviors (EX1 and EX2) and protein folding kinetics for the amide protons that can only exchange by global unfolding in a three-state system including native (N), intermediate (I), and unfolded (U) states. For these slowly exchanging amide protons, it is shown that the existence of an intermediate (I) has no effect on the HX behavior in an off-pathway three-state system (I↔U↔N). On the other hand, in an on-pathway three-state system (U↔I↔N), the existence of a stable folding intermediate has profound effect on the HX behavior. It is shown that fast refolding from the unfolded state to the stable intermediate state alone does not guarantee EX2 behavior. The rate of refolding from the intermediate state to the native state also plays a crucial role in determining whether EX1 or EX2 behavior should occur. This is mainly due to the fact that only amide protons in the native state are observed in the hydrogen exchange experiment. These new concepts suggest that caution needs to be taken if one tries to derive the kinetic events of protein folding from equilibrium hydrogen exchange experiments

  18. Nonlocal exchange and kinetic-energy density functionals for electronic systems

    International Nuclear Information System (INIS)

    Glossman, M.D.; Rubio, A.; Balbas, L.C.; Alonso, J.A.

    1992-01-01

    The nonlocal weighted density approximation (WDA) to the exchange and kinetic-energy functionals of many electron systems proposed several years ago by Alonso and Girifalco is used to compute, within the framework of density functional theory, the ground-state electronic density and total energy of noble gas atoms and of neutral jellium-like sodium clusters containing up to 500 atoms. These results are compared with analogous calculations using the well known Thomas-Fermi-Weizsacker-Dirac (TFWD) approximations for the kinetic (TFW) and exchange (D) energy density functionals. An outstanding improvement of the total and exchange energies, of the density at the nucleus and of the expectation values is obtained for atoms within the WDA scheme. For sodium clusters the authors notice a sizeable contribution of the nonlocal effects to the total energy and to the density profiles. In the limit of very large clusters these effects should affect the surface energy of the bulk metal

  19. Neutralization kinetics of charged polymer surface

    Energy Technology Data Exchange (ETDEWEB)

    Mukherjee, S. [Surface Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India); Mukherjee, M. [Surface Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India)], E-mail: manabendra.mukherjee@saha.ac.in

    2008-04-15

    In case of photoemission spectroscopy of an insulating material the data obtained from the charged surface are normally distorted due to differential charging. Recently, we have developed a controlled surface neutralization technique to study the kinetics of the surface charging. Using this technique and the associated data analysis scheme with an effective charging model, quantitative information from the apparently distorted photoemission data from PTFE surfaces were extracted. The surface charging was controlled by tuning the electron flood current as well as the X-ray intensity. The effective model was found to describe the charging consistently for both the cases. It was shown that the non-linear neutralization response of differential charging around a critical neutralizing electron flux or a critical X-ray emission current was due to percolation of equipotential surface domains. The obtained value of the critical percolation exponent {gamma} close to unity indicates a percolation similar to that of avalanche breakdown or chain reaction.

  20. Kinetics of the high temperature oxygen exchange reaction on {sup 238}PuO{sub 2} powder

    Energy Technology Data Exchange (ETDEWEB)

    Whiting, Christofer E., E-mail: chris.whiting@udri.udayton.edu [University of Dayton – Research Institute, 300 College Park, Dayton, OH 45469-0172 (United States); Du, Miting; Felker, L. Kevin; Wham, Robert M. [Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, TN 37831 (United States); Barklay, Chadwick D.; Kramer, Daniel P. [University of Dayton – Research Institute, 300 College Park, Dayton, OH 45469-0172 (United States)

    2015-12-15

    Oxygen exchange reactions performed on PuO{sub 2} suggest the reaction is influenced by at least three mechanisms: an internal chemical reaction, surface mobility of active species/defects, and surface exchange of gaseous oxygen with lattice oxygen. Activation energies for the surface mobility and internal chemical reaction are presented. Determining which mechanism is dominant appears to be a complex function including at least specific surface area and temperature. Thermal exposure may also impact the oxygen exchange reaction by causing reductions in the specific surface area of PuO{sub 2}. Previous CeO{sub 2} surrogate studies exhibit similar behavior, confirming that CeO{sub 2} is a good qualitative surrogate for PuO{sub 2}, in regards to the oxygen exchange reaction. Comparison of results presented here with previous work on the PuO{sub 2} oxygen exchange reaction allows complexities in the previous work to be explained. These explanations allowed new conclusions to be drawn, many of which confirm the conclusions presented here. - Highlights: • PuO{sub 2} Oxygen exchange kinetics can be influenced by at least 3 different mechanisms. • An internal chemical reaction controls the rate at high temperature and large SSA. • Surface mobility and surface exchange influence rate at lower temperatures and SSA. • Exchange temperatures may alter SSA and make data difficult to interpret.

  1. Electrostatic influence of local cysteine environments on disulfide exchange kinetics.

    Science.gov (United States)

    Snyder, G H; Cennerazzo, M J; Karalis, A J; Field, D

    1981-11-10

    The ionic strength dependence of the bimolecular rate constant for reaction of the negative disulfide 5,5'-dithiobis (2-nitrobenzoic acid) with cysteines in fragments of naturally occurring proteins was determined by stopped-flow spectroscopy. The Debye-Hückel relationship was applied to determine the effective charge at the cysteine and thereby determine the extent to which nearby neighbors in the primary sequence influence the kinetics. Corrections for the secondary salt effect on cysteine pKs were determined by direct spectrometric pH titration of sulfhydryl groups or by observation of the ionic strength dependence of kinetics of cysteine reaction with the neutral disulfide 2,2'-dithiodipyridine. Quantitative expressions was verified by model studies with N-acetyl-cystein. At ionic strengths equal to or greater than 20 mM, the net charge at the polypeptide cysteine site is the sum of the single negative charge of the thiolate anion and the charges of the amino acids immediately preceding and following the cysteine in the primary sequence. At lower ionic strengths, more distant residues influence kinetics. At pH 7.0, 23 degree C, and an ionic strength of 20 mM, rate constants for reaction of the negative disulfide with a cysteine having two positive neighbors, one positive and one neutral neighbor, or two neutral neighbors are 132000, 3350, and 367 s-1 M-1, respectively. This corresponds to a contribution to the activation energy of 0.65- 1.1 kcal/mol per ion pair involved in collision between the cysteine and disulfide regions. The results permit the estimation that cysteine local environments may provide a means of achieving a 10(6)-fold range in rate constants in disulfide exchange reactions in random-coil proteins. This range may prove useful in developing strategies for directing disulfide pairing in synthetic proteins.

  2. Kinetics and thermodynamic for sorption of arsenate by Lanthanum-exchanged zeolite

    International Nuclear Information System (INIS)

    Mohd Jelas Haron; Saiful Adli Masdan; Mohd Zobir Hussein; Zulkarnain Zainal; Anuar Kassim

    2007-01-01

    Zeolites are crystalline, hydrated aluminosilicate containing exchangeable alkaline and alkaline earth cations in their structural frameworks. Since zeolites have permanent negative charges on their surfaces, they have no affinity for anions. However recent studies have shown that modification of zeolites with certain surfactants or metal cations yield sorbents with a strong affinity for many anions. In this paper, modification of zeolites (zeolite A, X and ZSM5) were performed by exchange of naturally occurring cations with lanthanum ion that forms low solubility arsenate salt. The exchanged zeolites were used to sorb arsenate from aqueous solution. Among parameters investigated were effect of pH, arsenate initial concentrations, contact time and temperature. The maximum exchanged capacity of La (III) ion was obtained when using solution with initial pH of 4. Zeolite X gives the highest La (III) exchanged capacity compared to other zeolites. The results showed that As (V) sorption by La-zeolites occurred at about pH 6.5 and increased as pH increased and reaching maximum at equilibrium pH about 7.8. On the other hand, almost no arsenate sorption occurred on un exchanged zeolites. This indicates that La (III) ion on the exchanged zeolites is taking part on the As(V) sorption via surface precipitation. The results also showed that the sorption capacities increased with increasing initial As (V) concentrations. The sorption followed Langmuir model with maximum sorption capacities of 0.41, 0.21 and 0.19 mmol/g at 25 degree Celsius for La exchanged zeolite X (La-ZX), La exchanged zeolite ZSM5 (La-ZSM) and La exchanged zeolite A (La-ZA), respectively. The amounts of sorption of As (V) by La exchanged zeolite increased as temperature increased from 25 to 70 degree Celsius indicating that the process is endothermic. The free energy changes ( ΔG degree) for the sorption at 25 degree Celsius were -10.25, -9.65 and -8.49 kJ/ mol for La-ZX, La-ZSM and La-ZA, respectively. The

  3. Kinetics of particle deposition at heterogeneous surfaces

    Science.gov (United States)

    Stojiljković, D. Lj.; Vrhovac, S. B.

    2017-12-01

    The random sequential adsorption (RSA) approach is used to analyze adsorption of spherical particles of fixed diameter d0 on nonuniform surfaces covered by square cells arranged in a square lattice pattern. To characterize such pattern two dimensionless parameters are used: the cell size α and the cell-cell separation β, measured in terms of the particle diameter d0. Adsorption is assumed to occur if the particle (projected) center lies within a cell area. We focus on the kinetics of deposition process in the case when no more than a single disk can be placed onto any square cell (α deposition process is not consistent with the power law behavior. However, if the geometry of the pattern approaches towards ;noninteracting conditions; (β > 1), when adsorption on each cell can be decoupled, approach of the coverage fraction θ(t) to θJ becomes closer to the exponential law. Consequently, changing the pattern parameters in the present model allows to interpolate the deposition kinetics between the continuum limit and the lattice-like behavior. Structural properties of the jammed-state coverings are studied in terms of the radial distribution function g(r) and spatial distribution of particles inside the cell. Various, non-trivial spatial distributions are observed depending on the geometry of the pattern.

  4. Treatment of polymer surfaces in plasma Part I. Kinetic model

    International Nuclear Information System (INIS)

    Tabaliov, N A; Svirachev, D M

    2006-01-01

    The surface tension of the polymer materials depends on functional groups over its surface. As a result from the plasma treatment the kind and concentration of the functional groups can be changed. In the present work, the possible kinetic reactions are defined. They describe the interaction between the plasma and the polymer surface of polyethylene terephthalate (PET). Basing on these reactions, the systems of differential kinetic equations are suggested. The solutions are obtained analytically for the system kinetic equations at defined circumstances

  5. Hydrogen exchange kinetics changes upon formation of the soybean trypsin inhibitor: trypsin complex

    International Nuclear Information System (INIS)

    Woodward, C.K.; Ellis, L.M.

    1975-01-01

    The hydrogen exchange kinetics of the complex of trypsin--soybean trypsin inhibitor (Kunitz) have been compared to the calculated sum of the exchange kinetics for the inhibitor and trypsin measured separately. The exchange rates observed for the complex are substantially less than the sum of the exchange rates in the two individual proteins. These results cannot be accounted for by changes in intermolecular or intramolecular hydrogen bonding. The decrease in exchange rates in the complex are ascribed to changes in solvent accessibility in the component proteins. (U.S.)

  6. Nickel speciation and complexation kinetics in freshwater by ligand exchange and DPCSV

    NARCIS (Netherlands)

    Han Bin Xue,; Jansen, S.; Prasch, A.; Sigg, L.

    2001-01-01

    A technique of ligand exchange with DMG (dimethylglyoxime) and DPCSV was applied to determine Ni speciation in lake, river, and groundwater samples. The working conditions related to ligand-exchange equilibrium were optimized, and the ligand-exchange kinetics were examined. The observed

  7. Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

    KAUST Repository

    Hong, Jongsup

    2013-10-01

    The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

  8. Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

    KAUST Repository

    Hong, Jongsup; Kirchen, Patrick; Ghoniem, Ahmed F.

    2013-01-01

    The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

  9. Ion Exchange Equilibrium and Kinetic Properties of Polyacrylate Films and Applications to Chemical Analysis and Environmental Decontamination

    Science.gov (United States)

    Tanner, Stephen P.

    1997-01-01

    One of the goals of the original proposal was to study how cross-linking affects the properties of an ion exchange material(IEM) developed at Lewis Research Center. However, prior to the start of this work, other workers at LERC investigated the effect of cross-linking on the properties of this material. Other than variation in the ion exchange capacity, the chemical characteristics were shown to be independent of the cross-linking agent, and the degree of cross-linking. New physical forms of the film were developed (film, supported film, various sizes of beads, and powder). All showed similar properties with respect to ion exchange equilibria but the kinetics of ion exchange depended on the surface area per unit mass; the powder form of the IEM exchanging much more rapidly than the other forms. The research performed under this grant was directed towards the application of the IEM to the analysis of metal ions at environmental concentrations.

  10. Surface exchange kinetics and chemical diffusivities of BaZr{sub 0.2}Ce{sub 0.65}Y{sub 0.15}O{sub 3−δ} by electrical conductivity relaxation

    Energy Technology Data Exchange (ETDEWEB)

    Lim, Dae-Kwang; Jeon, Sang-Yun; Singh, Bhupendra [Ionics Lab, School of Materials Science and Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwang-Ju 500-757 (Korea, Republic of); Park, Jun-Young [Department of Advanced Materials Engineering, Sejong University, Seoul 143-747 (Korea, Republic of); Song, Sun-Ju, E-mail: song@chonnam.ac.kr [Ionics Lab, School of Materials Science and Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwang-Ju 500-757 (Korea, Republic of)

    2014-10-15

    Highlights: • Electrical conductivity relaxation in BaCe{sub 0.65}Zr{sub 0.2}Y{sub 0.15}O{sub 3−δ} was monitored. • Monotonic relaxation behavior was observed during oxidation/reduction. • Nonmonotonic twofold relaxation behavior was observed during hydration/dehydration. • Surface exchange coefficients and diffusivities of O and H were calculated. - Abstract: Perovskite-type oxide BaCe{sub 0.65}Zr{sub 0.2}Y{sub 0.15}O{sub 3−δ} (BCZY2015) was synthesized by a solid state reaction method. BCZY2015 samples were characterized by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The time dependent variation in electrical conductivity of BCZY2015 was monitored during the oxidation/reduction in oxygen partial pressure (pO{sub 2}) range of −2.28 ⩽ log (pO{sub 2}/atm) ⩽ −0.68 at a fixed water vapor pressure (pH{sub 2}O), and during the hydration/dehydration in −3.15 ⩽ log (pH{sub 2}O/atm) ⩽ −2.35 range in air. The electrical conductivity showed a monotonic relaxation behavior by the ambipolar diffusion of V{sub o}{sup ··} and OH{sub o}{sup ·} during the oxidation/reduction and the relaxation process was governed by the diffusivity of oxygen (D-tilde{sub vO}). On the other hand, during the hydration/dehydration process, a non-monotonic twofold relaxation behavior was observed due to the decoupled diffusion of H and O components with the mediation of holes, and the conductivity relaxation process was governed by the diffusivities of both H (D-tilde{sub iH}) and O (D-tlde{sub vH}). The values of surface exchange coefficients and diffusivities of oxygen and hydrogen were calculated from Fick’s second law by the nonlinear least squares fitting of the conductivity data, as proposed by Yoo et al. (2008)

  11. Comparative study on ion-isotopic exchange reaction kinetics by application of tracer technique

    International Nuclear Information System (INIS)

    Lokhande, R.S.; Singare, P.U.

    2007-01-01

    The radioactive isotopes 131 I and 82 Br were used to trace the ion-isotopic exchange reactions using industrial grade ion exchange resins Amberlite IRA-400. The experiments were performed to understand the effect of temperature and concentration of ionic solution on kinetics of exchange reactions. Both the exchange reactions were greatly influenced by rise in temperature, which result in higher percentage of ions exchanged. For bromide ion-isotopic exchange reactions, the calculated values of specific reaction rate/min -1 , and amount of ions exchanged/mmol were obtained higher than that for iodide ion-isotopic exchange reactions under identical experimental conditions. The observed variation in the results for two ion-isotopic exchange reactions was due to the difference in the ionic size of bromide and iodide ions. (orig.)

  12. Surface Modification and Surface - Subsurface Exchange Processes on Europa

    Science.gov (United States)

    Phillips, C. B.; Molaro, J.; Hand, K. P.

    2017-12-01

    The surface of Jupiter's moon Europa is modified by exogenic processes such as sputtering, gardening, radiolysis, sulfur ion implantation, and thermal processing, as well as endogenic processes including tidal shaking, mass wasting, and the effects of subsurface tectonic and perhaps cryovolcanic activity. New materials are created or deposited on the surface (radiolysis, micrometeorite impacts, sulfur ion implantation, cryovolcanic plume deposits), modified in place (thermal segregation, sintering), transported either vertically or horizontally (sputtering, gardening, mass wasting, tectonic and cryovolcanic activity), or lost from Europa completely (sputtering, plumes, larger impacts). Some of these processes vary spatially, as visible in Europa's leading-trailing hemisphere brightness asymmetry. Endogenic geologic processes also vary spatially, depending on terrain type. The surface can be classified into general landform categories that include tectonic features (ridges, bands, cracks); disrupted "chaos-type" terrain (chaos blocks, matrix, domes, pits, spots); and impact craters (simple, complex, multi-ring). The spatial distribution of these terrain types is relatively random, with some differences in apex-antiapex cratering rates and latitudinal variation in chaos vs. tectonic features. In this work, we extrapolate surface processes and rates from the top meter of the surface in conjunction with global estimates of transport and resurfacing rates. We combine near-surface modification with an estimate of surface-subsurface (and vice versa) transport rates for various geologic terrains based on an average of proposed formation mechanisms, and a spatial distribution of each landform type over Europa's surface area. Understanding the rates and mass balance for each of these processes, as well as their spatial and temporal variability, allows us to estimate surface - subsurface exchange rates over the average surface age ( 50myr) of Europa. Quantifying the timescale

  13. Kinetics of exchange of a tracer in soil and clay samples

    International Nuclear Information System (INIS)

    Zanotti, J.C.; Facetti, J.F.

    1971-01-01

    The kinetics of exchange of a Na tracer in soil and clay samples, provides with a reliable and convenient method for the determination of the different soil fraction ahd their CEC values, In addition, the analysis of the exchanges curves can be used for the identification of the clay present in the soil

  14. Kinetics of exchange of a tracer in soil and clay samples

    Energy Technology Data Exchange (ETDEWEB)

    Zanotti, J C; Facetti, J F [Asuncion Nacional Univ. (Paraguay). Inst. de Ciencias

    1971-01-01

    The kinetics of exchange of a Na tracer in soil and clay samples, provides with a reliable and convenient method for the determination of the different soil fraction ahd their CEC values, In addition, the analysis of the exchanges curves can be used for the identification of the clay present in the soil.

  15. Some considerations on the treatment of the kinetic data of heterogeneous isotope exchange

    International Nuclear Information System (INIS)

    Koernyei, J.; Szirtes, L.; Lakatos, M.

    1985-01-01

    A direct curve simulation treatment was worked out for the evaluation of the kinetic curves of heterogeneous isotope exchange. Based on the data obtained by a personal computer, some considerations were made on the transport processes in the fully and half exchanged sodium forms of crystalline zirconium phosphate. (author)

  16. Kinetics of tritium isotope exchange between liquid pyrrole and gaseous hydrogen

    International Nuclear Information System (INIS)

    Stolarz, A.

    1994-01-01

    The kinetics of tritium isotope exchange between liquid pyrrole and gaseous hydrogen has been studied over the temperature range of 290-303 K. The reaction was carried out in the presence of platinum black but in spite of that, it appeared to be relatively slow. The kinetics of the exchange reaction studied could be described by the simple McKay equation. The results obtained suggest that diffusion is the rate-determining step. A mechanism of exchange is proposed. (author) 10 refs.; 2 figs.; 1 tab

  17. The load and release characteristics on a strong cationic ion-exchange fiber: kinetics, thermodynamics, and influences.

    Science.gov (United States)

    Yuan, Jing; Gao, Yanan; Wang, Xinyu; Liu, Hongzhuo; Che, Xin; Xu, Lu; Yang, Yang; Wang, Qifang; Wang, Yan; Li, Sanming

    2014-01-01

    Ion-exchange fibers were different from conventional ion-exchange resins in their non-cross-linked structure. The exchange was located on the surface of the framework, and the transport resistance reduced significantly, which might mean that the exchange is controlled by an ionic reaction instead of diffusion. Therefore, this work aimed to investigate the load and release characteristics of five model drugs with the strong cationic ion-exchange fiber ZB-1. Drugs were loaded using a batch process and released in United States Pharmacopoeia (USP) dissolution apparatus 2. Opposing exchange kinetics, suitable for the special structure of the fiber, were developed for describing the exchange process with the help of thermodynamics, which illustrated that the load was controlled by an ionic reaction. The molecular weight was the most important factor to influence the drug load and release rate. Strong alkalinity and rings in the molecular structures made the affinity between the drug and fiber strong, while logP did not cause any profound differences. The drug-fiber complexes exhibited sustained release. Different kinds and concentrations of counter ions or different amounts of drug-fiber complexes in the release medium affected the release behavior, while the pH value was independent of it. The groundwork for in-depth exploration and further application of ion-exchange fibers has been laid.

  18. Kinetics of transesterification of methyl acetate and n-octanol catalyzed by cation exchange resins

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yong; Gao, Li; Li, Xiying; Mao, Liqun [Henan University, Kaifeng (China); Wei, Min [Henan University of Technology, Zhengzhou (China)

    2013-05-15

    The transesterification kinetics of methyl acetate with n-octanol to octyl acetate and methanol were studied using Amberlyst 15 as catalyst in a batch stirred reactor. The influence of the agitation speed, particle size, temperature, catalyst loading, and initial reactants molar ratio was investigated in detail. A pseudo-homogeneous (PH) kinetic model was applied to correlate the experimental data in the temperature range of 313.15 K to 328.15 K. The estimated kinetic parameters made the calculated results in good agreement with the experimental data. A kinetic model describing the transesterification reaction catalyzed by cation exchange resins was developed.

  19. Surface - atmosphere exchange of ammonia over grazed pasture

    NARCIS (Netherlands)

    Plantaz, M.A.H.G.

    1998-01-01

    This thesis deals with the exchange of ammonia between the atmosphere and grazed pasture in an area of intensive livestock breeding. The term exchange is used because gaseous ammonia can be taken up (dry deposition) as well as released (emission) by this type of surface.
    Ammonia exchange

  20. Strontium-free rare earth perovskite ferrites with fast oxygen exchange kinetics: Experiment and theory

    Science.gov (United States)

    Berger, Christian; Bucher, Edith; Windischbacher, Andreas; Boese, A. Daniel; Sitte, Werner

    2018-03-01

    The Sr-free mixed ionic electronic conducting perovskites La0.8Ca0.2FeO3-δ (LCF82) and Pr0.8Ca0.2FeO3-δ (PCF82) were synthesized via a glycine-nitrate process. Crystal structure, phase purity, and lattice constants were determined by XRD and Rietveld analysis. The oxygen exchange kinetics and the electronic conductivity were obtained from in-situ dc-conductivity relaxation experiments at 600-800 °C and 1×10-3≤pO2/bar≤0.1. Both LCF82 and PCF82 show exceptionally fast chemical surface exchange coefficients and chemical diffusion coefficients of oxygen. The oxygen nonstochiometry of LCF82 and PCF82 was determined by precision thermogravimetry. A point defect model was used to calculate the thermodynamic factors of oxygen and to estimate self-diffusion coefficients and ionic conductivities. Density Functional Theory (DFT) calculations on the crystal structure, oxygen vacancy formation as well as oxygen migration energies are in excellent agreement with the experimental values. Due to their favourable properties both LCF82 and PCF82 are of interest for applications in solid oxide fuel cell cathodes, solid oxide electrolyser cell anodes, oxygen separation membranes, catalysts, or electrochemical sensors.

  1. NMR studies of proton exchange kinetics in aqueous formaldehyde solutions.

    Science.gov (United States)

    Rivlin, Michal; Eliav, Uzi; Navon, Gil

    2014-05-01

    Aqueous solutions of formaldehyde, formalin, are commonly used for tissue fixation and preservation. Treatment with formalin is known to shorten the tissue transverse relaxation time T2. Part of this shortening is due to the effect of formalin on the water T2. In the present work we show that the shortening of water T2 is a result of proton exchange between water and the major constituent of aqueous solutions of formaldehyde, methylene glycol. We report the observation of the signal of the hydroxyl protons of methylene glycol at 2ppm to high frequency of the water signal that can be seen at low temperatures and at pH range of 6.0±1.5 and, at conditions where it cannot be observed by the single pulse experiment, it can be detected indirectly through the water signal by the chemical exchange saturation transfer (CEST) experiment. The above finding made it possible to obtain the exchange rate between the hydroxyl protons of the methylene glycol and water in aqueous formaldehyde solutions, either using the dispersion of the spin-lattice relaxation rate in the rotating frame (1/T1ρ) or, at the slow exchange regime, from the line width hydroxyl protons of methylene glycol. The exchange rate was ∼10(4)s(-1) at pH 7.4 and 37°C, the activation energy, 50.2kJ/mol and its pH dependence at 1.1°C was fitted to: k (s(-1))=520+6.5×10(7)[H(+)]+3.0×10(9)[OH(-)]. Copyright © 2014. Published by Elsevier Inc.

  2. Surface kinetic temperature mapping using satellite spectral data in ...

    African Journals Online (AJOL)

    The result revealed that despite the limited topographic differences of the rift lakes and their proximity, the surface kinetic temperature difference is high, mainly due to groundwater and surface water fluxes. From thermal signature analysis two hot springs below the lake bed of Ziway were discovered. The various hot springs ...

  3. Isotope exchange kinetic of phosphorus in soils from Pernambuco State -Brazil

    International Nuclear Information System (INIS)

    Figueiredo, F.J.B. de.

    1989-12-01

    The applicability of isotopic exchange kinetics of 32 p to characterize phosphorus available to plants and to diagnose the reactivity of soil-fertilizer-P in six soils from Pernambuco is described. This methodology was compared with anion exchange resin, isotopic exchange equilibrium methods (E-value and L-value) and P absorption by plants. The first greenhouse experiment had the following treatments: 1) with P and, 2) with addition of 43.7 mg P/Kg of soil, incubated for O, 42 and 84 days before seeding. The kinetic of isotopic exchange (KIE), resin-P and E-value were determined before seeding and after harvesting pearl millet grown for 42 days. Results indicated that the KIE parameters rated the soils more efficiently, in terms of available P and soil-fertilizer-P reactivity, than resin-P, E-value and L-value. (author). 38 refs, 2 figs, 18 tabs

  4. Application of personal computers to study the kinetics of heterogeneous isotopic exchange

    International Nuclear Information System (INIS)

    Koernyei, Jozsef; Lakatos, Mihaly

    1985-01-01

    The kinetics of some heterogeneous isotopic exchange reactions of alkaline metal ions between solid (crystalline zirconium phosphate) and liquid phases were investigated. Ion diffusion in solid phase was considered as rate controlling step. The Laplace transformation solution of Fick's II law was used with a Sinclair ZX Spectrum personal computer. In some cases the exchange reaction should be regarded as a superposition of diffusion and a first order process. (author)

  5. Method of relative comparison of the thermohydraulic efficiency of heat exchange intensification in channels of heat-exchange surfaces

    International Nuclear Information System (INIS)

    Dubrovskij, E.V.; Vasil'ev, V.Ya.

    2002-01-01

    One introduces a technique to compare relatively thermohydraulic efficiency of heat transfer intensification in channels of heat exchange surfaces of any design types. It is shown that one should compare thermohydraulic efficiency of heat exchange intensification as to the thermal power of heat exchangers and pressure losses in channels with turbulators and in polished channels of heat exchange surfaces on the basis of dimensions of heat exchangers, their heat exchange surfaces and at similar (as to Re numbers) modes of coolant flow [ru

  6. Ion-Isotopic Exchange Reaction Kinetics using Anion Exchange Resins Dowex 550A LC and Indion-930A

    Directory of Open Access Journals (Sweden)

    P.U. Singare

    2014-06-01

    Full Text Available The present paper deals with the characterization of ion exchange resins Dowex 550A LC and Indion-930A based on kinetics of ion-isotopic exchange reactions for which the short lived radioactive isotopes 131I and 82Br were used as a tracers. The study was performed for different concentration of ionic solution varying from 0.001 mol/L to 0.004 mol/L and temperature in the range of 30.0 °C to 45.0 °C. The results indicate that as compared to bromide ion-isotopic exchange reaction, iodide exchange reaction take place at the faster rate. For both the ion-isotopic exchange reactions, under identical experimental conditions, the values of specific reaction rate increases with increase in the ionic concentration and decreases with rise in temperature. It was observed that at 35.00C, 1.000 g of ion exchange resins and 0.002 mol/L labeled iodide ion solution for iodide ion-isotopic exchange reaction, the values of specific reaction rate (min-1, amount of ion exchanged (mmol, initial rate of ion exchange (mmol/min and log Kd were 0.270, 0.342, 0.092 and 11.8 respectively for Dowex 550A LC resin, which was higher than the respective values of 0.156, 0.241, 0.038 and 7.4 as that obtained for Indion-930A resins. From the results, it appears that Dowex 550A LC resins show superior performance over Indion-930A resins under identical experimental conditions.

  7. LSM Microelectrodes: Kinetics and Surface Composition

    DEFF Research Database (Denmark)

    Hansen, Karin Vels; Norrman, Kion; Jacobsen, Torben

    2015-01-01

    spectroscopy and cyclic voltammetry were performed on electrodes with diameters of 20–100 μm in oxygen, air and nitrogen both at open circuit voltage and at anodic and cathodic polarization. In situ conductance mapping, ex situ surface analysis by time-of-flight secondary ion mass spectrometry, and scanning...

  8. Kinetic-energy functionals studied by surface calculations

    DEFF Research Database (Denmark)

    Vitos, Levente; Skriver, Hans Lomholt; Kollár, J.

    1998-01-01

    The self-consistent jellium model of metal surfaces is used to study the accuracy of a number of semilocal kinetic-energy functionals for independent particles. It is shown that the poor accuracy exhibited by the gradient expansion approximation and most of the semiempirical functionals in the lo...... density, high gradient limit may be subtantially improved by including locally a von Weizsacker term. Based on this, we propose a simple one-parameter Pade's approximation, which reproduces the exact Kohn-Sham surface kinetic energy over the entire range of metallic densities....

  9. Relating surface chemistry and oxygen surface exchange in LnBaCo2O(5+δ) air electrodes.

    Science.gov (United States)

    Téllez, Helena; Druce, John; Kilner, John A; Ishihara, Tatsumi

    2015-01-01

    The surface and near-surface chemical composition of electroceramic materials often shows significant deviations from that of the bulk. In particular, layered materials, such as cation-ordered LnBaCo2O(5+δ) perovskites (Ln = lanthanide), undergo surface and sub-surface restructuring due to the segregation of the divalent alkaline-earth cation. These processes can take place during synthesis and processing steps (e.g. deposition, sintering or annealing), as well as at temperatures relevant for the operation of these materials as air electrodes in solid oxide fuel cells and electrolysers. Furthermore, the surface segregation in these double perovskites shows fast kinetics, starting at temperatures as low as 400 °C over short periods of time and leading to a decrease in the transition metal surface coverage exposed to the gas phase. In this work, we use a combination of stable isotope tracer labeling and surface-sensitive ion beam techniques to study the oxygen transport properties and their relationship with the surface chemistry in ordered LnBaCo2O(5+δ) perovskites. Time-of-Flight Secondary-Ion Mass Spectrometry (ToF-SIMS) combined with (18)O isotope exchange was used to determine the oxygen tracer diffusion (D*) and surface exchange (k*) coefficients. Furthermore, Low Energy Ion Scattering (LEIS) was used for the analysis of the surface and near surface chemistry as it provides information from the first mono-atomic layer of the materials. In this way, we could relate the compositional modifications (e.g. cation segregation) taking place at the electrochemically-active surface during the exchange at high temperatures and the oxygen transport properties in double perovskite electrode materials to further our understanding of the mechanism of the surface exchange process.

  10. Untangling surface oxygen exchange effects in YBa2Cu3O6+x thin films by electrical conductivity relaxation.

    Science.gov (United States)

    Cayado, P; Sánchez-Valdés, C F; Stangl, A; Coll, M; Roura, P; Palau, A; Puig, T; Obradors, X

    2017-05-31

    The kinetics of oxygen incorporation (in-diffusion process) and excorporation (out-diffusion process), in YBa 2 Cu 3 O 6+x (YBCO) epitaxial thin films prepared using the chemical solution deposition (CSD) methodology by the trifluoroacetate route, was investigated by electrical conductivity relaxation measurements. We show that the oxygenation kinetics of YBCO films is limited by the surface exchange process of oxygen molecules prior to bulk diffusion into the films. The analysis of the temperature and oxygen partial pressure influence on the oxygenation kinetics has drawn a consistent picture of the oxygen surface exchange process enabling us to define the most likely rate determining step. We have also established a strategy to accelerate the oxygenation kinetics at low temperatures based on the catalytic influence of Ag coatings thus allowing us to decrease the oxygenation temperature in the YBCO thin films.

  11. Kinetics of ethylenediaminetetraacetate exchange of americium (3) with copper (2) in aqueous solution

    International Nuclear Information System (INIS)

    Nikitenko, S.I.; Martynenko, L.I.; Pechurova, N.I.

    1985-01-01

    By the method of spectrophotometry exchange kinetics in the AmA - -Cu 2+ , where A 4- -ethylenediaminetetraacetate, is studied. The values of exchange rate constants and thermodynamic activation parameters have been found. It is shown that exchange of central ions is rialized according to the dissociative mechanism with formation of intermediate protonated complexes and according to the associative mechanism with formation of binuclear intermediates. The exchange mechanisms identity for AmA - and LnA - , where Ln 3+ -RE cations of cerium subgroup is proved. It is assumed that values of activation entropy in exchange processes are determined by the radius of the leaving cation and of activation enthalpy - by the peculiarities of the electronic structure

  12. Kinetics of isotopic exchange between calcium molybdate and molybdate ions in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Atun, G.; Ayar, N.; Bilgin, B. [Istanbul Univ. (Turkey). Dept. of Chemistry, Fac. of Engineering; Bodur, N.; Ayyildiz, H. [Cekmece Nuclear Research and Training Center, Istanbul (Turkey)

    2007-07-01

    The heterogeneous isotopic anion exchange kinetics and equilibria between calcium molybdate and sodium molybdate solutions have been studied by using {sup 99}Mo as tracer in batch experiments. The values of exchange ratio lower than unity suggest that rate-limiting step is particle diffusion process and the effect of re-crystallization can be neglected. The self-diffusion coefficients calculated using both Paterson's and Nernst-Plank approximations are increased by the temperature. The observed values for isotope exchange characteristics such as exchange fractions, exchanging amounts and fractional attainment of equilibrium are consistent with those of their calculated values. Activation energy and thermodynamic parameters calculated based on transition state theory indicate the existence of both energy and entropy barrier in the system. (orig.)

  13. Kinetics of isotopic exchange between calcium molybdate and molybdate ions in aqueous solution

    International Nuclear Information System (INIS)

    Atun, G.; Ayar, N.; Bilgin, B.

    2007-01-01

    The heterogeneous isotopic anion exchange kinetics and equilibria between calcium molybdate and sodium molybdate solutions have been studied by using 99 Mo as tracer in batch experiments. The values of exchange ratio lower than unity suggest that rate-limiting step is particle diffusion process and the effect of re-crystallization can be neglected. The self-diffusion coefficients calculated using both Paterson's and Nernst-Plank approximations are increased by the temperature. The observed values for isotope exchange characteristics such as exchange fractions, exchanging amounts and fractional attainment of equilibrium are consistent with those of their calculated values. Activation energy and thermodynamic parameters calculated based on transition state theory indicate the existence of both energy and entropy barrier in the system. (orig.)

  14. Kinetic study of ion exchange in phosphoric acid chelating resin

    International Nuclear Information System (INIS)

    Brikci-Nigassa, Mounir; Hamouche, Hafida

    1995-11-01

    Uranium may be recovered as a by product of wet phosphoric acid using a method based on specific ion exchange resins. These resins called chelates contain amino-phosphonic functional groups. The resin studied in this work is a purolite S-940; uranium may be loaded on this resin from 30% P2O5 phosphoric acid in its reduced state. The influence of different parameters on the successive steps of the process have been studied in batch experiments: uranium reduction, loading and oxydation. Uranium may be eluted with ammonium carbonate and the resin regeneration may be done with hydrochloric acid.Ferric ions reduce the effective resin capacity considerably and inert fixation conditions are proposed to enhance uranium loading

  15. Charge exchange of muons in gases: I. Kinetic equations

    International Nuclear Information System (INIS)

    Turner, R.E.

    1983-06-01

    Kinetic equations for the spin density operators of the diamagnetic and paramagnetic states of the positive muon are obtained for the description of the slowing-down process encountered when high energy muons thermalize in a single component gas. The motion of this two species system is generated by the Liouville superoperators associated with the diamagnetic and paramagnetic spin Hamiltonians and by time-dependent rate superoperators which depict the probabilities per collision that an electron is captured or lost. These rates are translational averages of the appropriate Boltzmann collision operators. That is, they are momentum and position integrals of the product of either the electron capture or loss total cross section with the single particle translational density operators for the muon (or muonium) and a gas particle. These rates are time dependent because the muon (or muonium) translational density operator is time dependent. The initial amplitudes and phases of the observed thermal spin polarization in μSR experiments are then obtained in terms of the spin density operators emerging from the stopping regime

  16. Charge exchange of muons in gases. Kinetic equations

    International Nuclear Information System (INIS)

    Turner, R.E.

    1983-01-01

    Kinetic equations for the spin-density operators of the diamagnetic and paramagnetic states of the positive muon are obtained for the description of the slowing-down process encountered when high-energy muons thermalize in a single-component gas. The motion of this two-species system is generated by the Liouville superoperators associated with the diamagnetic and paramagnetic spin Hamiltonians and by time-dependent rate superoperators which depict the probabilities per collision that an electron is captured or lost. These rates are translational averages of the appropriate Boltzmann collision operators. That is, they are momentum and position integrals of the product of either the electron capture or loss total cross section with the single-particle translational density operators for the muon (or muonium) and a gas particle. These rates are time dependent because the muon (or muonium) translational density operator is time dependent. The initial amplitudes and phases of the observed thermal spin polarization in muon-spin-rotation (μSR) experiments are then obtained in terms of the spin-density operators emerging from the stopping regime

  17. Kinetic theory of surface waves in plasma jets

    International Nuclear Information System (INIS)

    Shokri, B.

    2002-01-01

    The kinetic theory analysis of surface waves propagating along a semi-bounded plasma jet is presented. The frequency spectra and their damping rate are obtained in both the high and low frequency regions. Finally, the penetration of the static field in the plasma jet under the condition that the plasma jet velocity is smaller than the sound velocity is studied

  18. Aspartate beta-decarboxylase from Alcaligenes faecalis: carbon-13 kinetic isotope effect and deuterium exchange experiments

    International Nuclear Information System (INIS)

    Rosenberg, R.M.; O'Leary, M.H.

    1985-01-01

    The authors have measured the 13 C kinetic isotope effect at pH 4.0, 5.0, 6.0, and 6.5 and in D 2 O at pH 5.0 and the rate of D-H exchange of the alpha and beta protons of aspartic acid in D 2 O at pH 5.0 for the reaction catalyzed by the enzyme aspartate beta-decarboxylase from Alcaligenes faecalis. The 13 C kinetic isotope effect, with a value of 1.0099 +/- 0.0002 at pH 5.0, is less than the intrinsic isotope effect for the decarboxylation step, indicating that the decarboxylation step is not entirely rate limiting. The authors have been able to estimate probable values of the relative free energies of the transition states of the enzymatic reaction up to and including the decarboxylation step from the 13 C kinetic isotope effect and the rate of D-H exchange of alpha-H. The pH dependence of the kinetic isotope effect reflects the pKa of the pyridine nitrogen of the coenzyme pyridoxal 5'-phosphate but not that of the imine nitrogen. A mechanism is proposed for the exchange of aspartate beta-H that is consistent with the stereochemistry suggested earlier

  19. Surfaces of Microparticles in Colloids: Structure and Molecular Adsorption Kinetics

    Science.gov (United States)

    Dai, Hai-Lung

    2002-03-01

    Surfaces of micron and sub-micron size particles in liquid solution are probed by second harmonic generation (SHG) facilitated with femtosecond laser pulses. The particles probed include inorganic objects such as carbon black and color pigments, polymeric species like polystyrene beads, and biological systems such as blood cells and ecoli. In the experiments, dye molecules are first adsorbed onto the particle surface to allow generation of second harmonics upon light irradiation. Competition for adsorption between these surface dye molecules and the molecules of interest in the solution is then monitored by the SHG signal to reveal the molecular adsorption kinetics and surface structure. Specifically, surfactant adsorption on polymer surfaces, the structure of carbon black surface, and protein adsorption on biological surfaces, monitored by this technique, will be discussed.

  20. Reconstruction of Cell Surface Densities of Ion Pumps, Exchangers, and Channels from mRNA Expression, Conductance Kinetics, Whole-Cell Calcium, and Current-Clamp Voltage Recordings, with an Application to Human Uterine Smooth Muscle Cells.

    Directory of Open Access Journals (Sweden)

    Jolene Atia

    2016-04-01

    Full Text Available Uterine smooth muscle cells remain quiescent throughout most of gestation, only generating spontaneous action potentials immediately prior to, and during, labor. This study presents a method that combines transcriptomics with biophysical recordings to characterise the conductance repertoire of these cells, the 'conductance repertoire' being the total complement of ion channels and transporters expressed by an electrically active cell. Transcriptomic analysis provides a set of potential electrogenic entities, of which the conductance repertoire is a subset. Each entity within the conductance repertoire was modeled independently and its gating parameter values were fixed using the available biophysical data. The only remaining free parameters were the surface densities for each entity. We characterise the space of combinations of surface densities (density vectors consistent with experimentally observed membrane potential and calcium waveforms. This yields insights on the functional redundancy of the system as well as its behavioral versatility. Our approach couples high-throughput transcriptomic data with physiological behaviors in health and disease, and provides a formal method to link genotype to phenotype in excitable systems. We accurately predict current densities and chart functional redundancy. For example, we find that to evoke the observed voltage waveform, the BK channel is functionally redundant whereas hERG is essential. Furthermore, our analysis suggests that activation of calcium-activated chloride conductances by intracellular calcium release is the key factor underlying spontaneous depolarisations.

  1. Transient atomic behavior and surface kinetics of GaN

    International Nuclear Information System (INIS)

    Moseley, Michael; Billingsley, Daniel; Henderson, Walter; Trybus, Elaissa; Doolittle, W. Alan

    2009-01-01

    An in-depth model for the transient behavior of metal atoms adsorbed on the surface of GaN is developed. This model is developed by qualitatively analyzing transient reflection high energy electron diffraction (RHEED) signals, which were recorded for a variety of growth conditions of GaN grown by molecular-beam epitaxy (MBE) using metal-modulated epitaxy (MME). Details such as the initial desorption of a nitrogen adlayer and the formation of the Ga monolayer, bilayer, and droplets are monitored using RHEED and related to Ga flux and shutter cycles. The suggested model increases the understanding of the surface kinetics of GaN, provides an indirect method of monitoring the kinetic evolution of these surfaces, and introduces a novel method of in situ growth rate determination.

  2. Transient atomic behavior and surface kinetics of GaN

    Science.gov (United States)

    Moseley, Michael; Billingsley, Daniel; Henderson, Walter; Trybus, Elaissa; Doolittle, W. Alan

    2009-07-01

    An in-depth model for the transient behavior of metal atoms adsorbed on the surface of GaN is developed. This model is developed by qualitatively analyzing transient reflection high energy electron diffraction (RHEED) signals, which were recorded for a variety of growth conditions of GaN grown by molecular-beam epitaxy (MBE) using metal-modulated epitaxy (MME). Details such as the initial desorption of a nitrogen adlayer and the formation of the Ga monolayer, bilayer, and droplets are monitored using RHEED and related to Ga flux and shutter cycles. The suggested model increases the understanding of the surface kinetics of GaN, provides an indirect method of monitoring the kinetic evolution of these surfaces, and introduces a novel method of in situ growth rate determination.

  3. Kinetics of the exchange of oxygen between carbon dioxide and carbonate in aqueous solution

    International Nuclear Information System (INIS)

    Tu, C.K.; Silverman, D.N.

    1975-01-01

    A kinetic analysis of the exchange of oxygen between carbon dioxide and carbonate ion in alkaline, aqueous solutions is presented. The exchange was observed by placing 18 O-labeled carbonate, not enriched in 13 C, into solution with 13 C-enriched carbonate, not enriched in 18 O. The rate of depletion of 18 O from the 12 C-containing species and the rate of appearance of 18 O in the 13 C-containing species was measured by mass spectrometry. From these data, the second-order rate constant for the reaction between carbon dioxide and carbonate which results in the exchange of oxygen at 25 0 is 114 +- 11 M -1 sec -1 . It is emphasized that this exchange of oxygen between species of CO 2 in solution must be recognized in studies using 18 O labels to determine the fate of CO 2 in biochemical and physiological processes. (auth)

  4. Kinetic computer modeling of microwave surface-wave plasma production

    International Nuclear Information System (INIS)

    Ganachev, Ivan P.

    2004-01-01

    Kinetic computer plasma modeling occupies an intermediate position between the time consuming rigorous particle dynamic simulation and the fast but rather rough cold- or warm-plasma fluid models. The present paper reviews the kinetic modeling of microwave surface-wave discharges with accent on recent kinetic self-consistent models, where the external input parameters are reduced to the necessary minimum (frequency and intensity of the applied microwave field and pressure and geometry of the discharge vessel). The presentation is limited to low pressures, so that Boltzmann equation is solved in non-local approximation and collisional electron heating is neglected. The numerical results reproduce correctly the bi-Maxwellian electron energy distribution functions observed experimentally. (author)

  5. Kinetics of zinc uptake and exchange by primary cultures of rat hepatocytes

    International Nuclear Information System (INIS)

    Pattison, S.E.; Cousins, R.J.

    1986-01-01

    The kinetics of 65 Zn 2+ uptake and exchange by hepatocytes in primary culture have been examined in detail to provide a basis for analyzing hormonal regulation of hepatic zinc metabolism. 65 Zn 2+ uptake was found to be a biphasic process. The slow phase represents an exchange between Zn 2+ in the medium and preexisting, intracellular zinc pools. This exchange rate was saturable with a medium zinc concentration of 9.5 microM eliciting one-half the maximum exchange rate and a maximum exchange rate of 9.9 pmol Zn 2+ . min-1 . mg protein-1 in the presence of bovine serum albumin. In the absence of albumin, a secondary, nonsaturable uptake rate was observed. The slow phase was relatively selective, and of the divalent transition metal ions tested, only Cd 2+ and Mn 2+ caused inhibition. The rate of exchange suggests total hepatocyte zinc has a turnover rate of approximately 30 h. The fast phase of 65 Zn 2+ reflects net Zn 2+ accumulation into a labile pool. The initial rates for this process were too fast to be measured accurately, but steady-state measurements allowed determination of the labile pool size. The pool dimensions saturated in the presence [Kapp = 28.6 microM; pool capacity = 0.44 nmol Zn 2+ /mg protein] and absence [Kapp = 11.8 microM; pool capacity = 0.34 nmol Zn 2+ /mg protein] of bovine serum albumin. Kinetics and equilibria of Zn 2+ uptake into the labile pool suggest that the latter acts as a source of Zn 2+ for the slow-exchange phase. Dexamethasone stimulated slow Zn 2+ exchange and also increased the labile pool size. The data suggest physiological factors alter hepatic zinc metabolism by influencing both intracellular Zn 2+ pools

  6. Back-exchange: a novel approach to quantifying oxygen diffusion and surface exchange in ambient atmospheres.

    Science.gov (United States)

    Cooper, Samuel J; Niania, Mathew; Hoffmann, Franca; Kilner, John A

    2017-05-17

    A novel two-step Isotopic Exchange (IE) technique has been developed to investigate the influence of oxygen containing components of ambient air (such as H 2 O and CO 2 ) on the effective surface exchange coefficient (k*) of a common mixed ionic electronic conductor material. The two step 'back-exchange' technique was used to introduce a tracer diffusion profile, which was subsequently measured using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The isotopic fraction of oxygen in a dense sample as a function of distance from the surface, before and after the second exchange step, could then be used to determine the surface exchange coefficient in each atmosphere. A new analytical solution was found to the diffusion equation in a semi-infinite domain with a variable surface exchange boundary, for the special case where D* and k* are constant for all exchange steps. This solution validated the results of a numerical, Crank-Nicolson type finite-difference simulation, which was used to extract the parameters from the experimental data. When modelling electrodes, D* and k* are important input parameters, which significantly impact performance. In this study La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF6428) was investigated and it was found that the rate of exchange was increased by around 250% in ambient air compared to high purity oxygen at the same pO 2 . The three experiments performed in this study were used to validate the back-exchange approach and show its utility.

  7. Kinetics of H-D exchange in olefins with complicating reactions

    International Nuclear Information System (INIS)

    Trokhimets, A.I.

    1979-01-01

    The kinetics of H-D-exchange is considered for olefins under conditions when simple and complicated exchange occur together with hydrogenation. If hydrogenation takes place in the system, it is theoretically impossible to derive the integrated rate equation for the accumulation of deuterium in the olefin. The variation of the concentration of different deuteroolefins during the process can be calculated numerically. A method is proposed for evaluating the contribution of individual steps to the overall process and determining the rate constants of the most important reactions. (author)

  8. Ion-exchange behaviour of hydrous zirconia in mixed solvents: capacity and kinetics of exchange

    International Nuclear Information System (INIS)

    Misak, N.Z.; Ghoneimy, H.F.

    1982-01-01

    The capacity of the Li + form of hydrous zirconia for Na + and Cs + increases in the presence of methanol. This may be due to the greater stability of Li + in methanol/water than in pure water and to dehydration of Na + and Cs + and their stronger interaction with the exchange sites, which may facilitate their replacing Li + . The ion-exchange capacity of zirconia for NO 3 - , Cl - and Br - is almost the same in aqueous solution and is not affected by addition of up to 90% (v/v) methanol, which probably shows that these anions are electrostatically bound in zirconia without specific interactions. The internal diffusion coefficients of the Na + /H + and Cl - /OH - systems decrease in the presence of alcohol: the decrease is highest with methanol and similar for ethanol and propan-2-ol. This is discussed in the light of ion solvation and alcohol penetration inside zirconia. (author)

  9. Removal of Congo Red from Aqueous Solution by Anion Exchange Membrane (EBTAC): Adsorption Kinetics and Themodynamics

    Science.gov (United States)

    Khan, Muhammad Imran; Akhtar, Shahbaz; Zafar, Shagufta; Shaheen, Aqeela; Khan, Muhammad Ali; Luque, Rafael; ur Rehman, Aziz

    2015-01-01

    The adsorption behavior of anionic dye congo red (CR) from aqueous solutions using an anion exchange membrane (EBTAC) has been investigated at room temperature. The effect of several factors including contact time, membrane dosage, ionic strength and temperature were studied. Kinetic models, namely pseudo-first-order and pseudo-second-order, liquid film diffusion and Elovich models as well as Bangham and modified freundlich Equations, were employed to evaluate the experimental results. Parameters such as adsorption capacities, rate constant and related correlation coefficients for every model were calculated and discussed. The adsorption of CR on anion exchange membranes followed pseudo-second-order Kinetics. Thermodynamic parameters, namely changes in Gibbs free energy (∆G°), enthalpy (∆H°) and entropy (∆S°) were calculated for the adsorption of congo red, indicating an exothermic process. PMID:28793430

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

    Science.gov (United States)

    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.

  11. Novel exchange mechanisms in the surface diffusion of oxides

    International Nuclear Information System (INIS)

    Harris, Duncan J; Lavrentiev, Mikhail Yu; Harding, John H; Allan, Neil L; Purton, John A

    2004-01-01

    We use temperature-accelerated dynamics to show the importance of exchange mechanisms in surface diffusion and growth of simple oxides. Such mechanisms can dominate transport processes both on terraces and steps for both homoepitaxial and heteroepitaxial growth. We suggest that the mixing inevitable when an exchange mechanism is present must be considered when attempts are made to grow sharp interfaces in oxide nanostructures. (letter to the editor)

  12. Inhibition of ligand exchange kinetics via active-site trapping with an antibody fragment.

    Science.gov (United States)

    Oyen, David; Steyaert, Jan; Barlow, John N

    2014-04-01

    We describe the first example of an inhibitory antibody fragment (nanobody ca1697) that binds simultaneously to an enzyme (the enzyme dihydrofolate reductase from Escherichia coli) and its bound substrate (folate). Binding of the antibody to the substrate causes a 20-fold reduction in the rate of folate exchange kinetics. This work opens up the prospect of designing new types of antibody-based inhibitors of enzymes and receptors through suitable design of immunogens.

  13. Kinetics of radiation-induced precipitation at the alloy surface

    Science.gov (United States)

    Lam, N. Q.; Nguyen, T.; Leaf, G. K.; Yip, S.

    1988-05-01

    Radiation-induced precipitation of a new phase at the surface of an alloy during irradiation at elevated temperatures was studied with the aid of a kinetic model of segregation. The preferential coupling of solute atoms with the defect fluxes gives rise to a strong solute enrichment at the surface, which, if surpassing the solute solubility limit, leads to the formation of a precipitate layer. The moving precipitate/matrix interface was accommodated by means of a mathematical scheme that transforms spatial coordinates into a reference frame in which the boundaries are immobile. Sample calculations were performed for precipitation of the γ'-Ni 3Si layer on Ni-Si alloys undergoing electron irradiation. The dependences of the precipitation kinetics on the defect-production rate, irradiation temperature, internal defect sink concentration and alloy composition were investigated systematically.

  14. Kinetics of hydroxyethylethylenediaminetriacetate exchange of neodymium (3) with ytterbium (3) and gadolinium (3) aquaions

    International Nuclear Information System (INIS)

    Nikitenko, S.I.; Martynenko, L.I.; Petsurova, N.I.

    1985-01-01

    The exchange kinetic in the NdX-Ln 3+ , where X 3- is hydroxyethylethylenediamine triacetate, Ln 3+ -Yb 3+ , Cd 3+ is studied spectrophotometrically. It has been found that the stationary exchange reate is described by the kinetic equation: W=Ksub(1)csub.(NdX)sup(0)csub(H)+Ksub(2)csub(NdX)sup(0)csub(Ln)sup(0)(1). The exchange rate constant values are calulated at t=20 deg C and μ=0.1: K 1 =(4.5+-0.2)x10 3 (Yb 3+ ), (4.8+-0.3)x10 3 .(Gd 3+ ), K 2 =1.7+-0.2(Yb 3+ ), 0.9+-0.1(Gd 3+ ) l/molxmin. It is shown that the acidic dissociation mechanism corresponds to augend (1), the exchange associative mechanism - to addend. It is shown by the method of segments that Ln 3+ in intermediate complexes (NdXLn) 3+ is coordinated by X 3- hydroxyethylglicine group

  15. Determination of phosphorus in urban sewage sludge using the isotopic exchange kinetics method

    International Nuclear Information System (INIS)

    Rojas de Tramontini, Susana; Barbaro, Nestor O.; Lopez, Silvia C.

    1999-01-01

    The aim of this work was to assess the differences among soil available P, the use by the plants of sludge P, and of a water soluble fertilizer (Ca(H 2 PO 4 ) 2 ) P, using isotopic exchange kinetics methods. The sludge was provided by the Sewage Sludge Treatment Plant of Tucuman City, Argentina. The isotopic exchange kinetics experiment, in which the fate of carrier free 32 PO 4 added to the soil solution at a steady state was studied, gives information on soil P exchangeability. The experiment was carried out in the laboratory, where sewage sludge and water soluble fertilizer were added to soil samples taken at a depth of 0-25 and 25-40 cm. Changes in the soil P isotopically exchangeable within 1 minute measurements in the soil with sludge and in the soil with water soluble fertilizer showed that the 0-25 cm deep soil samples had a low P sorption capacity (r1 /R values were low). The sludge had high total and organic P, but the P in the soil solution was lower than the P provided by the water soluble fertilizer. Therefore, despite its higher total P content, this sludge contained slow available forms of P

  16. Kinetic models for goods exchange in a multi-agent market

    Science.gov (United States)

    Brugna, Carlo; Toscani, Giuseppe

    2018-06-01

    In this paper we introduce a system of kinetic equations describing an exchange market consisting of two populations of agents (dealers and speculators) expressing the same preferences for two goods, but applying different strategies in their exchanges. Similarly to the model proposed in Toscani et al. (2013), we describe the trading of the goods by means of some fundamental rules in price theory, in particular by using Cobb-Douglas utility functions for the exchange. The strategy of the speculators is to recover maximal utility from the trade by suitably acting on the percentage of goods which are exchanged. This microscopic description leads to a system of linear Boltzmann-type equations for the probability distributions of the goods on the two populations, in which the post-interaction variables depend from the pre-interaction ones in terms of the mean quantities of the goods present in the market. In this case, it is shown analytically that the strategy of the speculators can drive the price of the two goods towards a zone in which there is a branded utility for their group. Also, according to Toscani et al. (2013), the general system of nonlinear kinetic equations of Boltzmann type for the probability distributions of the goods on the two populations is described in details. Numerical experiments then show how the policy of speculators can modify the final price of goods in this nonlinear setting.

  17. Chemical bond as a test of density-gradient expansions for kinetic and exchange energies

    International Nuclear Information System (INIS)

    Perdew, J.P.; Levy, M.; Painter, G.S.; Wei, S.; Lagowski, J.B.

    1988-01-01

    Errors in kinetic and exchange contributions to the molecular bonding energy are assessed for approximate density functionals by reference to near-exact Hartree-Fock values. From the molecular calculations of Allan et al. and of Lee and Ghosh, it is demonstrated that the density-gradient expansion does not accurately describe the noninteracting kinetic contribution to the bonding energy, even when this expansion is carried to fourth order and applied in its spin-density-functional form to accurate Hartree-Fock densities. In a related study, it is demonstrated that the overbinding of molecules such as N 2 and F 2 , which occurs in the local-spin-density (LSD) approximation for the exchange-correlation energy, is not attributable to errors in the self-consistent LSD densities. Contrary to expectations based upon the Gunnarsson-Jones nodality argument, it is found that the LSD approximation for the exchange energy can seriously overbind a molecule even when bonding does not create additional nodes in the occupied valence orbitals. LSD and exact values for the exchange contribution to the bonding energy are displayed and discussed for several molecules

  18. Exchange energy of inhomogenous electron gas near a metal surface

    International Nuclear Information System (INIS)

    Miglio, L.; Tosi, M.P.; March, N.H.

    1980-12-01

    Using the first-order density matrix of an infinite-barrier model of a metal surface, the exchange energy density can be evaluated exactly as a function of distance z from the barrier. This result is compared with the local approximation -3/4e 2 (3/π)sup(1/3) rhosup(4/3)(z) where rho is the electron density in the model. The local approximation is demonstrated to be quantitatively accurate at all z. The integrated surface exchange energy is given to within 3% by the local theory. (author)

  19. Proton NMR investigation of heme pocket mobility in hemoglobin via hydrogen isotope exchange kinetics

    International Nuclear Information System (INIS)

    Han, K.

    1985-01-01

    Dynamic mobility of heme cavity, the active site of Hb, was investigated by analyzing the hydrogen isotope exchange kinetics of the proximal histidyl ring NH of various kinds of Hbs with the aid of the high field Fourier Transform 1 H NMR spectroscopy. The exchange reaction occurs faster in oxy or R-state Hb than in deoxy or T-state Hb and there exists a good correlation between the oxygen affinity of Hb and the heme pocket mobility reflected in the hydrogen exchange rate. The effect of pH on the exchange is dramatically different for the two subunits of Hb A. Studying the exchange characteristics of mutant Hbs and chemically modified Hbs not only showed the existence of three well-defined localized paths for transmission of conformational changes between different heme pockets through a 1 b 2 subunit interface, but also indicated that the heme pocket mobility is regulated by the quaternary state of Hb as well as by the ligation state of Hb. Finally, the effect of the quaternary state on the heme pocket mobility is separated from that of the ligation by following the exchange reactions in Hbs where only their quaternary structure transition can be achieved without changing their ligation states by adjusting experimental conditions such as adding inositol hexaphosphate

  20. Evaporation kinetics of sessile water droplets on micropillared superhydrophobic surfaces.

    Science.gov (United States)

    Xu, Wei; Leeladhar, Rajesh; Kang, Yong Tae; Choi, Chang-Hwan

    2013-05-21

    Evaporation modes and kinetics of sessile droplets of water on micropillared superhydrophobic surfaces are experimentally investigated. The results show that a constant contact radius (CCR) mode and a constant contact angle (CCA) mode are two dominating evaporation modes during droplet evaporation on the superhydrophobic surfaces. With the decrease in the solid fraction of the superhydrophobic surfaces, the duration of a CCR mode is reduced and that of a CCA mode is increased. Compared to Rowan's kinetic model, which is based on the vapor diffusion across the droplet boundary, the change in a contact angle in a CCR (pinned) mode shows a remarkable deviation, decreasing at a slower rate on the superhydrophobic surfaces with less-solid fractions. In a CCA (receding) mode, the change in a contact radius agrees well with the theoretical expectation, and the receding speed is slower on the superhydrophobic surfaces with lower solid fractions. The discrepancy between experimental results and Rowan's model is attributed to the initial large contact angle of a droplet on superhydrophobic surfaces. The droplet geometry with a large contact angle results in a narrow wedge region of air along the contact boundary, where the liquid-vapor diffusion is significantly restricted. Such an effect becomes minor as the evaporation proceeds with the decrease in a contact angle. In both the CCR and CCA modes, the evaporative mass transfer shows the linear relationship between mass(2/3) and evaporation time. However, the evaporation rate is slower on the superhydrophobic surfaces, which is more significant on the surfaces with lower solid fractions. As a result, the superhydrophobic surfaces slow down the drying process of a sessile droplet on them.

  1. Exchange of deuterium with hydrogen of zeolite catalyst surface

    International Nuclear Information System (INIS)

    Minachev, Kh.M.; Dmitriev, R.V.; Penchev, V.; Kanazirev, V.; Minchev, Kh.; Kasimov, Ch.K.; Bylgarska Akademiya na Naukite, Sofia. Inst. za Obshta i Organichna Khimiya; AN Azerbajdzhanskoj SSR, Baku. Inst. Neftekhimicheskikh Protsessov)

    1981-01-01

    Isotope heteromolecular exchange of hydrogen on the reduced nickel-containing zeolites takes places at the temperatures above 100 deg and it is controlled by activated hydrogen transfer from metal particles on the substrate surface. High-temperature redox treatment of nickel-containing zeolites results in the formation of large nickel crystallites on zeolite external faces. The rest part of nickel remains in zeolite pores and conditions a high promoting effect in the exchange reaction. Catalytic activity of reduced zeolites NiCaNaY in toluene disproportionation increases considerably only in the cases when nickel is introduced into zeolite by means of ion exchange. Close spatial location of nickel particles and OH groups promotes the procedure of both isotope exchange and disproportionation of toluene [ru

  2. Kinetic and mechanism studies of the adsorption of lead onto waste cow bone powder (WCBP) surfaces.

    Science.gov (United States)

    Cha, Jihoon; Cui, Mingcan; Jang, Min; Cho, Sang-Hyun; Moon, Deok Hyun; Khim, Jeehyeong

    2011-01-01

    This study examines the adsorption isotherms, kinetics and mechanisms of Pb²(+) sorption onto waste cow bone powder (WCBP) surfaces. The concentrations of Pb²(+) in the study range from 10 to 90 mg/L. Although the sorption data follow the Langmuir and Freundlich isotherm, a detailed examination reveals that surface sorption or complexation and co-precipitation are the most important mechanisms, along with possibly ion exchange and solid diffusion also contributing to the overall sorption process. The co-precipitation of Pb²(+) with the calcium hydroxyapatite (Ca-HAP) is implied by significant changes in Ca²(+) and PO₄³⁻ concentrations during the metal sorption processes. The Pb²(+) sorption onto the WCBP surface by metal complexation with surface functional groups such as ≡ POH. The major metal surface species are likely to be ≡ POPb(+). The sorption isotherm results indicated that Pb²(+) sorption onto the Langmuir and Freundlich constant q(max) and K( F ) is 9.52 and 8.18 mg g⁻¹, respectively. Sorption kinetics results indicated that Pb²(+) sorption onto WCBP was pseudo-second-order rate constants K₂ was 1.12 g mg⁻¹ h⁻¹. The main mechanism is adsorption or surface complexation (≡POPb(+): 61.6%), co-precipitation or ion exchange [Ca₃(.)₉₃ Pb₁(.)₀₇ (PO₄)₃ (OH): 21.4%] and other precipitation [Pb 50 mg L⁻¹ and natural pH: 17%). Sorption isotherms showed that WCBP has a much higher Pb²(+) removal rate in an aqueous solution; the greater capability of WCBP to remove aqueous Pb²(+) indicates its potential as another promising way to remediate Pb²(+)-contaminated media.

  3. Kinetics and exchange mechanism of Zn2+and Eu3+ ions on tin and zirconium silicates as a cation exchange materials

    International Nuclear Information System (INIS)

    Zakaria, E.S.; Ali, I.M.; Aly, H.F.

    2005-01-01

    Tin and zirconium silicates have been prepared with Sn/Si and Zr/Si molar ratios of 1 and 0.75, respectively. Kinetics and exchange studies of Zn 2+ and Eu 3+ ions on the prepared stannous and zirconium silicates have been carried out as a function of reaction temperature, particle diameters, solution concentration of the exchanging cations from water and alcohol-water mixture. The capacity of the exchangers for the studied cations from alcohol-water mixture was found higher than in pure aqueous solutions. The rate of exchange was dependent on particle diameters and independent on concentration of metal ions. The kinetic and thermodynamic parameters, vis. effective diffusion coefficients, activation energies and entropies of activation have been evaluated. Negative values of entropy, enthalpy and free energy of activation for Zn 2+ /M + and Eu 3+ /H + on both exchangers have been recorded at different conditions

  4. Kinetics of isotopic exchange of [1-3H]saccharides with hydrogen using palladium catalysts

    International Nuclear Information System (INIS)

    Akulov, G.P.; Kayumov, V.G.; Snetkova, E.V.; Kaminskij, Yu.L.

    1988-01-01

    The kinetics was studied of the isotopic exchange of [1- 3 H]saccharides with hydrogen on palladium catalysts. The effect was studied of different factors on the rate of isotopic exchange, e.g., of the composition and structure of saccharides, their concentration in the solution (C), the type of catalyst and of the buffer solution. It was found that by reduced rate of isotopic exchange with hydrogen, all studied saccharides may be arranged into a series independent of the type of catalyst in accordance with the sequence of declining coefficient of relative mobility of l-H atoms during the reaction. Linear dependence was found to exist between the rate constant of the isotopic exchange reaction (r) and the coefficient of relative lability. It was also found that in the range of low concentrations the observed rate constants of isotopic exchange were not dependent on concentration and in the range of higher concentrations, r decreased with increasing C. This character of dependence is justified by the side effect of the processes of sorption on the catalyst. (author). 3 figs., 1 tab., 4 refs

  5. Isotopic exchange reactions. Kinetics and efficiency of the reactors using them in isotopic separation

    International Nuclear Information System (INIS)

    Ravoire, Jean

    1979-11-01

    In the first part, some definitions and the thermodynamic and kinetic isotopic effect concepts are recalled. In the second part the kinetic laws are established, in homogeneous and heterogeneous medium (one component being on occasions present in both phases), without and with isotopic effects. Emphasis is put on application to separation of isotopes, the separation factor α being close to 1, one isotope being in large excess with respect to the other one. Isotopic transfer is then given by: J = Ka (x - y/α) where x and y are the (isotopic) mole fractions in both phases, Ka may be either the rate of exchange or a transfer coefficient which can be considered as the 'same in both ways' if α-1 is small compared to the relative error on the measure of Ka. The third part is devoted to isotopic exchange reactors. Relationships between their efficiency and kinetics are established in some simple cases: plug cocurrent flow reactors, perfectly mixed reactors, countercurrent reactors without axial mixing. We treat only cases where α and the up flow to down flow ratio is close to 1 so that Murphee efficiency approximately overall efficiency (discrete stage contactors). HTU (phase 1) approximately HTU (phase 2) approximately HETP (columns). In a fourth part, an expression of the isotopic separative power of reactors is proposed and discussed [fr

  6. Neutron scattering from myelin revisited: bilayer asymmetry and water-exchange kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Denninger, Andrew R. [Boston College, Chestnut Hill, MA 02467 (United States); Demé, Bruno; Cristiglio, Viviana [Institut Laue–Langevin (ILL), CS 20156, F-38042 Grenoble CEDEX 9 (France); LeDuc, Géraldine [European Synchrotron Radiation Facility (ESRF), CS 40220, F-38043 Grenoble CEDEX 9 (France); Feller, W. Bruce [NOVA Scientific Inc., Sturbridge, MA 01566 (United States); Kirschner, Daniel A., E-mail: kirschnd@bc.edu [Boston College, Chestnut Hill, MA 02467 (United States)

    2014-12-01

    The structure of internodal myelin in the rodent central and peripheral nervous systems has been determined using neutron diffraction. The kinetics of water exchange in these tissues is also described. Rapid nerve conduction in the central and peripheral nervous systems (CNS and PNS, respectively) of higher vertebrates is brought about by the ensheathment of axons with myelin, a lipid-rich, multilamellar assembly of membranes. The ability of myelin to electrically insulate depends on the regular stacking of these plasma membranes and on the presence of a number of specialized membrane-protein assemblies in the sheath, including the radial component, Schmidt–Lanterman incisures and the axo–glial junctions of the paranodal loops. The disruption of this fine-structure is the basis for many demyelinating neuropathies in the CNS and PNS. Understanding the processes that govern myelin biogenesis, maintenance and destabilization requires knowledge of myelin structure; however, the tight packing of internodal myelin and the complexity of its junctional specializations make myelin a challenging target for comprehensive structural analysis. This paper describes an examination of myelin from the CNS and PNS using neutron diffraction. This investigation revealed the dimensions of the bilayers and aqueous spaces of myelin, asymmetry between the cytoplasmic and extracellular leaflets of the membrane, and the distribution of water and exchangeable hydrogen in internodal multilamellar myelin. It also uncovered differences between CNS and PNS myelin in their water-exchange kinetics.

  7. Kinetic study of heavy metal ions removal by ion exchange in batch conical air spouted bed

    Directory of Open Access Journals (Sweden)

    T.M. Zewail

    2015-03-01

    Full Text Available Spouted bed contactor is a hybrid of fixed and fluidized bed contactors, which retains the advantages of each with good hydrodynamic conditions. The aim of the present study is to investigate the performance of a batch conical air spouted vessel for heavy metal removal by strong cation exchange resins (AMBERJET 1200 Na. The effect of various parameters such as type of heavy metal ions (Ni+2 and Pb+2, contact time, superficial air velocity and initial heavy metal ion concentration on % heavy metal ion removal has been investigated. It has been found that under optimum conditions 98% and 99% removal of Ni+2 and Pb+2 were achieved respectively. Several kinetic models were used to test the experimental data and to examine the controlling mechanism of the sorption process. The present results of Ni+2 and Pb+2 well fit pseudo second order kinetic model with a high correlation coefficient. Both film diffusion and intra-particle diffusion contribute to the ion exchange process. The present study revealed that spouted bed vessel may provide an effective alternative for conducting ion exchange reactions.

  8. Kinetics of ion exchange in the chelating resin Dowex A-1

    International Nuclear Information System (INIS)

    Matsuzuru, Hideo; Wadachi, Yoshiki

    1975-01-01

    The kinetics of ion exchanges of Ag + , Zn 2+ and Cr 3+ at extremely low concentrations on the chelating resin Dowex A-1 has been studied by means of finite volume method. The rate of exchanges for both Ag + and Zn 2+ is dependent on the ionic strength, particle size of the resin and reaction temperature. At higher ionic strength (0.1 - 0.05) the kinetics is controlled by particle diffusion, whereas at lower ionic one (0.01 - 0.001) film diffusion is predominant. The apparent activation energy obtained is 3.84 kcal/mol for Ag + and 3.91 kcal/mol for Zn 2+ . The exchange rate of Cr 3+ obeys a first-order rate equation independent of the ionic strength and particle size of the resin. The apparent activation energy is 15.5 kcal/mol. These results support the view that the rate-determining step of this reaction is chelate formation reaction. (auth.)

  9. Real-time hydrogen/deuterium exchange kinetics via supercharged electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Sterling, Harry J; Williams, Evan R

    2010-11-01

    Amide hydrogen/deuterium exchange (HDX) rate constants of bovine ubiquitin in an ammonium acetate solution containing 1% of the electrospray ionization (ESI) "supercharging" reagent m-nitrobenzyl alcohol (m-NBA) were obtained using top-down, electron transfer dissociation (ETD) tandem mass spectrometry (MS). The supercharging reagent replaces the acid and temperature "quench" step in the conventional MS approach to HDX experiments by causing rapid protein denaturation to occur in the ESI droplet. The higher charge state ions that are produced with m-NBA are more unfolded, as measured by ion mobility, and result in higher fragmentation efficiency and higher sequence coverage with ETD. Single amino acid resolution was obtained for 44 of 72 exchangeable amide sites, and summed kinetic data were obtained for regions of the protein where adjacent fragment ions were not observed, resulting in an overall spatial resolution of 1.3 residues. Comparison of these results with previous values from NMR indicates that the supercharging reagent does not cause significant structural changes to the protein in the initial ESI solution and that scrambling or back-exchange is minimal. This new method for top-down HDX-MS enables real-time kinetic data measurements under physiological conditions, similar to those obtained using NMR, with comparable spatial resolution and significantly better sensitivity.

  10. Kinetics of the exchange between fibrous manganese dioxide and Mn2+ ions in solution

    International Nuclear Information System (INIS)

    Rophael, M.W.

    1983-01-01

    The rate of exchange between fibrous manganese dioxide epsilon-MnO 2 and a 0.1 M MnSO 4 solution at 25 0 C and pH 2.0 was higher than the corresponding rate at pH 5.4. When the solid was washed with dilute acid (pH 2.0) before the exchange at pH 2.0, the results of the exchange at the two pH values were similar. When epsilon-MnO 2 was partially reduced with N 2 H 4 .H 2 O solution before the exchange, the rate of exchange was appreciably higher than that obtained for the unreduced solid. The exchange, at nearly pH 2.0, between epsilon-MnO 2 and various concentrations of Mn(NO 3 ) 2 solutions was increased to a small extent as the concentration increased tenfold. The exchange was followed by using 56 Mn-labelled MnO 2 and by measuring the β activity acquired by the Mn 2+ ion solution. The activity induced in the solid MnO 2 was produced by irradiation with thermal neutrons from a 241 Am- 9 Be laboratory neutron source. The neutron activation of manganese oxides has the following advantages: (i) a relatively high level of activity can be induced in the 55 Mn of the irradiated oxide because of its 100% abundance and its high neutron activation cross section, whereas the oxygen is unaffected; (ii) the half-life of the product 56 Mn is 9274 s which is convenient for kinetic studies; (iii) the activity produced almost decays in 24 h. (Auth.)

  11. Gas phase 1H NMR studies and kinetic modeling of dihydrogen isotope equilibration catalyzed by Ru-nanoparticles under normal conditions: dissociative vs. associative exchange.

    Science.gov (United States)

    Limbach, Hans-Heinrich; Pery, Tal; Rothermel, Niels; Chaudret, Bruno; Gutmann, Torsten; Buntkowsky, Gerd

    2018-04-25

    The equilibration of H2, HD and D2 between the gas phase and surface hydrides of solid organic-ligand-stabilized Ru metal nanoparticles has been studied by gas phase 1H NMR spectroscopy using closed NMR tubes as batch reactors at room temperature and 800 mbar. When two different nanoparticle systems, Ru/PVP (PVP ≡ polyvinylpyrrolidone) and Ru/HDA (HDA ≡ hexadecylamine) were exposed to D2 gas, only the release of HD from the hydride containing surface could be detected in the initial stages of the reaction, but no H2. In the case of Ru/HDA also the reverse experiment was performed where surface deuterated nanoparticles were exposed to H2. In that case, the conversion of H2 into gaseous HD was detected. In order to analyze the experimental kinetic and spectroscopic data, we explored two different mechanisms taking into account potential kinetic and equilibrium H/D isotope effects. Firstly, we explored the dissociative exchange mechanism consisting of dissociative adsorption of dihydrogen, fast hydride surface diffusion and associative desorption of dihydrogen. It is shown that if D2 is the reaction partner, only H2 will be released in the beginning of the reaction, and HD only in later reaction stages. The second mechanism, dubbed here associative exchange consists of the binding of dihydrogen to Ru surface atoms, followed by a H-transfer to or by H-exchange with an adjacent hydride site, and finally of the associative desorption of dihydrogen. In that case, in the exchange with D2, only HD will be released in the beginning of the reaction. Our experimental results are not compatible with the dissociative exchange but can be explained in terms of the associative exchange. Whereas the former will dominate at low temperatures and pressures, the latter will prevail around room temperature and normal pressures where transition metal nanoparticles are generally used as reaction catalysts.

  12. Study of hydrogen mobility by hydrogen-deuterium exchange. II. Theoretical kinetic study in alkyl and amino-alkyl pyrimidines

    International Nuclear Information System (INIS)

    Pompon, Alain

    1975-01-01

    Alkyl groups bound to the pyrimidine ring can be deuterium substituted on the carbon adjacent to the ring, in acidic D 2 O; kinetic equations corresponding to various exchange mechanism hypothesis are established. It is shown that theoretical and experimental results can be compared in order to precise the mechanism and to measure the characteristic parameters of the exchange reaction [fr

  13. Lateral interactions and non-equilibrium in surface kinetics

    Science.gov (United States)

    Menzel, Dietrich

    2016-08-01

    Work modelling reactions between surface species frequently use Langmuir kinetics, assuming that the layer is in internal equilibrium, and that the chemical potential of adsorbates corresponds to that of an ideal gas. Coverage dependences of reacting species and of site blocking are usually treated with simple power law coverage dependences (linear in the simplest case), neglecting that lateral interactions are strong in adsorbate and co-adsorbate layers which may influence kinetics considerably. My research group has in the past investigated many co-adsorbate systems and simple reactions in them. We have collected a number of examples where strong deviations from simple coverage dependences exist, in blocking, promoting, and selecting reactions. Interactions can range from those between next neighbors to larger distances, and can be quite complex. In addition, internal equilibrium in the layer as well as equilibrium distributions over product degrees of freedom can be violated. The latter effect leads to non-equipartition of energy over molecular degrees of freedom (for products) or non-equal response to those of reactants. While such behavior can usually be described by dynamic or kinetic models, the deeper reasons require detailed theoretical analysis. Here, a selection of such cases is reviewed to exemplify these points.

  14. Kinetics of boron ions sorption from solution by inorganic anion exchanger of MNH type

    International Nuclear Information System (INIS)

    Leont'eva, G.V.

    1990-01-01

    By the method of restricted volume in case of boron excess in solution kinetics of boron sorption by inorganic anion-exchanger of the composition (Mg 0.55 Ni 0.45 )(OH) 2 has been studied. The sorption was carried out from solution containing Na + , K + , Ca 2+ , Mg 2+ , Cl - , SO 4 2- , CO 3 2- , HCO 3 at 283, 293, 303 and 313 K and pH 8.1, while the density of solution was 1225 kg/m 3 . The sorption mechanism was considered. It is shown that heterogeneity of the character of kinetic curves is caused by the change in the mechanism of limiting stages of the sorption

  15. Wave-particle energy exchange directly observed in a kinetic Alfvén-branch wave.

    Science.gov (United States)

    Gershman, Daniel J; F-Viñas, Adolfo; Dorelli, John C; Boardsen, Scott A; Avanov, Levon A; Bellan, Paul M; Schwartz, Steven J; Lavraud, Benoit; Coffey, Victoria N; Chandler, Michael O; Saito, Yoshifumi; Paterson, William R; Fuselier, Stephen A; Ergun, Robert E; Strangeway, Robert J; Russell, Christopher T; Giles, Barbara L; Pollock, Craig J; Torbert, Roy B; Burch, James L

    2017-03-31

    Alfvén waves are fundamental plasma wave modes that permeate the universe. At small kinetic scales, they provide a critical mechanism for the transfer of energy between electromagnetic fields and charged particles. These waves are important not only in planetary magnetospheres, heliospheres and astrophysical systems but also in laboratory plasma experiments and fusion reactors. Through measurement of charged particles and electromagnetic fields with NASA's Magnetospheric Multiscale (MMS) mission, we utilize Earth's magnetosphere as a plasma physics laboratory. Here we confirm the conservative energy exchange between the electromagnetic field fluctuations and the charged particles that comprise an undamped kinetic Alfvén wave. Electrons confined between adjacent wave peaks may have contributed to saturation of damping effects via nonlinear particle trapping. The investigation of these detailed wave dynamics has been unexplored territory in experimental plasma physics and is only recently enabled by high-resolution MMS observations.

  16. Wave-Particle Energy Exchange Directly Observed in a Kinetic Alfven-Branch Wave

    Science.gov (United States)

    Gershman, Daniel J.; F-Vinas, Adolfo; Dorelli, John C.; Boardsen, Scott A. (Inventor); Avanov, Levon A.; Bellan, Paul M.; Schwartz, Steven J.; Lavraud, Benoit; Coffey, Victoria N.; Chandler, Michael O.; hide

    2017-01-01

    Alfven waves are fundamental plasma wave modes that permeate the universe. At small kinetic scales they provide a critical mechanism for the transfer of energy between electromagnetic fields and charged particles. These waves are important not only in planetary magnetospheres, heliospheres, and astrophysical systems, but also in laboratory plasma experiments and fusion reactors. Through measurement of charged particles and electromagnetic fields with NASAs Magnetospheric Multiscale (MMS) mission, we utilize Earths magnetosphere as a plasma physics laboratory. Here we confirm the conservative energy exchange between the electromagnetic field fluctuations and the charged particles that comprise an undamped kinetic Alfven wave. Electrons confined between adjacent wave peaks may have contributed to saturation of damping effects via non-linear particle trapping. The investigation of these detailed wave dynamics has been unexplored territory in experimental plasma physics and is only recently enabled by high-resolution MMS observations.

  17. Kinetics of conformational changes of fibronectin adsorbed onto model surfaces.

    Science.gov (United States)

    Baujard-Lamotte, L; Noinville, S; Goubard, F; Marque, P; Pauthe, E

    2008-05-01

    Fibronectin (FN), a large glycoprotein found in body fluids and in the extracellular matrix, plays a key role in numerous cellular behaviours. We investigate FN adsorption onto hydrophilic bare silica and hydrophobic polystyrene (PS) surfaces using Fourier transform infrared spectroscopy-attenuated total reflection (FTIR-ATR) in aqueous medium. Adsorption kinetics using different bulk concentrations of FN were followed for 2h and the surface density of adsorbed FN and its time-dependent conformational changes were determined. When adsorption occurs onto the hydrophilic surface, FN molecules keep their native conformation independent of the adsorption conditions, but the amount of adsorbed FN increases with time and the bulk concentration. Although the protein surface density is the same on the hydrophobic PS surface, this has a strong impact on the average conformation of the adsorbed FN layer. Indeed, interfacial hydration changes induced by adsorption onto the hydrophobic surface lead to a decrease in unhydrated beta-sheet content and cause an increase in hydrated beta-strand and hydrated random domain content of adsorbed FN. This conformational change is mainly dependent on the bulk concentration. Indeed, at low bulk concentrations, the secondary structures of adsorbed FN molecules undergo strong unfolding, allowing an extended and hydrated conformation of the protein. At high bulk concentrations, the molecular packing reduces the unfolding of the stereoregular structures of the FN molecules, preventing stronger spreading of the protein.

  18. Solution Exchange Lithography: A Versatile Tool for Sequential Surface Engineering

    Science.gov (United States)

    Pester, Christian; Mattson, Kaila; Bothman, David; Klinger, Daniel; Lee, Kenneth; Discekici, Emre; Narupai, Benjaporn; Hawker, Craig

    The covalent attachment of polymers has emerged as a viable strategy for the preparation of multi-functional surfaces. Patterned, surface-grafted polymer brushes provide spatial control over wetting, mechanical, biological or electronic properties, and allow fabrication of `intelligent' substrates which selectively adapt to their environment. However, the route towards patterned polymer brush surfaces often remains challenging, creating a demand for more efficient and less complicated fabrication strategies. We describe the design and application of a novel experimental setup to combine light-mediated and flow chemistry for the fabrication of hierarchical surface-grafted polymer brushes. Using light-mediated, surface initiated controlled radical polymerization and post-functionalization via well-established, and highly efficient chemistries, polymer brush films of previously unimaginable complexity are now shown to be accessible. This methodology allows full flexibility to exchange both lithographic photomasks and chemical environments in-situ, readily affording multidimensional thin film architectures, all from uniformly functionalized substrates.

  19. Isotopic exchange between CO2 and H2O and labelling kinetics of photosynthetic oxygen

    International Nuclear Information System (INIS)

    Gerster, Richard

    1971-01-01

    The reaction of carbon dioxide with water has been studied by measuring the rate of oxygen exchange between C 18 O 2 and H 2 16 O. The mathematical treatment of the kinetics allows to determine with accuracy the diffusion flow between the gas and the liquid phase, in the same way as the CO 2 hydration rate. The velocity constant of this last process, whose value gives the in situ enzymatic activity of carbonic anhydrase, has been established in the case of chloroplast and Euglena suspensions and of aerial leaves. The study of the isotopic exchange between C 18 O 2 and a vegetable submitted to alternations of dark and light has allowed to calculate the isotopic abundance of the metabolized CO 2 whose value has been compared to that of the intracellular water and that of photosynthetic oxygen. In addition, a new method using 13 C 18 O 2 gives the means to measure with accuracy eventual isotopic effects. The labelling kinetics of the oxygen evolved by Euglena suspensions whose water has been enriched with 18 O have been established at different temperatures. (author) [fr

  20. Kinetic Behavior of Exchange-Driven Growth with Catalyzed-Birth Processes

    Science.gov (United States)

    Wang, Hai-Feng; Lin, Zhen-Quan; Kong, Xiang-Mu

    2006-12-01

    Two catalyzed-birth models of n-species (n>=2) aggregates with exchange-driven growth processes are proposed and compared. In the first one, the exchange reaction occurs between any two aggregates Amk and Amj of the same species with the rate kernels Km(k,j) = Kmkj (m = 1,2,...,n, n>=2), and aggregates of An species catalyze a monomer-birth of Al species (l = 1,2,...,n-1) with the catalysis rate kernel Jl(k,j) = Jlkjυ. The kinetic behaviors are investigated by means of the mean-field theory. We find that the evolution behavior of aggregate-size distribution alk(t) of Al species depends crucially on the value of the catalysis rate parameter υ: (i) alk(t) obeys the conventional scaling law in the case of υ0. In the second model, the mechanism of monomer-birth of An-species catalyzed by Al species is added on the basis of the first model, that is, the aggregates of Al and An species catalyze each other to cause monomer-birth. The kinetic behaviors of Al and An species are found to fall into two categories for the different υ: (i) growth obeying conventional scaling form with υ0.

  1. Gas exchange kinetics following concentric-eccentric isokinetic arm and leg exercise.

    Science.gov (United States)

    Drescher, U; Mookerjee, S; Steegmanns, A; Knicker, A; Hoffmann, U

    2017-06-01

    To evaluate the effects of exercise velocity (60, 150, 240deg∙s -1 ) and muscle mass (arm vs leg) on changes in gas exchange and arterio-venous oxygen content difference (avDO 2 ) following high-intensity concentric-eccentric isokinetic exercise. Fourteen subjects (26.9±3.1years) performed a 3×20-repetition isokinetic exercise protocol. Recovery beat-to-beat cardiac output (CO) and breath-by-breath gas exchange were recorded to determine post-exercise half-time (t 1/2 ) for oxygen uptake (V˙O 2 pulm), carbon dioxide output (V˙CO 2 pulm), and ventilation (V˙ E ). Significant differences of the t 1/2 values were identified between 60 and 150deg∙s -1 . Significant differences in the t 1/2 values were observed between V˙O 2 pulm and V˙CO 2 pulm and between V˙CO 2 pulm and V˙ E . The time to attain the first avDO 2 -peak showed significant differences between arm and leg exercise. The present study illustrates, that V˙O 2 pulm kinetics are distorted due to non-linear CO dynamics. Therefore, it has to be taken into account, that V˙O 2 pulm may not be a valuable surrogate for muscular oxygen uptake kinetics in the recovery phases. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Hydrogen-exchange kinetics of the indole NH proton of the buried tryptophan in the constant fragment of the immunoglobulin light chain

    International Nuclear Information System (INIS)

    Kawata, Y.; Goto, Y.; Hamaguchi, K.; Hayashi, F.; Kobayashi, Y.; Kyogoku, Y.

    1988-01-01

    The constant fragment of the immunoglobulin light chain (type λ) has two trytophyl residues at positions 150 and 187. Trp-150 is buried in the interior, and Trp-187 lies on the surface of the molecule. The hydrogen-deuterium exchange kinetics of the indole NH proton Trp-150 were studied at various pH values at 25 0 C by 1 H nuclear magnetic resonance. Exchange rates were approximately first order in hydroxyl ion dependence above pH 8, were relatively independent of pH between pH 7 and 8, and decreased below pH 7. On the assumption that the exchange above pH 8 proceeds through local fluctuations of the protein molecule, the exchange rates between pH 7 and 8 through global unfolding were estimated. The exchange rate constant within this pH range at 25 0 C thus estimated was consistent with that of the global unfolding of the constant fragment under the same conditions as those reported previously. The activation energy for the exchange process at pH 7.8 was the same as that for the unfolding process by 2 M guanidine hydrochloride. The exchange rates of backbone NH protons were almost the same as that of the indole NH proton of Trp-150 at pH 7.l. These observations also indicated that the exchange between pH 7 and 8 occurs through global unfolding of the protein molecule and is rate-limited by the unfolding. At around pH 9, on the other hand, the activation energy for the exchange process of the indole NH proton of Trp-150 was smaller than that for the unfolding process, and the exchange rates differed according to the different signals of backbone NH protons. These findings together with the pH dependence of the rate constant indicated that exchange due to local fluctuations is predominant above pH 8

  3. Kinetics and mechanism of ligand-exchange reactions of Cd(II) chelates

    Energy Technology Data Exchange (ETDEWEB)

    Nivorozhkin, L.E.; Kalabin, G.A.; Nivorozhkin, A.L.; Valeev, R.B.; Minkin, V.I.

    1987-03-01

    Tetrahedral Cd(II) bis(5-thio(or seleno)pyrazole-4-carboxaldiminates) of types II and III have been synthesized for the first time. The kinetics of the degenerate ligand exchange and enantiomerization of the complexes obtained have been studied by dynamic /sup 111/Cd, /sup 77/Se, and /sup 1/H (s = 1/2) NMR. The rate of intramolecular enantiomerization (k = 1/tau) is more than an order of magnitude greater than the corresponding values for processes of degenerate ligand exchange (a second-order reaction) determined from the dynamics of the averaging of the /sup 111/Cd-/sup 77/Se and /sup 111/Cd-N=CH spin-spin coupling constants. The cleavage and formation processes of the Cd-Se and Cd-N bonds are isoenergetic (..delta.. G/sub 298//sup not equal to/ = 14.4 kcal/mole for chelate II with X = Se and R = CH/sub 2/C/sub 6/H/sub 5/). The free energies of activation of degenerate ligand exchange determined form the dynamics of the averaging of the /sup 111/Cd N=CH spin-spin coupling constant increase from 12.7 to 17.9 kcal/mole along the following series for R: C/sub 2/H/sub 5/ < Ar < CH/sub 2/C/sub 6/H/sub 5/ < t-C/sub 4/H/sub 9/ < cyclo-C/sub 6/H/sub 11/. Replacement of the sulfur atom in the chelate ring by selenium results in increases in the rates of ligand exchange. A mechanism of degenerate ligand exchange has been proposed.

  4. Ion-exchange Resin Catalyzed Esterification of Lactic Acid with Isopropanol: a Kinetic Study

    Directory of Open Access Journals (Sweden)

    Amrit P. Toor

    2011-05-01

    Full Text Available The kinetic behavior of esterification of lactic acid with isopropanol over an acidic cation exchange resin, Amberlyst 15, was studied under isothermal condition. Isopropyl lactate synthesized in this reaction is an important pharmaceutical intermediate. The experiments were carried out in a stirred batch reactor in the temperature range of 323.15 to 353.15 K. The effect of various parameters such as temperature, molar ratio and catalyst loading was studied. Variation in parameters on rate of reaction demonstrated that the reaction was intrinsically controlled. Kinetic modeling was performed using Eley-Rideal model which acceptably fits the experimental data. The activation energy was found to be 22.007 kJ/mol and frequency factor was 0.036809 l2 g-1 mol-1 min-1 for forward reaction. The value of entropy for the forward reaction was found to be 182.317 J K-1 mol-1 . © 2011 BCREC UNDIP. All rights reserved(Received: 19th January 2011, Revised: 16th March 2011; Accepted: 16th March 2011[How to Cite: A.P. Toor, M. Sharma, S. Thakur, and R. K. Wanchoo. (2011. Ion-exchange Resin Catalyzed Esterification of Lactic Acid with Isopropanol: a Kinetic Study. Bulletin of Chemical Reaction Engineering and Catalysis, 6(1: 39-45. doi:10.9767/bcrec.6.1.791.39-45][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.1.791.39-45 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/791 ] | View in  

  5. Kinetic Behaviors of a Competitive Population and Fitness System in Exchange-Driven Growth

    International Nuclear Information System (INIS)

    Lu Ke; Lin Zhenquan; Sun Yunfei

    2008-01-01

    We proposed an aggregation model of two species aggregates of fitness and population to study the interaction between the two species in their exchange-driven processes of the same species by introducing the monomer birth of fitness catalyzed by the population, where the fitness aggregates perform self-death process and the population aggregates perform self-birth process. The kinetic behaviors of the aggregate size distributions of the fitness and population were analyzed by the rate equation approach with their exchange rate kernel K 1 (k,j) = K 1 kj and K 2 (k,j) = K 2 kj, the fitness aggregate's self-death rate kernel J 1 (k) = J 1 k, population aggregate's self-birth rate kernel J 2 (k) = J 2 k and population-catalyzed fitness birth rate kernel I(k,j) = Ikj v . The kinetic behavior of the fitness was found depending crucially on the parameter v, which reflects the dependence of the population-catalyzed fitness birth rate on the size of the catalyst (population) aggregate. (i) In the v ≤ 0 case, the effect of catalyzed-birth of fitness is rather weak and the exchange-driven aggregation and self-death of the fitness dominate the process, and the fitness aggregate size distribution a k (t) does not have scale form. (ii) When v > 0, the effect of the population-catalyzed birth of fitness gets strong enough, and the catalyzed-birth and self-death of the fitness aggregates, together with the self-birth of the population aggregates dominate the evolution process of the fitness aggregates. The aggregate size distribution a k (t) approaches a generalized scaling form

  6. Isotopic exchange kinetics of zinc ions in Zn-A zeolite

    Energy Technology Data Exchange (ETDEWEB)

    Radak, V M; Gal, I J; Salai, J J [Belgrade Univ. (Yugoslavia)

    1976-01-01

    The isotopic exchange kinetics of Zn/sup 2 +/ ions in hydrated Zn-A zeolite of composition (Znsub(5.55)Nasub(0.90)(A10/sub 2/)/sub 12/(Si0/sub 2/)/sub 12/.aq) have been investigated by measuring the fractional attainment of isotopic equilibrium between a ZnCl/sub 2/ solution and a /sup 65/Zn-labelled Zn-A zeolite (30 and 45 ..mu..m particle radii) as a function of time, in the temperature range 25 to 60/sup 0/C. The exchange mechanism is a two-step process which has been resolved, using the Brown-Sherry-Krambeck model (J.Phys.Chem.;75:3846(1971)) into diffusion in the solid particles, with Zn/sup 2 +/ diffusivity of D = 10sup(-3.97 + -0.03) exp(-Esub(D)/RT)m/sup 2/ s/sup -1/, Esub(D) = 67.1 +- 0.5 kJ molee/sup -1/, and an intracrystalline first-order exchange between bound and mobile Zn/sup 2 +/ ions in the network, with a rate constant of k/sub 2/ = 10sup(3.05 +- 0.25) exp(-Esub(k)/RT)s/sup -1/, Esub(k) = 56.5 +- 1.5 kJ mol/sup -1/.

  7. Site-Specific Hydrogen Isotope Composition of Propane: Mass spectrometric methods, equilibrium temperature dependence, and kinetics of exchange

    Science.gov (United States)

    Xie, H.; Ponton, C.; Kitchen, N.; Lloyd, M. K.; Lawson, M.; Formolo, M. J.; Eiler, J. M.

    2016-12-01

    Intramolecular isotope ordering can constrain temperatures of synthesis, mechanisms of formation, and/or source substrates of organic compounds. Here we explore site-specific hydrogen isotope variations of propane. Statistical thermodynamic models predict that at equilibrium methylene hydrogen (-CH2-) in propane will be 10's of per mil higher in D/H ratio than methyl hydrogen (-CH3) at geologically relevant temperatures, and that this difference is highly temperature dependent ( 0.5-1 ‰/°C). Chemical-kinetic controls on site-specific D/H in propane could constrain the mechanisms, conditions and extents of propane synthesis or destruction. We have developed a method for measuring the difference in D/H ratio between methylene and methyl hydrogen in propane by gas source mass spectrometry. The data were measured using the Thermo Fisher Double Focusing Sector high resolution mass spectrometer (DFS), and involve comparison of the D/H ratios of molecular ion (C3H8+) and the ethyl fragmental ion (C2H5+). We demonstrate the accuracy and precision of this method through analysis of D-labeled and independently analyzed propanes. In the exchange experiments, propane was heated (100-200 oC) either alone or in the presence of D-enriched water (δD=1,1419 ‰ SMOW), with or without one of several potentially catalytic substrates for hours to weeks. Propane was found to exchange hydrogen with water vigorously at 200 °C in the presence of metal catalysts. In the presence of Ni catalyst, methylene hydrogen exchanges 2.5 times faster than methyl hydrogen. Hydrogen exchange in the presence of Pd catalyst is more effective and can equilibrate hydrogen isotope distribution on propane on the order of 7 days. Isotopic exchange in the presence of natural materials have also been tested, but is only measurable in the methylene group at 200 °C. High catalytic activity of Pd permits attainment of a bracketed, time-invariant equilibrium state that we use to calibrate the site

  8. Rate theory of solvent exchange and kinetics of Li(+) - BF4 (-)/PF6 (-) ion pairs in acetonitrile.

    Science.gov (United States)

    Dang, Liem X; Chang, Tsun-Mei

    2016-09-07

    In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li(+) and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li(+) in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li(+)-[BF4] and Li(+)-[PF6] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li(+). We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li(+)-[BF4] and Li(+)-[PF6] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.

  9. Equilibrium isotope exchange kinetics of native and site-specific mutant forms of E. coli aspartate transcarbamoylase

    International Nuclear Information System (INIS)

    Wedler, F.C.; Hsuanyu, Y.; Kantrowitz, E.R.

    1987-01-01

    Isotope exchange kinetics at equilibrium (EIEK) have been used to probe the kinetic and regulatory mechanisms of native aspartate transcarbamoylase (ATCase) from E. coli at pH 7.0, 30 0 . Substrate saturation patterns were most consistent with a preferred order random kinetic mechanism: C-P prior to L-Asp, C-Asp released before Pi, with the Asp ↔ C-Asp exchange rate 5X faster than C-P ↔ Pi. Computer simulations allow one to fit the EIEK experimental data and to arrive at the best set of kinetic constants for a given enzyme state. These approaches have been applied to modified ATCase. Bound CTP and ATP were observed, respectively, to inhibit and activate differentially Asp ↔ C-Asp, but not C-P ↔ Pi, indicating that these modifiers alter the association-dissociation rates of L-Asp and C-Asp but not of C-P or Pi. Low levels of PALA activated both exchange rates (due to shifting the T-R equilibrium), but higher [PALA] completely blocked both exchanges. The effects of a site-specific mutation of Tyr240 Phe have been similarly probed by EIEK methods. The Phe240 mutant enzyme exhibited kinetic properties markedly different from native ATCase: the data indicate that Phe240 ATCase is much closer to an R-state enzyme than is native enzyme

  10. Isotopic modeling of water and sodium distribution and exchange kinetics in 7 stable hemodialysis patients

    International Nuclear Information System (INIS)

    Chamoiseau, S.; Bertrou, L.; Pujo, J.M.; Massol, M.

    1988-01-01

    Sequential serum sampling over 24 h. has been performed in 7 hemodialysis patients after simultaneous intra-venous injection of tritiated water and 24 Na. Each time-activity curve fits a biexponential pattern. A compartment analysis leads to describe either a simple but incomplete single compartment model or a much more satisfactory open two-compartment mamillary model featuring 2 intercompartment transfer rate constants k 21 and k 12 , and a loss out of the system, k 01 . These constants can be related to intrabody resistances to sodium and water transfers. Compartment analysis allows a comprehensive quantitated description of the exchange and transfer kinetics of sodium and water throughout the system. Evidence for a sodium reservoir, probably located in bone, can be drawn from the results and leads to propose a strategy for a targetted bone sodium removal [fr

  11. Kinetics and mechanism of photoaccelerated isotope exchange between U(VI) and U(IV) in oxalate solutions

    International Nuclear Information System (INIS)

    Shaban, I.S.; Owreit, M.F.; Nikitenko, S.I.

    1992-01-01

    A kinetic study of thermal and photoaccelerated U(IV)-U(VI) isotope exchange has been carried out in oxalate solutions at 11-40 deg C. The rate and quantum yield were determined as a function of U(IV), U(VI) and oxalate concentration, wavelength of incident light, temperature and absorbed dose of γ-radiation. The kinetic equations for thermal and photoaccelerated exchange have been obtained. It was assumed that the mechanism of exchange involves formation of U(V) as an intermediate, followed by slow exchange between U(V) and U(IV). The isokinetic dependence confirms the identity of limiting stages for thermal and photostimulated exchange. The upper component of photoexcited T 1 level of uranyl is supposed to be the most reactive in the process of U(V) generation. It was observed that the small doses of γ-radiation evoke the acceleration of isotope exchange, however, at D>100 krad the rate of exchange is reduced to the level of thermal exchange. (author) 8 refs.; 4 figs.; 2 tabs

  12. Kinetic Behavior of Exchange-Driven Growth with Catalyzed-Birth Processes

    International Nuclear Information System (INIS)

    Wang Haifeng; Lin Zhenquan; Kong Xiangmu

    2006-01-01

    Two catalyzed-birth models of n-species (n≥2) aggregates with exchange-driven growth processes are proposed and compared. In the first one, the exchange reaction occurs between any two aggregates A m k and A m j of the same species with the rate kernels K m (k,j) = K m kj (m = 1,2,...,n, n≥2), and aggregates of A n species catalyze a monomer-birth of A l species (l = 1,2,...,n-1) with the catalysis rate kernel J l (k,j) = J l kj υ . The kinetic behaviors are investigated by means of the mean-field theory. We find that the evolution behavior of aggregate-size distribution a l k (t) of A l species depends crucially on the value of the catalysis rate parameter υ: (i) a l k (t) obeys the conventional scaling law in the case of υ≤0, (ii) a l k (t) satisfies a modified scaling form in the case of υ>0. In the second model, the mechanism of monomer-birth of A n -species catalyzed by A l species is added on the basis of the first model, that is, the aggregates of A l and A n species catalyze each other to cause monomer-birth. The kinetic behaviors of A l and A n species are found to fall into two categories for the different υ: (i) growth obeying conventional scaling form with υ≤0, (ii) gelling at finite time with υ>0.

  13. Heat and turbulent kinetic energy budgets for surface layer cooling induced by the passage of Hurricane Frances (2004)

    Science.gov (United States)

    Huang, Peisheng; Sanford, Thomas B.; Imberger, JöRg

    2009-12-01

    Heat and turbulent kinetic energy budgets of the ocean surface layer during the passage of Hurricane Frances were examined using a three-dimensional hydrodynamic model. In situ data obtained with the Electromagnetic-Autonomous Profiling Explorer (EM-APEX) floats were used to set up the initial conditions of the model simulation and to compare to the simulation results. The spatial heat budgets reveal that during the hurricane passage, not only the entrainment in the bottom of surface mixed layer but also the horizontal water advection were important factors determining the spatial pattern of sea surface temperature. At the free surface, the hurricane-brought precipitation contributed a negligible amount to the air-sea heat exchange, but the precipitation produced a negative buoyancy flux in the surface layer that overwhelmed the instability induced by the heat loss to the atmosphere. Integrated over the domain within 400 km of the hurricane eye on day 245.71 of 2004, the rate of heat anomaly in the surface water was estimated to be about 0.45 PW (1 PW = 1015 W), with about 20% (0.09 PW in total) of this was due to the heat exchange at the air-sea interface, and almost all the remainder (0.36 PW) was downward transported by oceanic vertical mixing. Shear production was the major source of turbulent kinetic energy amounting 88.5% of the source of turbulent kinetic energy, while the rest (11.5%) was attributed to the wind stirring at sea surface. The increase of ocean potential energy due to vertical mixing represented 7.3% of the energy deposited by wind stress.

  14. Investigation of ammonia air-surface exchange processes in a ...

    Science.gov (United States)

    Recent assessments of atmospheric deposition in North America note the increasing importance of reduced (NHx = NH3 + NH4+) forms of nitrogen (N) relative to oxidized forms. This shift in in the composition of inorganic nitrogen deposition has both ecological and policy implications. Deposition budgets developed from inferential models applied at the landscape scale, as well as regional and global chemical transport models, indicate that NH3 dry deposition contributes a significant portion of inorganic N deposition in many areas. However, the bidirectional NH3 flux algorithms employed in these models have not been extensively evaluated for North American conditions (e.g, atmospheric chemistry, meteorology, biogeochemistry). Further understanding of the processes controlling NH3 air-surface exchange in natural systems is critically needed. Based on preliminary results from the Southern Appalachian Nitrogen Deposition Study (SANDS), this presentation examines processes of NH3 air-surface exchange in a deciduous montane forest at the Coweeta Hydrologic Laboratory in western North Carolina. A combination of measurements and modeling are used to investigate net fluxes of NH3 above the forest and sources and sinks of NH3 within the canopy and forest floor. Measurements of biogeochemical NH4+ pools are used to characterize emission potential and NH3 compensation points of canopy foliage (i.e., green vegetation), leaf litter, and soil and their relation to NH3 fluxes

  15. Stomatal kinetics and photosynthetic gas exchange along a continuum of isohydric to anisohydric regulation of plant water status.

    Science.gov (United States)

    Meinzer, Frederick C; Smith, Duncan D; Woodruff, David R; Marias, Danielle E; McCulloh, Katherine A; Howard, Ava R; Magedman, Alicia L

    2017-08-01

    Species' differences in the stringency of stomatal control of plant water potential represent a continuum of isohydric to anisohydric behaviours. However, little is known about how quasi-steady-state stomatal regulation of water potential may relate to dynamic behaviour of stomata and photosynthetic gas exchange in species operating at different positions along this continuum. Here, we evaluated kinetics of light-induced stomatal opening, activation of photosynthesis and features of quasi-steady-state photosynthetic gas exchange in 10 woody species selected to represent different degrees of anisohydry. Based on a previously developed proxy for the degree of anisohydry, species' leaf water potentials at turgor loss, we found consistent trends in photosynthetic gas exchange traits across a spectrum of isohydry to anisohydry. More anisohydric species had faster kinetics of stomatal opening and activation of photosynthesis, and these kinetics were closely coordinated within species. Quasi-steady-state stomatal conductance and measures of photosynthetic capacity and performance were also greater in more anisohydric species. Intrinsic water-use efficiency estimated from leaf gas exchange and stable carbon isotope ratios was lowest in the most anisohydric species. In comparisons between gas exchange traits, species rankings were highly consistent, leading to species-independent scaling relationships over the range of isohydry to anisohydry observed. © 2017 John Wiley & Sons Ltd.

  16. Group IV nanocrystals with ion-exchangeable surface ligands and methods of making the same

    Science.gov (United States)

    Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; Anderson, Nicholas C.; Beard, Matthew C.; Neale, Nathan R.

    2018-01-09

    Methods are described that include reacting a starting nanocrystal that includes a starting nanocrystal core and a covalently bound surface species to create an ion-exchangeable (IE) nanocrystal that includes a surface charge and a first ion-exchangeable (IE) surface ligand ionically bound to the surface charge, where the starting nanocrystal core includes a group IV element.

  17. Focus State Roadway Departure Safety Plans and High Friction Surface Treatments Peer Exchange : an RPSCB Peer Exchange

    Science.gov (United States)

    2014-08-01

    This report summarizes the Focus State Roadway Departure Safety Plans and High Friction Surface Treatments Peer Exchange, held in Birmingham, Alabama, sponsored by the Federal Highway Administration (FHWA) Office of Safetys Roadway Safety Professi...

  18. Effects of surface exchange anisotropy in Heisenberg ferromagnetic insulators

    International Nuclear Information System (INIS)

    Selzer, S.; Majlis, N.

    1982-03-01

    We consider an fcc semi-infinite ferromagnetic insulator displaying an anisotropic exchange interaction between spins on the (111) surface plane of the form Jsub(parallel)[Ssub(i)sup(x)Ssub(j)sup(x)+Ssub(i)sup(y)Ssub(j)sup(y )+etaSsub(i)sup(z)Ssub(j)sup(z)], assuming all other interactions isotropic. A self-consistent RPA calculation is performed, with a Green function method valid for any spin S, up to the bulk transition temperature Tsub(c)sup(b), by imposing that the magnetization of the third layer equals the bulk value. For eta sufficiently large, the surface magnetization is non-zero for T>Tsub(c)sup(b), up to a transition temperature Tsub(c)sup(s)(eta) whenever eta>=etasub(c)>1, where Tsub(c)sup(s)(etasub(c))=Tsub(c)sup(b). For T>Tsub(c)sup(b) the system is equivalent to a film of three layers, where the magnetization of the third one is identically zero as a boundary condition. A discontinuity of the derivative in the curve of the magnetization of the first two layers vs. temperature is found at Tsub(c)sup(b). The results show clearly a cross-over from Heisenberg to Ising behaviour at the surface. (author)

  19. Experimental investigation of thermal conductivity coefficient and heat exchange between fluidized bed and inclined exchange surface

    Directory of Open Access Journals (Sweden)

    B. Stojanovic

    2009-06-01

    Full Text Available The paper presents experimental research of thermal conductivity coefficients of the siliceous sand bed fluidized by air and an experimental investigation of the particle size influence on the heat transfer coefficient between fluidized bed and inclined exchange surfaces. The measurements were performed for the specific fluidization velocity and sand particle diameters d p=0.3, 0.5, 0.9 mm. The industrial use of fluidized beds has been increasing rapidly in the past 20 years owing to their useful characteristics. One of the outstanding characteristics of a fluidized bed is that it tends to maintain a uniform temperature even with nonuniform heat release. On the basis of experimental research, the influence of the process's operational parameters on the obtained values of the bed's thermal conductivity has been analyzed. The results show direct dependence of thermal conductivity on the intensity of mixing, the degree of fluidization, and the size of particles. In the axial direction, the coefficients that have been treated have values a whole order higher than in the radial direction. Comparison of experimental research results with experimental results of other authors shows good agreement and the same tendency of thermal conductivity change. It is well known in the literature that the value of the heat transfer coefficient is the highest in the horizontal and the smallest in the vertical position of the heat exchange surface. Variation of heat transfer, depending on inclination angle is not examined in detail. The difference between the values of the relative heat transfer coefficient between vertical and horizontal heater position for all particle sizes reduces by approximately 15% with the increase of fluidization rate.

  20. Experimental Characterization and Modelization of Ion Exchange Kinetics for a Carboxylic Resin in Infinite Solution Volume Conditions. Application to Monovalent-Trivalent Cations Exchange

    Energy Technology Data Exchange (ETDEWEB)

    Picart, S.; Mokhtari, H.; Jobelin, I. [CEA Marcoule, Nucl Energy Div, RadioChem and Proc Dept, Actinides Chem and Convers Lab, F-30207 Bagnols Sur Ceze (France); Ramiere, I. [Fuel Simulat Lab, Fuel Study Dept, F-13108 St Paul Les Durance (France)

    2010-07-01

    This study is devoted to the characterization of ion exchange inside a microsphere of carboxylic resin. It aims at describing the kinetics of this exchange reaction which is known to be controlled by interdiffusion in the particle. The fractional attainment of equilibrium function of time depends on the concentration of the cations in the resin which can be modelled by the Nernst-Planck equation. A powerful approach for the numerical resolution of this equation is introduced in this paper. This modeling is based on the work of Helfferich but involves an implicit numerical scheme which reduces the computational cost. Knowing the diffusion coefficients of the cations in the resin and the radius of the spherical exchanger, the kinetics can be hence completely determined. When those diffusion parameters are missing, they can be deduced by fitting experimental data of fractional attainment of equilibrium. An efficient optimization tool coupled with the implicit resolution has been developed for this purpose. A monovalent/trivalent cation exchange had been experimentally characterized for a carboxylic resin. Diffusion coefficients and concentration profiles in the resin were then deduced through this new model. (authors)

  1. Experimental Characterization and Modelization of Ion Exchange Kinetics for a Carboxylic Resin in Infinite Solution Volume Conditions. Application to Monovalent-Trivalent Cations Exchange

    International Nuclear Information System (INIS)

    Picart, S.; Mokhtari, H.; Jobelin, I.; Ramiere, I.

    2010-01-01

    This study is devoted to the characterization of ion exchange inside a microsphere of carboxylic resin. It aims at describing the kinetics of this exchange reaction which is known to be controlled by interdiffusion in the particle. The fractional attainment of equilibrium function of time depends on the concentration of the cations in the resin which can be modelled by the Nernst-Planck equation. A powerful approach for the numerical resolution of this equation is introduced in this paper. This modeling is based on the work of Helfferich but involves an implicit numerical scheme which reduces the computational cost. Knowing the diffusion coefficients of the cations in the resin and the radius of the spherical exchanger, the kinetics can be hence completely determined. When those diffusion parameters are missing, they can be deduced by fitting experimental data of fractional attainment of equilibrium. An efficient optimization tool coupled with the implicit resolution has been developed for this purpose. A monovalent/trivalent cation exchange had been experimentally characterized for a carboxylic resin. Diffusion coefficients and concentration profiles in the resin were then deduced through this new model. (authors)

  2. Kinetic study of the isotopic exchange of Na+ and Zn2+ ions on iron and chromium titanates

    International Nuclear Information System (INIS)

    Zakaria, E.S.; Ali, I.M.; Aly, H.F.

    2004-01-01

    Iron(III) (FeTi) and chromium (III) titanates (CrTi) were prepared as cation exchange materials in a granular form. The rate of the isotopic exchange of Na + /*Na + and Zn 2+ /*Zn 2+ between aqueous solution and iron(III) and chromium(III) titanates in Na + or Zn 2+ form has been carried out radiometrically in the 25-60 deg C temperature range. The exchange rate is controlled by a particle diffusion mechanism and experimental and theoretical approaches have been used to obtain the rate of diffusion through the spherical particles of the exchangers. The values of self diffusion (D-bar) of Na + and Zn 2+ ions were measured at different operation conditions, particle size, reaction temperatures and drying temperatures of the matrix. The values of kinetic and thermodynamic parameters were calculated and their significance discussed. (author)

  3. Kinetic Study on the Sorption of Te (IV), Ce (III) and Eu (III) on some Inorganic Ion Exchangers

    International Nuclear Information System (INIS)

    El-Sweify, F.H.; Shehata, M.K.K.; El-Shazly, E.A.A.

    2008-01-01

    The sorption behaviour of Te (IV), Ce (III) and Eu (III) on zirconium phosphate (Zr P) and ceric tungstate under various conditions was studied. Some factors affecting the sorption kinetics of the aforementioned metal ions on both ion exchangers were investigated. These factors were: hydrogen ion concentration in the absence of complexing agents, contact time, particle size of the two mentioned ion exchangers, metal in concentration and temperature. Radioactive isotopes were used for tracing the corresponding elements. Some physical parameters related to the sorption process were calculated from the obtained data

  4. Variations in calcite growth kinetics with surface topography: molecular dynamics simulations and process-based growth kinetics modelling

    NARCIS (Netherlands)

    Wolthers, M.; Di Tommaso, D.; Du, Zhimei; de Leeuw, Nora H.

    2013-01-01

    It is generally accepted that cation dehydration is the rate-limiting step to crystal growth from aqueous solution. Here we employ classical molecular dynamics simulations to show that the water exchange frequency at structurally distinct calcium sites in the calcite surface varies by about two

  5. The effect of surface-bulk potential difference on the kinetics of intercalation in core-shell active cathode particles

    Science.gov (United States)

    Kazemiabnavi, Saeed; Malik, Rahul; Orvananos, Bernardo; Abdellahi, Aziz; Ceder, Gerbrand; Thornton, Katsuyo

    2018-04-01

    Surface modification of active cathode particles is commonly observed in battery research as either a surface phase evolving during the cycling process, or intentionally engineered to improve capacity retention, rate capability, and/or thermal stability of the cathode material. Here, a continuum-scale model is developed to simulate the galvanostatic charge/discharge of a cathode particle with core-shell heterostructure. The particle is assumed to be comprised of a core material encapsulated by a thin layer of a second phase that has a different open-circuit voltage. The effect of the potential difference between the surface and bulk phases (Ω) on the kinetics of lithium intercalation and the galvanostatic charge/discharge profiles is studied at different values of Ω, C-rates, and exchange current densities. The difference between the Li chemical potential in the surface and bulk phases of the cathode particle results in a concentration difference between these two phases. This leads to a charge/discharge asymmetry in the galvanostatic voltage profiles, causing a decrease in the accessible capacity of the particle. These effects are more significant at higher magnitudes of surface-bulk potential difference. The proposed model provides detailed insight into the kinetics and voltage behavior of the intercalation/de-intercalation processes in core-shell heterostructure cathode particles.

  6. Soil solution phosphorus turnover: derivation, interpretation, and insights from a global compilation of isotope exchange kinetic studies

    Science.gov (United States)

    Helfenstein, Julian; Jegminat, Jannes; McLaren, Timothy I.; Frossard, Emmanuel

    2018-01-01

    The exchange rate of inorganic phosphorus (P) between the soil solution and solid phase, also known as soil solution P turnover, is essential for describing the kinetics of bioavailable P. While soil solution P turnover (Km) can be determined by tracing radioisotopes in a soil-solution system, few studies have done so. We believe that this is due to a lack of understanding on how to derive Km from isotopic exchange kinetic (IEK) experiments, a common form of radioisotope dilution study. Here, we provide a derivation of calculating Km using parameters obtained from IEK experiments. We then calculated Km for 217 soils from published IEK experiments in terrestrial ecosystems, and also that of 18 long-term P fertilizer field experiments. Analysis of the global compilation data set revealed a negative relationship between concentrations of soil solution P and Km. Furthermore, Km buffered isotopically exchangeable P in soils with low concentrations of soil solution P. This finding was supported by an analysis of long-term P fertilizer field experiments, which revealed a negative relationship between Km and phosphate-buffering capacity. Our study highlights the importance of calculating Km for understanding the kinetics of P between the soil solid and solution phases where it is bioavailable. We argue that our derivation can also be used to calculate soil solution turnover of other environmentally relevant and strongly sorbing elements that can be traced with radioisotopes, such as zinc, cadmium, nickel, arsenic, and uranium.

  7. Kinetic Behavior of Aggregation-Exchange Growth Process with Catalyzed-Birth

    International Nuclear Information System (INIS)

    Han Anjia; Chen Yu; Lin Zhenquan; Ke Jianhong

    2007-01-01

    We propose an aggregation model of a two-species system to mimic the growth of cities' population and assets, in which irreversible coagulation reactions and exchange reactions occur between any two aggregates of the same species, and the monomer-birth reactions of one species occur by the catalysis of the other species. In the case with population-catalyzed birth of assets, the rate kernel of an asset aggregate B k of size k grows to become an aggregate B k+1 through a monomer-birth catalyzed by a population aggregate A j of size j is J(k,j) = Jkj λ . And in mutually catalyzed birth model, the birth rate kernels of population and assets are H(k,j) = Hkj η and J(k,j) = Jkj λ , respectively. The kinetics of the system is investigated based on the mean-field theory. In the model of population-catalyzed birth of assets, the long-time asymptotic behavior of the assets aggregate size distribution obeys the conventional or modified scaling form. In mutually catalyzed birth system, the asymptotic behaviors of population and assets obey the conventional scaling form in the case of η = λ = 0, and they obey the modified scaling form in the case of η = 0,λ = 1. In the case of η = λ = 1, the total mass of population aggregates and that of asset aggregates both grow much faster than those in population-catalyzed birth of assets model, and they approaches to infinite values in finite time.

  8. Extracting surface diffusion coefficients from batch adsorption measurement data: application of the classic Langmuir kinetics model.

    Science.gov (United States)

    Chu, Khim Hoong

    2017-11-09

    Surface diffusion coefficients may be estimated by fitting solutions of a diffusion model to batch kinetic data. For non-linear systems, a numerical solution of the diffusion model's governing equations is generally required. We report here the application of the classic Langmuir kinetics model to extract surface diffusion coefficients from batch kinetic data. The use of the Langmuir kinetics model in lieu of the conventional surface diffusion model allows derivation of an analytical expression. The parameter estimation procedure requires determining the Langmuir rate coefficient from which the pertinent surface diffusion coefficient is calculated. Surface diffusion coefficients within the 10 -9 to 10 -6  cm 2 /s range obtained by fitting the Langmuir kinetics model to experimental kinetic data taken from the literature are found to be consistent with the corresponding values obtained from the traditional surface diffusion model. The virtue of this simplified parameter estimation method is that it reduces the computational complexity as the analytical expression involves only an algebraic equation in closed form which is easily evaluated by spreadsheet computation.

  9. Ion Exchange Kinetics of some Heavy Metals from Aqueous Solutions onto Poly(Acrylic Acid-Acrylo nitrle) Potassium Titanate

    International Nuclear Information System (INIS)

    El-Shorbagy, M.M.; El-Sadek, A.A.

    2012-01-01

    Composite inorganic-organic absorbers represent a group of inorganic ion exchangers modified using binding organic materials for preparation of larger size particles heaving higher granular strength. Such modification of originally powdered or microcrystalline inorganic ion exchangers makes their application in peaked beds possible-modified polyacrylonitrile (PAN) has been used as a universal binding polymer for a number of inorganic ion exchangers. The kinetic of ion exchange and sorption capacity of such composite absorbers is not influenced by the binding polymer mentioned above. These composites have been tested for separation and concentration of various contaminants from aqueous solutions. Their high selectivity and sorption efficiency are advantageous for treatment of various industrial waste waters. Removal of natural or artificial and the heavy metals, Pb, Cd and Zn ions. the influence of initial metal ion concentration and ph on metal ion removal has been studied. The process was found to follow a first order rate kinetics. The intra-particle diffusion of ions through pores in the adsorbent was to be the main rate limiting step. The selectivity order towards the ions was Pb(II) > Cd(II) > Zn(II)

  10. Kinetics of exchange between zero-, one-, and two-hydrogen-bonded states of methyl and ethyl acetate in methanol.

    Science.gov (United States)

    Chuntonov, Lev; Pazos, Ileana M; Ma, Jianqiang; Gai, Feng

    2015-03-26

    It has recently been shown that the ester carbonyl stretching vibration can be used as a sensitive probe of local electrostatic field in molecular systems. To further characterize this vibrational probe and extend its potential applications, we studied the kinetics of chemical exchange between differently hydrogen-bonded (H-bonded) ester carbonyl groups of methyl acetate (MA) and ethyl acetate (EA) in methanol. We found that, while both MA and EA can form zero, one, or two H-bonds with the solvent, the population of the 2hb state in MA is significantly smaller than that in EA. Using a combination of linear and nonlinear infrared measurements and numerical simulations, we further determined the rate constants for the exchange between these differently H-bonded states. We found that for MA the chemical exchange reaction between the two dominant states (i.e., 0hb and 1hb states) has a relaxation rate constant of 0.14 ps(-1), whereas for EA the three-state chemical exchange reaction occurs in a predominantly sequential manner with the following relaxation rate constants: 0.11 ps(-1) for exchange between 0hb and 1hb states and 0.12 ps(-1) for exchange between 1hb and 2hb states.

  11. Surface Area, and Oxidation Effects on Nitridation Kinetics of Silicon Powder Compacts

    Science.gov (United States)

    Bhatt, R. T.; Palczer, A. R.

    1998-01-01

    Commercially available silicon powders were wet-attrition-milled from 2 to 48 hr to achieve surface areas (SA's) ranging from 1.3 to 70 sq m/g. The surface area effects on the nitridation kinetics of silicon powder compacts were determined at 1250 or 1350 C for 4 hr. In addition, the influence of nitridation environment, and preoxidation on nitridation kinetics of a silicon powder of high surface area (approximately equals 63 sq m/g) was investigated. As the surface area increased, so did the percentage nitridation after 4 hr in N2 at 1250 or 1350 C. Silicon powders of high surface area (greater than 40 sq m/g) can be nitrided to greater than 70% at 1250 C in 4 hr. The nitridation kinetics of the high-surface-area powder compacts were significantly delayed by preoxidation treatment. Conversely, the nitridation environment had no significant influence on the nitridation kinetics of the same powder. Impurities present in the starting powder, and those accumulated during attrition milling, appeared to react with the silica layer on the surface of silicon particles to form a molten silicate layer, which provided a path for rapid diffusion of nitrogen and enhanced the nitridation kinetics of high surface area silicon powder.

  12. Kinetic parameters, collision rates, energy exchanges and transport coefficients of non-thermal electrons in premixed flames at sub-breakdown electric field strengths

    KAUST Repository

    Bisetti, Fabrizio; El Morsli, Mbark

    2014-01-01

    The effects of an electric field on the collision rates, energy exchanges and transport properties of electrons in premixed flames are investigated via solutions to the Boltzmann kinetic equation. The case of high electric field strength, which

  13. Evaluation of Scaling Approaches for the Oceanic Dissipation Rate of Turbulent Kinetic Energy in the Surface Ocean

    Science.gov (United States)

    Esters, L. T.; Ward, B.; Sutherland, G.; Ten Doeschate, A.; Landwehr, S.; Bell, T. G.; Christensen, K. H.

    2016-02-01

    The air-sea exchange of heat, gas and momentum plays an important role for the Earth's weather and global climate. The exchange processes between ocean and atmosphere are influenced by the prevailing surface ocean dynamics. This surface ocean is a highly turbulent region where there is enhanced production of turbulent kinetic energy (TKE). The dissipation rate of TKE (ɛ) in the surface ocean is an important process for governing the depth of both the mixing and mixed layers, which are important length-scales for many aspects of ocean research. However, there exist very limited observations of ɛ under open ocean conditions and consequently our understanding of how to model the dissipation profile is very limited. The approaches to model profiles of ɛ that exist, differ by orders of magnitude depending on their underlying theoretical assumption and included physical processes. Therefore, scaling ɛ is not straight forward and requires open ocean measurements of ɛ to validate the respective scaling laws. This validated scaling of ɛ, is for example required to produce accurate mixed layer depths in global climate models. Errors in the depth of the ocean surface boundary layer can lead to biases in sea surface temperature. Here, we present open ocean measurements of ɛ from the Air-Sea Interaction Profiler (ASIP) collected during several cruises in different ocean basins. ASIP is an autonomous upwardly rising microstructure profiler allowing undisturbed profiling up to the ocean surface. These direct measurements of ɛ under various types of atmospheric and oceanic conditions along with measurements of atmospheric fluxes and wave conditions allow us to make a unique assessment of several scaling approaches based on wind, wave and buoyancy forcing. This will allow us to best assess the most appropriate ɛ-based parameterisation for air-sea exchange.

  14. Kinetic bottlenecks to chemical exchange rates for deep-sea animals - Part 1: Oxygen

    Science.gov (United States)

    Hofmann, A. F.; Peltzer, E. T.; Brewer, P. G.

    2012-10-01

    Ocean warming will reduce dissolved oxygen concentrations which can pose challenges to marine life. Oxygen limits are traditionally reported simply as a static concentration thresholds with no temperature, pressure or flow rate dependency. Here we treat the oceanic oxygen supply potential for heterotrophic consumption as a dynamic molecular exchange problem analogous to familiar gas exchange processes at the sea surface. A combination of the purely physico-chemical oceanic properties temperature, hydrostatic pressure, and oxygen concentration defines the ability of the ocean to supply oxygen to any given animal. This general oceanic oxygen supply potential is modulated by animal specific properties such as the diffusive boundary layer thickness to define and limit maximal oxygen supply rates. Here we combine all these properties into formal, mechanistic equations defining novel oceanic properties that subsume various relevant classical oceanographic parameters to better visualize, map, comprehend, and predict the impact of ocean deoxygenation on aerobic life. By explicitly including temperature and hydrostatic pressure into our quantities, various ocean regions ranging from the cold deep-sea to warm, coastal seas can be compared. We define purely physico-chemical quantities to describe the oceanic oxygen supply potential, but also quantities that contain organism-specific properties which in a most generalized way describe general concepts and dependencies. We apply these novel quantities to example oceanic profiles around the world and find that temperature and pressure dependencies of diffusion and partial pressure create zones of greatest physical constriction on oxygen supply typically at around 1000 m depth, which coincides with oxygen concentration minimum zones. In these zones, which comprise the bulk of the world ocean, ocean warming and deoxygenation have a clear negative effect for aerobic life. In some shallow and warm waters the enhanced diffusion and

  15. SOLVENT EFFECTS ON THE HYDRATION OF CYCLOHEXENE CATALYZED BY A STRONG ACID ION-EXCHANGE RESIN .2. EFFECT OF SULFOLANE ON THE REACTION-KINETICS

    NARCIS (Netherlands)

    PANNEMAN, HJ; BEENACKERS, AACM

    The kinetics of the' hydration of cyclohexene, catalyzed by a strong acid ion-exchange resin, have been studied in a packed bed reactor at temperatures between 353 and 413 K and a pressure of 20 bar. The kinetic rate constants were measured as a function of temperature and solvent composition (0-90

  16. Gas-Phase Hydrogen-Deuterium Exchange Labeling of Select Peptide Ion Conformer Types: a Per-Residue Kinetics Analysis.

    Science.gov (United States)

    Khakinejad, Mahdiar; Kondalaji, Samaneh Ghassabi; Tafreshian, Amirmahdi; Valentine, Stephen J

    2015-07-01

    The per-residue, gas-phase hydrogen deuterium exchange (HDX) kinetics for individual amino acid residues on selected ion conformer types of the model peptide KKDDDDDIIKIIK have been examined using ion mobility spectrometry (IMS) and HDX-tandem mass spectrometry (MS/MS) techniques. The [M + 4H](4+) ions exhibit two major conformer types with collision cross sections of 418 Å(2) and 446 Å(2); the [M + 3H](3+) ions also yield two different conformer types having collision cross sections of 340 Å(2) and 367 Å(2). Kinetics plots of HDX for individual amino acid residues reveal fast- and slow-exchanging hydrogens. The contributions of each amino acid residue to the overall conformer type rate constant have been estimated. For this peptide, N- and C-terminal K residues exhibit the greatest contributions for all ion conformer types. Interior D and I residues show decreased contributions. Several charge state trends are observed. On average, the D residues of the [M + 3H](3+) ions show faster HDX rate contributions compared with [M + 4H](4+) ions. In contrast the interior I8 and I9 residues show increased accessibility to exchange for the more elongated [M + 4H](4+) ion conformer type. The contribution of each residue to the overall uptake rate showed a good correlation with a residue hydrogen accessibility score model calculated using a distance from charge site and initial incorporation site for nominal structures obtained from molecular dynamic simulations (MDS).

  17. Kinetics of the radiation-induced exchange reactions of H2, D2, and T2: a review

    International Nuclear Information System (INIS)

    Pyper, J.W.; Briggs, C.K.

    1978-01-01

    Mixtures of H 2 --T 2 or D 2 --T 2 will exchange to produce HT or DT due to catalysis by the tritium β particle. The kinetics of the reaction D 2 + T 2 = 2DT may play an important role in designing liquid or solid targets of D 2 --DT--T 2 for implosion fusion, and distillation schemes for tritium cleanup systems in fusion reactors. Accordingly, we have critically reviewed the literature for information on the kinetics and mechanism of radiation-induced self-exchange reactions among the hydrogens. We found data for the reaction H 2 + T 2 = 2HT in the gas phase and developed a scheme based on these data to predict the halftime to equilibrium for any gaseous H 2 + T 2 mixture at ambient temperature with an accuracy of +-10 percent. The overall order of the H 2 + T 2 = 2HT reaction is 1.6 based on an initial rate treatment of the data. The most probable mechanism for radiation-induced self-exchange reaction is an ion-molecule chain mechanism

  18. Kinetics of radioisotope exchange between brine and rock in a geothermal system

    International Nuclear Information System (INIS)

    Hammond, D.E.; Zukin, J.G.; Teh-Lung Ku

    1988-01-01

    A wide range of isotopes in the /sup 238/U, /sup 235/U, and /sup 232/Th decay chains was measured in geothermal brines collected from two production zones at 1898 and 3220 m in the Salton Sea Scientific Drilling Project well. High concentrations of radium, radon, and lead isotopes are generated and maintained by the input of these isotopes from solid phases into brine by both recoil and leaching processes, by the high chloride content of the brine which complexes radium and lead, and by the apparent absence of suitable unoccupied adsorption sites. In contrast, uranium, thorium, actinium, bismuth, and polonium isotopes all have low concentrations due to their efficient sorption from brine to rock. Measurements of short-lived isotopes in these decay series yield insights regarding the mechanisms controlling radioisotope exchange, and they permit estimation of rates of brine-rock interaction. For example, the /sup 228/Ac//sup 228/Ra activity ratio of 0.2 in brines indicates that the mean residence time of actinium in solution before sorption onto solid surfaces is less than 2.5 hours

  19. Growth kinetics of metastable (331) nanofacet on Au and Pt(110) surfaces

    International Nuclear Information System (INIS)

    Ndongmouo, U.T.; Houngninou, E.; Hontinfinde, F.

    2006-12-01

    A theoretical epitaxial growth model with realistic barriers for surface diffusion is investigated by means of kinetic Monte Carlo simulations to study the growth modes of metastable (331) nanofacets on Au and Pt(110) surfaces. The results show that under experimental atomic fluxes, the (331) nanofacets grow by 2D nucleation at low temperature in the submonolayer regime. A metastable growth phase diagram that can be useful to experimentalists is presented and looks similar to the one found for the stationary growth of the bcc(001) surface in the kinetic 6-vertex model. (author)

  20. Kinetic energy distributions of ions after surface collisions

    International Nuclear Information System (INIS)

    Short, R.T.; Todd, P.J.; Grimm, C.C.

    1991-01-01

    As a part of the development of an organic ion microprobe, to be used for imaging of particular organic compounds in biological tissue, various methods of quadrupole-based tandem mass spectroscopy (MS/MS) have been investigated. High transmission efficiency is essential for the success of the organic ion microprobe, due to expected low analyte concentrations in biological tissue and the potential for sample damage from prolonged exposure to the primary ion beam. MS/MS is necessary for organic ion imaging because of the complex nature of the biological matrices. The goal of these studies of was to optimize the efficiency of daughter ion production and transmission by first determining daughter ion properties and then designing ion optics based on those properties. The properties of main interest are daughter ion kinetic energy and angular distribution. 1 fig

  1. Features of the kinetics of heterogeneous reactions with phase transformations on catalyst surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Berman, A D; Krylov, O V

    1978-01-01

    This paper presents a review of 41 bibliographic references to experiments on the adsorption of various gases (e.g., carbon monoxide, formic acid, ammonia, and oxygen) on metals (e.g., nickel, molybdenum, and platinum) and oxides covers observations of two-dimensional phases during adsorption; the kinetics of adsorption and catalysis associated with two-dimensional phase transitions; and several approximate models for describing the kinetics of heterogeneous catalysis which account for two-dimensional phase transformations on catalyst surfaces.

  2. Kinetic bottlenecks to chemical exchange rates for deep-sea animals II: Carbon dioxide

    Science.gov (United States)

    Hofmann, A. F.; Peltzer, E. T.; Brewer, P. G.

    2012-11-01

    Increased ocean acidification from fossil fuel CO2 invasion, from temperature-driven changes in respiration, and from possible leakage from sub-seabed geologic CO2 disposal has aroused concern over the impacts of elevated CO2 concentrations on marine life. Discussion of these impacts has so far focused only on changes in the oceanic bulk fluid properties (ΔpH, Δ[∑CO2] etc.) as the critical variable and with a major focus on carbonate shell dissolution. Here we describe the rate problem for animals that must export CO2 at about the same rate at which O2 is consumed. We analyze the basic properties controlling CO2 export within the diffusive boundary layer around marine animals in an ocean changing in temperature (T) and CO2 concentration in order to compare the challenges posed by O2 uptake under stress with the equivalent problem of CO2 expulsion. The problem is more complex than that for a non-reactive gas since, as with gas exchange of CO2 at the air-sea interface, the influence of the ensemble of reactions within the CO2-HCO3--CO32- acid-base system needs to be considered. These reactions significantly facilitate CO2 efflux compared to O2 intake at equal temperature, pressure and flow rate under typical oceanic concentrations.The effect of these reactions can be described by an enhancement factor. For organisms, this means mechanically increasing flow over their surface to thin the boundary layer as is required to alleviate O2 stress seems not necessary to facilitate CO2 efflux. Nevertheless the elevated pCO2 cost most likely is non-zero. Regionally as with O2 the combination of T, P, and pH/pCO2 creates a zone of maximum CO2 stress at around 1000 m depth. But the net result is that, for the problem of gas exchange with the bulk ocean, the combination of an increasing T combined with declining O2 poses a greater challenge to marine life than does increasing CO2. The relationships developed here allow a more accurate prediction of the impacts on marine life

  3. The kinetics of tritium-hydrogen exchange in xanthosine, theobromine and monomethylated derivatives of xanthine

    International Nuclear Information System (INIS)

    Jelinska, M.; Szydlowski, J.; Sobkowski, J.

    1979-01-01

    Tritium exchange at C-8 of xanthosine, theobromine, 1-, 3-and 7-methylxanthine in water has been studied. The rates of detritiation of these compounds have been determined over a pH range at constant temperature. Several mechanisms of exchange involving various ionic forms of substrate operating at different pH have been suggested. (author)

  4. Kinetic Analysis of Lactose Exchange in Proteoliposomes Reconstituted with Purified lac Permease

    NARCIS (Netherlands)

    Lolkema, Julius S.; Carrasco, Nancy; Kaback, H. Ronald

    1991-01-01

    Lactose exchange catalyzed by purified lac permease reconstituted into proteoliposomes was analyzed with unequal concentrations of lactose on either side of the membrane and at low pH so as to prevent equilibration of the two pools. Exchange with external concentrations below 1.0 mM is a

  5. An experimental study on the effect of carbonic anhydrase on the oxygen isotope exchange kinetics and equilibrium in the carbonic acid system

    Science.gov (United States)

    Uchikawa, J.; Zeebe, R. E.

    2011-12-01

    Stable oxygen isotopes of marine biogenic carbonates are often depleted in 18O relative to the values expected for thermodynamic equilibrium with ambient seawater. One possibility is that 18O-depletion in carbonates is kinetically controlled. The kinetic isotope effect associated with the hydration of CO2 results in 18O-depleted HCO3-. If the HCO3- is utilized before re-establishing equilibrium with ambient water under rapid calcification, the 18O-depletion will be recorded in carbonates. But one caveat in this kinetic model is the fact that many marine calcifiers posses carbonic anhydrase, a zinc-bearing enzyme that catalyzes the CO2 hydration reaction. It is expected that this enzyme accelerates 18O-equilibration in the carbonic acid system by facilitating direct oxygen isotope exchange between HCO3- and H2O via CO2 hydration. Clearly this argues against the conceptual framework of the kinetic model. Yet the critical variable here is the effectiveness of the carbonic anhydrase, which is likely to depend on its concentration and the carbonate chemistry of the aqueous medium. It is also hitherto unknown whether the presence of carbonic anhydrase alters the equilibrium oxygen isotope fractionations between dissolved carbonate species and water. We performed a series of quantitative inorganic carbonate precipitation experiments to examine the changes in the oxygen isotope equilibration time as a function of carbonic anhydrase concentrations. We conducted experiments at pH 8.3 and 8.9. These pH values are similar to the average surface ocean pH and the elevated pH levels observed within calcification microenvironments of certain corals and planktonic foraminifera. A summary of our new experimental results will be presented.

  6. Air/surface exchange processes of mercury and their linkage to atmospheric pools

    International Nuclear Information System (INIS)

    Bahlmann, Enno; Ebinghaus, Ralf

    2001-01-01

    The atmospheric mercury cycle is strongly linked to the terrestrial, aquatic and biologic cycle of mercury via air/surface exchange processes. In order to quantify mercury fluxes from and to the atmosphere to predict local and regional source contributions the methods for flux measurements as well as the physicochemical factors controlling air/surface exchange processes must be assessed. We will describe methods for the determination of mercury and mercury species in ambient air which are basic for investigation of air/surface exchange processes. Further on we will describe approaches for studying the physicochemical factors controlling this processes by using a new laboratory flux measurement system. (author)

  7. Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path

    International Nuclear Information System (INIS)

    Opitz, Alexander K.; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Juergen

    2011-01-01

    Highlights: → Oxygen exchange kinetics of Pt on YSZ investigated by means of Pt model electrodes. → Two different geometry dependencies of the polarization resistance identified. → At higher temperatures the oxygen exchange reaction proceeds via a Pt surface path. → At lower temperatures a bulk path through the Pt thin film electrode is discussed. - Abstract: The oxygen exchange kinetics of platinum on yttria-stabilized zirconia (YSZ) was investigated by means of geometrically well-defined Pt microelectrodes. By variation of electrode size and temperature it was possible to separate two temperature regimes with different geometry dependencies of the polarization resistance. At higher temperatures (550-700 deg. C) an elementary step located close to the three phase boundary (TPB) with an activation energy of ∼1.6 eV was identified as rate limiting. At lower temperatures (300-400 deg. C) the rate limiting elementary step is related to the electrode area and exhibited a very low activation energy in the order of 0.2 eV. From these observations two parallel pathways for electrochemical oxygen exchange are concluded. The nature of these two elementary steps is discussed in terms of equivalent circuits. Two combinations of parallel rate limiting reaction steps are found to explain the observed geometry dependencies: (i) Diffusion through an impurity phase at the TPB in parallel to diffusion of oxygen through platinum - most likely along Pt grain boundaries - as area-related process. (ii) Co-limitation of oxygen diffusion along the Pt|YSZ interface and charge transfer at the interface with a short decay length of the corresponding transmission line (as TPB-related process) in parallel to oxygen diffusion through platinum.

  8. Thin film growth behaviors on strained fcc(111) surface by kinetic Monte Carlo

    International Nuclear Information System (INIS)

    Doi, Y; Matsunaka, D; Shibutani, Y

    2009-01-01

    We study Ag islands grown on strained Ag(111) surfaces using kinetic Monte Carlo (KMC) simulations. We employed KMC parameters of activation energy and attempt frequency estimated by nudged elastic band (NEB) method and vibration analyses. We investigate influences of surface strain and substrate temperature on film growth. As the biaxial surface strain increases, the island density increases. As temperature increases, the shape of the island changes from dendric to hexagonal and the island density increases.

  9. Ion Exchange Kinetics of CO2+ Ions In the Particles of Some Organic and Inorganic Sorbents

    International Nuclear Information System (INIS)

    El-Naggar, I.M.; Abou-Messalam, M.M; Shady, S.A.

    2000-01-01

    The rate of exchange and diffusion mechanism of Co 2+ and Zn 2+ on the hydrogen form of cerium (IV) antimonate Ce/Sb and polyacrylamide acrylic acid resin impregnated with zirconium phosphate p(A M-A A) Zr-P was determined at different reaction temperatures 25,45 and 60 degree. The exchange rate was controlled by a particle diffusion mechanism and a limited batch technique. The effective diffusion coefficients of exchange reactions, values of activation energies, entropy of activation have been calculated and were confirmed by the B t versus t plots

  10. Kinetic study on ligand exchange reaction between EC and 99mTc-GH

    International Nuclear Information System (INIS)

    Wu Chunying; Luo Shineng; Fang Ping; Huang Heyun; Xie Minhao; Meng Hong

    1995-01-01

    The ligand exchange reaction between EC and 99m Tc-GH and its influence factors such as concentrations of EC and pH were described. The concentration of EC has no influence on the exchange reaction rate constant, while pH is the most important influence factor. The rate constants of ligand exchange reaction at different pH values were determined. The results showed that in order to make the labelling yield of 99m Tc-EC higher than 90%, pH of the reaction must be higher than 8

  11. Kinetic electron emission from highly oriented pyrolytic graphite surfaces induced by singly charged ions

    CERN Document Server

    Cernusca, S; Winter, H; Aumayr, F; Loerincik, J; Sroubek, Z

    2002-01-01

    We present total electron yields determined by current measurements for normal impact of H sup + , H sub 2 sup + , H sub 3 sup + , C sup + , N sup + and O sup + ions (E<=10 keV) on a clean highly oriented pyrolytic graphite surface. The kinetic energy of the projectiles has been varied from near threshold up to 10 keV. By comparing the results to similar data obtained for a polycrystalline Au surface the role of different target properties for kinetic electron emission can be analysed.

  12. Kinetic investigation of the immobilization of chromotropic acid derivatives onto anion exchange resin

    Directory of Open Access Journals (Sweden)

    Savić Jasmina

    2007-01-01

    Full Text Available The adsorption kinetics of pyrazol- (РАСА and imidazol-azo-chromo-tropic acid (IACA onto Dowex 1-X8 resin, as a function of the dye concentration and temperature were investigated at pH 4.5. The pseudo-first- and second-order kinetic models and intraparticle diffusion model were used to describe the obtained kinetic data. The adsorption rate constants were found to be in the order of magnitude 10-2 min-1 for all of the used kinetics models. The adsorption capacity increases with increasing initial dye concentration. The study of adsorption kinetics at different temperatures (in the range from 5 to 25 °C reveals an increase in the rate of adsorption and adsorption capacity with increasing temperature. The activation energy (in the case of РАСА 16.6 kJ/mol, and for IACA 11.3 kJ/mol was determined using the Arrhenius dependence. Electrostatic interactions between the dye and resin beads were shown to be the adsorption mechanism.

  13. Kinetics of isotopic exchange between strontium polymolybdate and strontium ions in aqueous solution

    International Nuclear Information System (INIS)

    Atun, Gulten; Bilgin, Binay; Kilislioglu, Ayben

    2002-01-01

    A heterogeneous isotopic exchange reaction of strontium polymolybdate in strontium chloride solution was studied using 90 Sr as a tracer. The effects of low and high strontium chloride concentration on the rate and mechanism of the isotopic exchange reaction were investigated. It was found that, at high concentrations, the rate is independent of strontium concentration, but, at low concentrations, the rate is proportional to the strontium concentration. These results support a hypothesis that, at low concentrations, the rate is controlled by film diffusion, whereas at high concentrations it is controlled by particle diffusion. Experiments were performed at 293, 303 and 313 K. Activation energy of isotopic exchange reaction and thermodynamic parameters ΔH*, ΔS*, and ΔG* were calculated using the Arrhenius and Eyring equations. The results also indicated that recrystallization is a predominant factor in the present exchange reaction

  14. Kinetics of isotopic exchange between strontium polymolybdate and strontium ions in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Atun, Gulten E-mail: gultena@istanbul.edu.tr; Bilgin, Binay; Kilislioglu, Ayben

    2002-06-01

    A heterogeneous isotopic exchange reaction of strontium polymolybdate in strontium chloride solution was studied using {sup 90}Sr as a tracer. The effects of low and high strontium chloride concentration on the rate and mechanism of the isotopic exchange reaction were investigated. It was found that, at high concentrations, the rate is independent of strontium concentration, but, at low concentrations, the rate is proportional to the strontium concentration. These results support a hypothesis that, at low concentrations, the rate is controlled by film diffusion, whereas at high concentrations it is controlled by particle diffusion. Experiments were performed at 293, 303 and 313 K. Activation energy of isotopic exchange reaction and thermodynamic parameters {delta}H*, {delta}S*, and {delta}G* were calculated using the Arrhenius and Eyring equations. The results also indicated that recrystallization is a predominant factor in the present exchange reaction.

  15. CHEMICAL REACTIONS ON ADSORBING SURFACE: KINETIC LEVEL OF DESCRIPTION

    Directory of Open Access Journals (Sweden)

    P.P.Kostrobii

    2003-01-01

    Full Text Available Based on the effective Hubbard model we suggest a statistical description of reaction-diffusion processes for bimolecular chemical reactions of gas particles adsorbed on the metallic surface. The system of transport equations for description of particles diffusion as well as reactions is obtained. We carry out the analysis of the contributions of all physical processes to the formation of diffusion coefficients and chemical reactions constants.

  16. Surface properties, solubility and dissolution kinetics of bamboo phytoliths

    Science.gov (United States)

    Fraysse, Fabrice; Pokrovsky, Oleg S.; Schott, Jacques; Meunier, Jean-Dominique

    2006-04-01

    Although phytoliths, constituted mainly by micrometric opal, exhibit an important control on silicon cycle in superficial continental environments, their thermodynamic properties and reactivity in aqueous solution are still poorly known. In this work, we determined the solubility and dissolution rates of bamboo phytoliths collected in the Réunion Island and characterized their surface properties via electrophoretic measurements and potentiometric titrations in a wide range of pH. The solubility product of "soil" phytoliths ( pKsp0=2.74 at 25 °C) is equal to that of vitreous silica and is 17 times higher than that of quartz. Similarly, the enthalpy of phytoliths dissolution reaction (ΔHr25-80°C=10.85kJ/mol) is close to that of amorphous silica but is significantly lower than the enthalpy of quartz dissolution. Electrophoretic measurements yield isoelectric point pH IEP = 1.2 ± 0.1 and 2.5 ± 0.2 for "soil" (native) and "heated" (450 °C heating to remove organic matter) phytoliths, respectively. Surface acid-base titrations allowed generation of a 2-p K surface complexation model. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 2 ⩽ pH ⩽ 12, were found to be intermediate between those of quartz and vitreous silica. The dissolution rate dependence on pH was modeled within the concept of surface coordination theory using the equation: R=k1·{>SiOH2+}n+k2·{>SiOH0}+k3·{>SiO-}m, where {> i} stands for the concentration of the surface species present at the SiO 2-H 2O interface, ki are the rate constants of the three parallel reactions and n and m represent the order of the proton- and hydroxy-promoted reactions, respectively. It follows from the results of this study that phytoliths dissolution rates exhibit a minimum at pH ˜ 3. This can explain their good preservation in the acidic soil horizons of Réunion Island. In terms of silicon biogeochemical cycle, phytoliths represent a large buffering reservoir

  17. The impact of surface coverage on the kinetics of electron transfer through redox monolayers on a silicon electrode surface

    International Nuclear Information System (INIS)

    Ciampi, Simone; Choudhury, Moinul H.; Ahmad, Shahrul Ainliah Binti Alang; Darwish, Nadim; Brun, Anton Le; Gooding, J.Justin

    2015-01-01

    Graphical abstract: The impact of surface coverage on the kinetics of electron transfer through redox monolayers on a silicon electrode surface. ABSTRACT: The impact of the coverage of ferrocene moieties, attached to a silicon electrode modified via hydrosilylation of a dialkyne, on the kinetics of electron transfer between the redox species and the electrode is explored. The coverage of ferrocene is controlled by varying the coupling time between azidomethylferrocene and the distal alkyne of the monolayer via the copper assisted azide-alkyne cycloaddition reaction. All other variables in the surface preparation are maintained identical. What is observed is that the higher the surface coverage of the ferrocene moieties the faster the apparent rates of electron transfer. This surface coverage-dependent kinetic effect is attributed to electrons hopping between ferrocene moieties across the redox film toward hotspots for the electron transfer event. The origin of these hotspots is tentatively suggested to result from minor amounts of oxide on the underlying silicon surface that reduce the barrier for the electron transfer.

  18. Theory of kinetics and equilibrium of ion exchange-adsorption and mechanism of extracting uranium from sea-water with titanic gel

    International Nuclear Information System (INIS)

    Ai Hongtao

    1989-01-01

    An isothermal equation for ion exchange-adsorption is derived by mass action law. The equation can be used to sum up empirical and semiempirical formulas of the exchange adsorption, such as Gapon Equation, Sips Formula, Langmuir Equation and Freundlich Formula. In this paper, by adopting the ion exchange reaction to act as the determining step of the ion exchange adsorption kinetics, and exchange-adsorption kinetics equation is derived. It is verified by he results of a series of experiments in which uranium is extracted form enriched sea-water and natural sea-water with hydrous titanium oxide (titanic gel). This equation can be used to explain not only the results of test which have been applied to prove fast intraparticle diffusion of liquid film deffusion mechanism, but also test data which can be expalined by the co-controlling fast intraparticle and liquid film diffusion, and the kinetic data which can not be clarified by diffusion mechanism. It is proposed that the mechanism of the exchange adsorption of uranium from sea-water with titanic gel is a cationic exchange reaction. A method for calculating the quantity of exchange-adsorption at equilibrium is also given

  19. Second Harmonic Correlation Spectroscopy: Theory and Principles for Determining Surface Binding Kinetics.

    Science.gov (United States)

    Sly, Krystal L; Conboy, John C

    2017-06-01

    A novel application of second harmonic correlation spectroscopy (SHCS) for the direct determination of molecular adsorption and desorption kinetics to a surface is discussed in detail. The surface-specific nature of second harmonic generation (SHG) provides an efficient means to determine the kinetic rates of adsorption and desorption of molecular species to an interface without interference from bulk diffusion, which is a significant limitation of fluorescence correlation spectroscopy (FCS). The underlying principles of SHCS for the determination of surface binding kinetics are presented, including the role of optical coherence and optical heterodyne mixing. These properties of SHCS are extremely advantageous and lead to an increase in the signal-to-noise (S/N) of the correlation data, increasing the sensitivity of the technique. The influence of experimental parameters, including the uniformity of the TEM00 laser beam, the overall photon flux, and collection time are also discussed, and are shown to significantly affect the S/N of the correlation data. Second harmonic correlation spectroscopy is a powerful, surface-specific, and label-free alternative to other correlation spectroscopic methods for examining surface binding kinetics.

  20. Enolate Stabilization by Anion-π Interactions: Deuterium Exchange in Malonate Dilactones on π-Acidic Surfaces.

    Science.gov (United States)

    Miros, François N; Zhao, Yingjie; Sargsyan, Gevorg; Pupier, Marion; Besnard, Céline; Beuchat, César; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2016-02-18

    Of central importance in chemistry and biology, enolate chemistry is an attractive topic to elaborate on possible contributions of anion-π interactions to catalysis. To demonstrate the existence of such contributions, experimental evidence for the stabilization of not only anions but also anionic intermediates and transition states on π-acidic aromatic surfaces is decisive. To tackle this challenge for enolate chemistry with maximal precision and minimal uncertainty, malonate dilactones are covalently positioned on the π-acidic surface of naphthalenediimides (NDIs). Their presence is directly visible in the upfield shifts of the α-protons in the (1) H NMR spectra. The reactivity of these protons on π-acidic surfaces is measured by hydrogen-deuterium (H-D) exchange for 11 different examples, excluding controls. The velocity of H-D exchange increases with π acidity (NDI core substituents: SO2 R>SOR>H>OR>OR/NR2 >SR>NR2 ). The H-D exchange kinetics vary with the structure of the enolate (malonates>methylmalonates, dilactones>dithiolactones). Moreover, they depend on the distance to the π surface (bridge length: 11-13 atoms). Most importantly, H-D exchange depends strongly on the chirality of the π surface (chiral sulfoxides as core substituents; the crystal structure of the enantiopure (R,R,P)-macrocycle is reported). For maximal π acidity, transition-state stabilizations up to -18.8 kJ mol(-1) are obtained for H-D exchange. The Brønsted acidity of the enols increases strongly with π acidity of the aromatic surface, the lowest measured pKa =10.9 calculates to a ΔpKa =-5.5. Corresponding to the deprotonation of arginine residues in neutral water, considered as "impossible" in biology, the found enolate-π interactions are very important. The strong dependence of enolate stabilization on the unprecedented seven-component π-acidity gradient over almost 1 eV demonstrates quantitatively that such important anion-π activities can be expected only from

  1. Kinetics of Microstructure Evolution during Gaseous Thermochemical Surface Treatment

    DEFF Research Database (Denmark)

    Somers, Marcel A.J.; Christiansen, Thomas

    2005-01-01

    The incorporation of nitrogen or carbon in steel is widely applied to provide major improvements in materials performance with respect to fatigue, wear, tribology and atmospheric corrosion. These improvements rely on a modification of the surface adjacent region of the material, by the (internal...... and the interplay with mechanical stress. In the present article a few examples, covering research on the interaction of carbon and/or nitrogen with iron-based metals, are included to illustrate the various aspects of gas-metal interactions....

  2. Kinetics of electrophilic exchange of lanthanide(3) and copper(2) ions in aqueous solutions of ethylenediaminetetraacetates

    International Nuclear Information System (INIS)

    Nikitenko, S.I.; Martynenko, L.I.; Pechurova, N.I.; Spitsyn, V.I.

    1984-01-01

    Electrophilic exchange in the MA - - Cu 2+ (M 3+ =La 3+ , P 2 3+ , Nd 3+ , Eu 3+ , Gd 3+ , Tb 3+ , Er 3+ , Yb 3+ , A 4- =ethylenediaminetetraacetate) systems is studied. Copper is chosen as a constituent cation, because the stability of the CuA 2+ - complex is higher than that of the MA - complex, besides the CuA 2- , is characterized by a high extinction coefficient E 280 =3200. Electrophilic exchange in the systems is shown to be realized through the acid dissociation mechanism and through the association mechanism. Consideration of the acid dissociation mechanism assumes that the exchange is limited by a break in the metal-oxygen bond in the intermediate protonated complex. In case of the association mechanism it is limited by a break in the metal-nitrogen bond in the intermediate binuclear complex. Rate constants of the limiting stage are calculated. Dependences of the rate constants of exchange on the stability of the complexes, the order number of the element, acidity of medium, Cu 2+ concentration are given. Differences are shown to exist between the exchange mechanisms in the studied: systems for the REE of cerium and yttrium subgroups

  3. Combined Yamamoto approach for simultaneous estimation of adsorption isotherm and kinetic parameters in ion-exchange chromatography.

    Science.gov (United States)

    Rüdt, Matthias; Gillet, Florian; Heege, Stefanie; Hitzler, Julian; Kalbfuss, Bernd; Guélat, Bertrand

    2015-09-25

    Application of model-based design is appealing to support the development of protein chromatography in the biopharmaceutical industry. However, the required efforts for parameter estimation are frequently perceived as time-consuming and expensive. In order to speed-up this work, a new parameter estimation approach for modelling ion-exchange chromatography in linear conditions was developed. It aims at reducing the time and protein demand for the model calibration. The method combines the estimation of kinetic and thermodynamic parameters based on the simultaneous variation of the gradient slope and the residence time in a set of five linear gradient elutions. The parameters are estimated from a Yamamoto plot and a gradient-adjusted Van Deemter plot. The combined approach increases the information extracted per experiment compared to the individual methods. As a proof of concept, the combined approach was successfully applied for a monoclonal antibody on a cation-exchanger and for a Fc-fusion protein on an anion-exchange resin. The individual parameter estimations for the mAb confirmed that the new approach maintained the accuracy of the usual Yamamoto and Van Deemter plots. In the second case, offline size-exclusion chromatography was performed in order to estimate the thermodynamic parameters of an impurity (high molecular weight species) simultaneously with the main product. Finally, the parameters obtained from the combined approach were used in a lumped kinetic model to simulate the chromatography runs. The simulated chromatograms obtained for a wide range of gradient lengths and residence times showed only small deviations compared to the experimental data. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Stomatal clustering in Begonia associates with the kinetics of leaf gaseous exchange and influences water use efficiency.

    Science.gov (United States)

    Papanatsiou, Maria; Amtmann, Anna; Blatt, Michael R

    2017-04-01

    Stomata are microscopic pores formed by specialized cells in the leaf epidermis and permit gaseous exchange between the interior of the leaf and the atmosphere. Stomata in most plants are separated by at least one epidermal pavement cell and, individually, overlay a single substomatal cavity within the leaf. This spacing is thought to enhance stomatal function. Yet, there are several genera naturally exhibiting stomata in clusters and therefore deviating from the one-cell spacing rule with multiple stomata overlaying a single substomatal cavity. We made use of two Begonia species to investigate whether clustering of stomata alters guard cell dynamics and gas exchange under different light and dark treatments. Begonia plebeja, which forms stomatal clusters, exhibited enhanced kinetics of stomatal conductance and CO2 assimilation upon light stimuli that in turn were translated into greater water use efficiency. Our findings emphasize the importance of spacing in stomatal clusters for gaseous exchange and plant performance under environmentally limited conditions. © The Author 2017. Published by Oxford University Press on behalf of the Society for Experimental Biology.

  5. Comparison of molecular dynamics and kinetic modeling of gas-surface interactions

    NARCIS (Netherlands)

    Frezzotti, A.; Gaastra - Nedea, S.V.; Markvoort, A.J.; Spijker, P.; Gibelli, L.

    2008-01-01

    The interaction of a dilute monatomic gas with a solid surface is studied byMolecular Dynamics (MD) simulations and by numerical solutions of a recently proposed kinetic model. Following previous investigations, the heat transport between parallel walls and Couette flow have been adopted as test

  6. Thermal-hydraulic performance of the finned surface of a compact heat exchanger

    International Nuclear Information System (INIS)

    Errasti Cabrera, Michel

    2015-01-01

    In this work the thermal-hydraulic behavior of the finned surface of a compact heat exchanger is obtained in tube-fin configuration corrugated (wavy). Through numerical simulation are determined average values ​​of intensification of heat transfer and pressure loss in the inter-channel finned. The objective is to characterize the surface to use as a reference, to make comparisons with other heat exchange surfaces enhanced using traditional techniques combined with more current, such as vortex generators. The study is conducted in laminar flow, with Reynolds numbers below 1000. In the working model compact exchanger tubes and corrugated fins (wavy) heat is described, and the results of the coefficient of overall heat transfer and the pressure drop are explained from the local characteristics of the velocity field and temperature inside the heat exchanger. (Full text)

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

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Gang; Wang, Yu; Wang, Junzhuan; Pan, Lijia; Yu, Linwei; Zheng, Youdou; Shi, Yi, E-mail: yshi@nju.edu.cn

    2017-08-31

    Highlights: • The KMC method is adopted to investigate the relationships between surface evolution and hydrogen thermal treatment conditions. • The reduction in surface roughness is divided into two stages at relatively low temperatures, both exhibiting exponential dependence on the time. • The optimized surface structure can be obtained by precisely adjusting thermal treatment temperatures and hydrogen pressures. - Abstract: The evolution of a two-dimensional silicon surface under hydrogen thermal treatment is studied by kinetic Monte Carlo simulations, focusing on the dependence of the migration behaviors of surface atoms on both the temperature and hydrogen pressure. We adopt different activation energies to analyze the influence of hydrogen pressure on the evolution of surface morphology at high temperatures. The reduction in surface roughness is divided into two stages, both exhibiting exponential dependence on the equilibrium time. Our results indicate that a high hydrogen pressure is conducive to obtaining optimized surfaces, as a strategy in the applications of three-dimensional devices.

  8. Making waves: Kinetic processes controlling surface evolution during low energy ion sputtering

    International Nuclear Information System (INIS)

    Chan, W.L.; Chason, Eric

    2007-01-01

    When collimated beams of low energy ions are used to bombard materials, the surface often develops a periodic pattern or ''ripple'' structure. Different types of patterns are observed to develop under different conditions, with characteristic features that depend on the substrate material, the ion beam parameters, and the processing conditions. Because the patterns develop spontaneously, without applying any external mask or template, their formation is the expression of a dynamic balance among fundamental surface kinetic processes, e.g., erosion of material from the surface, ion-induced defect creation, and defect-mediated evolution of the surface morphology. In recent years, a comprehensive picture of the different kinetic mechanisms that control the different types of patterns that form has begun to emerge. In this article, we provide a review of different mechanisms that have been proposed and how they fit together in terms of the kinetic regimes in which they dominate. These are grouped into regions of behavior dominated by the directionality of the ion beam, the crystallinity of the surface, the barriers to surface roughening, and nonlinear effects. In sections devoted to each type of behavior, we relate experimental observations of patterning in these regimes to predictions of continuum models and to computer simulations. A comparison between theory and experiment is used to highlight strengths and weaknesses in our understanding. We also discuss the patterning behavior that falls outside the scope of the current understanding and opportunities for advancement

  9. Oxygen isotope exchange kinetics between coexistent minerals and water in the Ertaibei granite pluton, northern Xinjiang

    Institute of Scientific and Technical Information of China (English)

    刘伟; 李志安; 赵志忠

    1996-01-01

    Coexistent minerals quartz, feldspar and biotite vary widely in δ18O value and display remarkable 18O/16O disequilibrium relations in the Ertaibei granite pluton, northern Xinjiang. The 18O/16O exchange reaction definitely occurred between granite and water. Initial δ18O values of the granite and exotic water are evaluated by the mass balance consideration. The results show that the 18O/16O exchange reaction is not necessarily accompanied by what geologists describe as petrological and mineralogiesl alteration effects, indicating that the exchange reaction occurs at a comparatively high temperature during subsolidus cooling of magmas. Exchange mechanism is mainly controlled by diffusion. It is demonstrated through quantitative modelling that the hydrothermal system associated with the Ertaibei pluton lived for 0.8-3 Ma, with a fluid flow rate of 3 × 10-14 mol · s-1 and water/rock (W/R) ratio of 0.79 - 3.08. Flow path and initial heterogeneity of the exotic metamorphic fluid are modelled with the δ1

  10. Dual Studies on a Hydrogen-Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect

    Science.gov (United States)

    Giles, Richard; Kim, Iris; Chao, Weyjuin Eric; Moore, Jennifer; Jung, Kyung Woon

    2014-01-01

    An efficient laboratory experiment has been developed for undergraduate students to conduct hydrogen-deuterium (H-D) exchange of resorcinol by electrophilic aromatic substitution using D[subscript 2]O and a catalytic amount of H[subscript 2]SO[subscript 4]. The resulting labeled product is characterized by [superscript 1]H NMR. Students also…

  11. Complex ion kinetics. Reaction rates on ion-exchange resins compared to those in water

    International Nuclear Information System (INIS)

    Liss, I.B.; Murmann, R.K.

    1975-01-01

    A comparison has been made between the rates in water and on an ion-exchange resin for the aquation of [(NH 3 ) 5 CoOReO 3 ] 2+ and [(H 2 O) 5 CrCl] 2+ and for the 18 O isotopic exchange of water with [(NH 3 ) 5 Co(OH 2 )] 3+ and ReO 4 - . The rate of water exchange on [(NH 3 ) 5 Co(OH 2 )] 3+ was not changed by association with Dowex 50W resins. Aquation of [(NH 3 ) 5 CoOReO 3 ] 2+ and water exchange on ReO 4 - had modified pH dependencies when associated with a resin. With the cobalt complex the rates were faster on the resin in the acidic region and slower on the resin in the basic region. A new term in the rate equation was observed when ReO 4 - was on the resin, first order in H + , while the other terms appear to be unchanged. Aquation of [(H 2 O) 5 CrCl] 2+ was much slower when it was absorbed on the resin. This was related to the known ionic strength effect of the reaction. (auth)

  12. Analytical Description of the H/D Exchange Kinetic of Macromolecule.

    Science.gov (United States)

    Kostyukevich, Yury; Kononikhin, Alexey; Popov, Igor; Nikolaev, Eugene

    2018-04-17

    We present the accurate analytical solution obtained for the system of rate equations describing the isotope exchange process for molecules containing an arbitrary number of equivalent labile atoms. The exact solution was obtained using Mathematica 7.0 software, and this solution has the form of the time-dependent Gaussian distribution. For the case when forward exchange considerably overlaps the back exchange, it is possible to estimate the activation energy of the reaction by obtaining a temperature dependence of the reaction degree. Using a previously developed approach for performing H/D exchange directly in the ESI source, we have estimated the activation energies for ions with different functional groups and they were found to be in a range 0.04-0.3 eV. Since the value of the activation energy depends on the type of functional group, the developed approach can have potential analytical applications for determining types of functional groups in complex mixtures, such as petroleum, humic substances, bio-oil, and so on.

  13. Working-state Morphologies of Ion Exchange Catalysts and Their Influence on Reaction Kinetics

    Czech Academy of Sciences Publication Activity Database

    Jeřábek, Karel; Hanková, Libuše; Holub, Ladislav

    2010-01-01

    Roč. 333, 1-2 (2010), s. 109-113 ISSN 1381-1169 Grant - others:DCH(US) BD20 Institutional research plan: CEZ:AV0Z40720504 Keywords : ion exchanger catalyst * morphology * esterification Subject RIV: CC - Organic Chemistry Impact factor: 2.872, year: 2010

  14. Application of tracer isotope in kinetic study of first order ion exchange reaction

    International Nuclear Information System (INIS)

    Lokhande, R.S.; Singare, P.U.

    1998-01-01

    Analysis of first order ion exchange reaction rates at different temperatures (27 deg- 48 degC) and particularly at low concentration of potassium iodide solution (electrolyte) ranging from 0.005 M to 0.040 M is carried out by application of radioactive tracer isotope 131 I. With increase in concentration of electrolyte, amount of iodide ion exchanged in millimoles increases. Specific reaction rates of ion exchange reaction are calculated for different temperatures and for different amount of ion exchange resins. It is observed that with increase in temperature, reaction rate increases but the increase is more pronounced for increase in amount of ion exchange resins. For 0.005 M solution of electrolyte, the reaction rate increases from 0.121 min -1 at 27 degC to 0.178 min -1 at 48 degC. For 0.005 M solution of electrolyte the reaction rate increases from 0.121 min -1 at 27 degC to 0.178 min 1 at 48 degC. For 0.005 M solution of electrolyte at 27 degC the reaction rate increases from 0.121 min -1 for 1.0 g of resin to 0.368 min -1 for 5.0 g of resin. From the reaction rates calculated at different temperatures, energy of activation in kJ/mole is calculated. It is observed that for 0.005 M solution of electrolyte, energy of activation is 4.62 kJ/mole which decreases to 2.87 kJ/mole for increase in concentration of electrolyte to 0.100 M. (author)

  15. Kinetics of final stages of spreading of melts on solid surfaces

    International Nuclear Information System (INIS)

    Khlynov, V.V.; Pastukhov, B.A.; Bokser, Eh.L.

    1978-01-01

    Kinetics of the spreading of Fe, Ni and Co melts over the surface of W-Re alloy (27% Re) was studied at 1580, 1500 and 1540 deg C, respectively. The time variant wetting spot radius and wetting angle were recorded using a modified Langmuir's method. Kinetic equations of the propagation of liquid interfacial layer and of the wetting, satisfactorily describing the obtained experimental data, have been derived. The melts have been found to spread by viscous flow and by migration atoms in small regions adjacent to the wetting perimeter

  16. Rate theory of solvent exchange and kinetics of Li+ − BF4−/PF6− ion pairs in acetonitrile

    International Nuclear Information System (INIS)

    Dang, Liem X.; Chang, Tsun-Mei

    2016-01-01

    In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li + and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li + in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li + -[BF 4 ] and Li + -[PF 6 ] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li + . We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li + -[BF 4 ] and Li + -[PF 6 ] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.

  17. Isotope exchange kinetic of phosphorus in soils from Pernambuco State -Brazil; Cinetica de diluicao isotopica de fosforo em solos de Pernambuco

    Energy Technology Data Exchange (ETDEWEB)

    Figueiredo, F J.B. de

    1989-12-01

    The applicability of isotopic exchange kinetics of {sup 32} p to characterize phosphorus available to plants and to diagnose the reactivity of soil-fertilizer-P in six soils from Pernambuco is described. This methodology was compared with anion exchange resin, isotopic exchange equilibrium methods (E-value and L-value) and P absorption by plants. The first greenhouse experiment had the following treatments: (1) with P and, (2) with addition of 43.7 mg P/Kg of soil, incubated for O, 42 and 84 days before seeding. The kinetic of isotopic exchange (KIE), resin-P and E-value were determined before seeding and after harvesting pearl millet grown for 42 days. Results indicated that the KIE parameters rated the soils more efficiently, in terms of available P and soil-fertilizer-P reactivity, than resin-P, E-value and L-value. (author). 38 refs, 2 figs, 18 tabs.

  18. Radiation exchange factors between specular inner surfaces of a rectangular enclosure such as transplant production unit

    International Nuclear Information System (INIS)

    Abdel-Ghany, Ahmed M.; Kozai, Toyoki

    2006-01-01

    General mathematical relations are presented for the specular exchange factors, F S , of diffuse radiation exchange between the inner surfaces of a rectangular enclosure. Three of these surfaces are specular reflectors, diffuse emitters and the fourth surface is a diffuse reflector, diffuse emitter. This enclosure can be used as a transplant production unit with artificial lighting for electric energy saving purposes. An image system and the crossed string method are used to derive these relations. The resulting expressions are conceptually simple and similar to the commonly known expressions of the exchange factors between diffuse surfaces, F. The accuracy of the presented F S relations was examined for different numbers of multiple reflections, N, on the specular surfaces and for different aspect ratios (ratio of the width, w to the height, h). The results proved that the relations are accurate and strongly satisfy the well-known relation of the radiation exchange between enclosure surfaces and satisfy the reciprocity relation. For any aspect ratio, considering N of 150 between highly reflective surfaces (ρ = 0.99) is sufficient to estimate the F S factors without any possible error. Using specular reflecting surfaces in such cases significantly reduces the electric energy consumption used for lighting

  19. Surface area of antimony oxide by isotope exchange and other methods

    Energy Technology Data Exchange (ETDEWEB)

    Rao, Y.K.; Acharya, B.V.; Rangamannar, B.

    1985-06-17

    Specific surface areas of antimony oxide samples, one commercial, the other prepared from antimony trichloride were measured by heterogeneous isotope exchange, gas adsorption, air permeability and microscopic methods. Specific surface areas obtained by these four methods for the two samples were compared and the observed differences are explained.

  20. Effect of microwave-assisted heating on chalcopyrite leaching of kinetics, interface temperature and surface energy

    Directory of Open Access Journals (Sweden)

    Tong Wen

    Full Text Available The microwave-assisted leaching was a new approach to intensify the copper recovery from chalcopyrite by hydrometallurgy. In this work, the effect of microwave-assisted heating on chalcopyrite leaching of kinetics, interfacial reaction temperature and surface energy were investigated. The activation energy of chalcopyrite leaching was affected indistinctively by the microwave-assisted heating (39.1 kJ/mol compared with the conventional heating (43.9 kJ/mol. However, the boiling point of the leaching system increased through microwave-assisted heating. Because of the improved boiling point and the selective heating of microwave, the interfacial reaction temperature increased significantly, which gave rise to the increase of the leaching recovery of copper. Moreover, the surface energy of the chalcopyrite through microwave-assisted heating was also enhanced, which was beneficial to strengthen the leaching of chalcopyrite. Keywords: Microwave-assisted heating, Chalcopyrite, Leaching kinetics, Interface temperature, Surface energy

  1. Influence of radioactivity on surface charging and aggregation kinetics of particles in the atmosphere.

    Science.gov (United States)

    Kim, Yong-Ha; Yiacoumi, Sotira; Lee, Ida; McFarlane, Joanna; Tsouris, Costas

    2014-01-01

    Radioactivity can influence surface interactions, but its effects on particle aggregation kinetics have not been included in transport modeling of radioactive particles. In this research, experimental and theoretical studies have been performed to investigate the influence of radioactivity on surface charging and aggregation kinetics of radioactive particles in the atmosphere. Radioactivity-induced charging mechanisms have been investigated at the microscopic level, and heterogeneous surface potential caused by radioactivity is reported. The radioactivity-induced surface charging is highly influenced by several parameters, such as rate and type of radioactive decay. A population balance model, including interparticle forces, has been employed to study the effects of radioactivity on particle aggregation kinetics in air. It has been found that radioactivity can hinder aggregation of particles because of similar surface charging caused by the decay process. Experimental and theoretical studies provide useful insights into the understanding of transport characteristics of radioactive particles emitted from severe nuclear events, such as the recent accident of Fukushima or deliberate explosions of radiological devices.

  2. Potential energy surfaces for nucleon exchanging in dinuclear systems

    International Nuclear Information System (INIS)

    Li Jianfeng; Xu Hushan; Li Wenfei; Zuo Wei; Li Junqing; Wang Nan; Zhao Enguang

    2003-01-01

    The experimental measurements have provided the evidence that the suppression of fusion cross-section caused by quasi-fission is very important for the synthesis of super-heavy nuclei by heavy ion collisions. The potential energy surface due to the nucleon transfer in the collision process is the driven potential, which governs the nucleon transfer, so that governs the competition between the fusion and quasi-fission. The dinuclear system potential energy surface also gives the information about the optimum projectile-target combination, as well as the optimum excitation energy for the synthesis of super-heavy nuclei by heavy ion collisions

  3. Radiation exchange between persons and surfaces for building energy simulations

    DEFF Research Database (Denmark)

    Vorre, Mette Havgaard; Jensen, Rasmus Lund; Dreau, Jerome Le

    2015-01-01

    Thermal radiation within buildings is a significant component of thermal comfort. Typically the methods applied for calculating view factors between a person and its building surfaces requires great computational time. This research developed a view factor calculation method suitable for building...

  4. Kinetic Monte Carlo simulation of surface segregation in Pd–Cu alloys

    International Nuclear Information System (INIS)

    Cheng, Feng; He, Xiang; Chen, Zhao-Xu; Huang, Yu-Gai

    2015-01-01

    The knowledge of surface composition and atomic arrangement is prerequisite for understanding of catalytic properties of an alloy catalyst. Gaining such knowledge is rather difficult, especially for those possessing surface segregation. Pd–Cu alloy is used in many fields and possesses surface segregation. In this paper kinetic Monte Carlo method is used to explore the surface composition and structure and to examine the effects of bulk composition and temperature on the surface segregation of Pd–Cu alloys. It is shown that the segregation basically completes within 900 s at 500 K. Below 900 K and within 20 min the enriched surface Cu atoms mainly come from the top five layers. For the first time we demonstrate that there exists a “bulk-inside flocking” or clustering phenomenon (the same component element congregates in bulk) in Pd–Cu alloys. Our results indicate that for alloys with higher Cu content there are small Pd ensembles like monomers, dimers and trimers with contiguous subsurface Pd atoms. - Highlights: • Kinetic Monte Carlo was first used to study surface segregation of Pd–Cu alloys. • Bulk-inside flocking (the same component element congregates in bulk) was observed. • Small Pd ensembles with contiguous subsurface Pd exist on surfaces of Cu-rich alloys

  5. Kinetic Monte Carlo simulation of surface segregation in Pd–Cu alloys

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Feng [Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Key Laboratory of Mesoscopic Chemistry of MOE, Nanjing University (China); He, Xiang [Nanjing Institute of Geography and Limnology, Chinese Academy of Sciences, Nanjing 210008 (China); Chen, Zhao-Xu, E-mail: zxchen@nju.edu.cn [Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Key Laboratory of Mesoscopic Chemistry of MOE, Nanjing University (China); Huang, Yu-Gai [Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Key Laboratory of Mesoscopic Chemistry of MOE, Nanjing University (China); JiangSu Second Normal University, Nanjing (China)

    2015-11-05

    The knowledge of surface composition and atomic arrangement is prerequisite for understanding of catalytic properties of an alloy catalyst. Gaining such knowledge is rather difficult, especially for those possessing surface segregation. Pd–Cu alloy is used in many fields and possesses surface segregation. In this paper kinetic Monte Carlo method is used to explore the surface composition and structure and to examine the effects of bulk composition and temperature on the surface segregation of Pd–Cu alloys. It is shown that the segregation basically completes within 900 s at 500 K. Below 900 K and within 20 min the enriched surface Cu atoms mainly come from the top five layers. For the first time we demonstrate that there exists a “bulk-inside flocking” or clustering phenomenon (the same component element congregates in bulk) in Pd–Cu alloys. Our results indicate that for alloys with higher Cu content there are small Pd ensembles like monomers, dimers and trimers with contiguous subsurface Pd atoms. - Highlights: • Kinetic Monte Carlo was first used to study surface segregation of Pd–Cu alloys. • Bulk-inside flocking (the same component element congregates in bulk) was observed. • Small Pd ensembles with contiguous subsurface Pd exist on surfaces of Cu-rich alloys.

  6. Plasma surface functionalization and dyeing kinetics of Pan-Pmma copolymers

    OpenAIRE

    Labay, C.; Canal, C.; Rodríguez, C.; Caballero, G.; Canal, J.M.

    2013-01-01

    Fiber surface modification with air corona plasma has been studied through dyeing kinetics under isothermal conditions at 30 °C on an acrylic-fiber fabric with a cationic dye (CI Basic Blue 3) analyzing the absorption, desorption and fixing on the surface of molecules having defined cationic character. The initial dyeing rate in the first 60 s indicates an increase of 58.3% in the dyeing rate due to the effect of corona plasma on the acrylic fiber surface. At the end of the dyeing process...

  7. Kinetics and equilibrium adsorption studies of dimethylamine (DMA) onto ion-exchange resin

    International Nuclear Information System (INIS)

    Hu Qinhai; Meng Yuanyuan; Sun Tongxi; Mahmood, Qaisar; Wu Donglei; Zhu Jianhang; Lu, George

    2011-01-01

    The fine grained resin ZGSPC106 was used to adsorb dimethylamine (DMA) from aqueous solution in the present research. Batch experiments were performed to examine the effects of initial pH of solution and agitation time on the adsorption process. The thermodynamics and kinetics of adsorption were also analyzed. The maximum adsorption was found at natural pH of DMA solution and equilibrium could be attained within 12 min. The equilibrium adsorption data were conformed satisfactorily to the Langmuir equation. The evaluation based on Langmuir isotherm gave the maximal static saturated adsorption capacity of 138.89 mg/g at 293 K. Various thermodynamic parameters such as free energy (ΔG o ), enthalpy (ΔH o ) and entropy (ΔS o ) showed that the adsorption was spontaneous, endothermic and feasible. DMA adsorption on ZGSPC106 fitted well to the pseudo-second-order kinetic model. Furthermore, the adsorption mechanism was discussed by Fourier transform infrared spectroscopy (FT-IR) analysis.

  8. SurfKin: an ab initio kinetic code for modeling surface reactions.

    Science.gov (United States)

    Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K

    2014-10-05

    In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts. Copyright © 2014 Wiley Periodicals, Inc.

  9. The kinetics of formation and transformation of silver atoms on solid surfaces subjected to ionizing irradiation

    International Nuclear Information System (INIS)

    Popovich, G.M.

    1988-01-01

    The paper discusses the results obtained in ESR-assisted studies of the kinetics of formation and transformation of silver atoms generated by γ-irradiation of silver-containing carriers. Three types of dependences have been established: (1) extreme; (2) saturation curves and (3) step-like. All the kinetic curves display, after a definite period of time, stable concentrations of adsorbed silver atoms per unit of the surface at a given temperature. Depending on the temperature of the experiment, the composition and nature of the carrier, the number of adsorbed silver ions, the irradiation dose and conditions of the experiment, a stable concentration of silver atoms at a given temperature may be equal to, higher or lower than the number of silver atoms measured immediately after γ-irradiation at a temperature of liquid nitrogen. A kinetic scheme is proposed to explain the obtained curves. The model suggests that the silver atoms adsorbed on the surface, as well as those formed after γ-irradiation, are bonded to the surface by various energies, which are related to heterogeneity of the carrier surface. (author)

  10. Predicting the bioavailability of phosphorus in soil amended with phosphate rocks using isotopic exchange kinetics

    International Nuclear Information System (INIS)

    Mohammad Edwin Syah Lubis; Zaharah Abd Rahman; Sharifuddin Abd Hamid

    1997-01-01

    Investigations on plant responses to applications of various forms and rates of P fertilizers usually involve glasshouse and/or field experiments. This traditional procedure assumes that whatever the soil-fertilizer-plant system, increase in total P uptake by plant between no P treatment (control) and fertilizer treatment equals the plant P uptake from fertilizer. This study uses the isotopic exchange techniques in the laboratory to predict bioavailability of P fertilizers without the need to conduct glasshouse or field experiments. Serdang series soil (Typic Paleudult) was incubated with 7 sources of P fertilizers comprising of triple superhosphate (TSP) and phosphate rocks from North Carolina (NCPR), Algeria (APR), Tunisia (TPR), Jordan (JPR), Christmas Island (CIPR) and China (CPR) at the rates of 0, 2, 4, 6 and 8g Kg-' soil with 20% moisture content at room temperature in three replications. The soils were sampled at 1, 3, 6 and 9 months after incubation and isotopically exchangeable p determined by the method of Fardeau and Jappe (1976). Intensity, quantity and capacity factors of soil P were calculated and the residual availability of these fertilizers were predicted. Phosphorus in solution was highest in TSP treated soil for all treatments. Among the phosphate rocks, NCPR at rate 8g kg-' soil gave the highest value while, CPR at rate 2 gave the lowest value. Thus showing that these PRs have different reactivities in this soil, where NCPR, APR, TPR and JPR were the reactive PR, while CIPR and CPR were the unreactive ones. The isotopically exchangeable P at one minute (1) in the soil sampled 9 months after incubation was found to correlate very well with plant P uptake by oil palm seedlings grown under the same conditions. Calculations made on the percentage of P derived from these fertilizers up to a period of more than one year after application showed that the reactive PRs to have more residual P made available to plants than the unreactive PR

  11. Kinetic Study of Esterification of Acetic Acid with n-butanol and isobutanol Catalyzed by Ion Exchange Resin

    Directory of Open Access Journals (Sweden)

    Amrit Pal Toor

    2011-05-01

    Full Text Available Esters are an important pharmaceutical intermediates and very useful perfumery agents. In this study the esterification of acetic acid with n-butanol and iso-butanol over an acidic cation exchange resin, Amberlyst 15 were carried out. The effects of certain parameters such as temperature, catalyst loading, initial molar ratio between reactants on the rate of reaction were studied. The experiments were conducted in a stirred batch reactor in the temperature range of 351.15 K to 366.15K.Variation of parameters on rate of reaction demonstrated that the reaction was intrinsically controlled.The activation energy for the esterification of acetic acid with n-butanol and iso butanol is found to be 28.45 k J/mol and 23.29 kJ/mol respectively. ©2011 BCREC UNDIP. All rights reserved.(Received: 16th December 2010, Revised: 19th March 2011; Accepted: 7th April 2011[How to Cite: A.P. Toor, M. Sharma, G. Kumar, and R. K. Wanchoo. (2011. Kinetic Study of Esterification of Acetic Acid with n-butanol and isobutanol Catalyzed by Ion Exchange Resin. Bulletin of Chemical Reaction Engineering and Catalysis, 6(1: 23-30. doi:10.9767/bcrec.6.1.665.23-30][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.1.665.23-30 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/665 ] | View in 

  12. Kinetics of solid-phase in ion exchange on tin hydrogen phosphate

    International Nuclear Information System (INIS)

    Kislitsyn, M.N.; Ketsko, V.A.; Yaroslavtsev, A.B.

    2004-01-01

    Solid state reactions in mixture of tin hydrogen phosphate and alkali metal (M=Na, K, Cs) chlorides have been studied both in the mode of polythermal heating and at a fixed temperature, using data of X-ray phase and thermogravimetric analyses. In the range 400-750 Deg C solid state ion exchange reactions occur in the systems studied and yield mono-- and dialkali phosphates MHSn(PO 4 ) 2 and M 2 Sn(PO 4 ) 2 . Counter diffusion coefficients for alkali metal cations and protons in the matrices of compositions MHSn(PO 4 ) 2 and M 2 Sn(PO 4 ) 2 have been determined [ru

  13. The role of cell walls and pectins in cation exchange and surface area of plant roots.

    Science.gov (United States)

    Szatanik-Kloc, A; Szerement, J; Józefaciuk, G

    2017-08-01

    We aimed to assess role of cell walls in formation of cation exchange capacity, surface charge, surface acidity, specific surface, water adsorption energy and surface charge density of plant roots, and to find the input of the cell wall pectins to the above properties. Whole roots, isolated cell walls and the residue after the extraction of pectins from the cell walls of two Apiaceae L. species (celeriac and parsnip) were studied using potentiometric titration curves and water vapor adsorption - desorption isotherms. Total amount of surface charge, as well as the cation exchange capacity were markedly higher in roots than in their cell walls, suggesting large contribution of other cell organelles to the binding of cations by the whole root cells. Significantly lower charge of the residues after removal of pectins was noted indicating that pectins play the most important role in surface charge formation of cell walls. The specific surface was similar for all of the studied materials. For the separated cell walls it was around 10% smaller than of the whole roots, and it increased slightly after the removal of pectins. The surface charge density and water vapor adsorption energy were the highest for the whole roots and the lowest for the cell walls residues after removal of pectins. The results indicate that the cell walls and plasma membranes are jointly involved in root ion exchange and surface characteristics and their contribution depends upon the plant species. Copyright © 2017 Elsevier GmbH. All rights reserved.

  14. Performance analyses of helical coil heat exchangers. The effect of external coil surface modification on heat exchanger effectiveness

    Science.gov (United States)

    Andrzejczyk, Rafał; Muszyński, Tomasz

    2016-12-01

    The shell and coil heat exchangers are commonly used in heating, ventilation, nuclear industry, process plant, heat recovery and air conditioning systems. This type of recuperators benefits from simple construction, the low value of pressure drops and high heat transfer. In helical coil, centrifugal force is acting on the moving fluid due to the curvature of the tube results in the development. It has been long recognized that the heat transfer in the helical tube is much better than in the straight ones because of the occurrence of secondary flow in planes normal to the main flow inside the helical structure. Helical tubes show good performance in heat transfer enhancement, while the uniform curvature of spiral structure is inconvenient in pipe installation in heat exchangers. Authors have presented their own construction of shell and tube heat exchanger with intensified heat transfer. The purpose of this article is to assess the influence of the surface modification over the performance coefficient and effectiveness. The experiments have been performed for the steady-state heat transfer. Experimental data points were gathered for both laminar and turbulent flow, both for co current- and countercurrent flow arrangement. To find optimal heat transfer intensification on the shell-side authors applied the number of transfer units analysis.

  15. Beneficial Effect of Surface Decorations on the Surface Exchange of Lanthanum Strontium Ferrite and Dual Phase Composites

    DEFF Research Database (Denmark)

    Ovtar, Simona; Søgaard, Martin; Song, Jia

    2016-01-01

    . These perovskites possess a mixed ionic and electronic conductivity (MIEC), which can be highly beneficial for the processes on oxygen electrode surfaces. The oxygen transport through a MIEC is determined by the rate of the oxygen exchange over the gas-solid interface and the diffusivity of oxide ions and electrons...

  16. Kinetics of exchange reaction between neodymium(3) transcyclohexanediaminetetraacetate and europium(3)- and holmium(3) aquo-ions in the H2O and D2O solutions

    International Nuclear Information System (INIS)

    Nikitenko, S.I.; Martynenko, L.I.; Pechurova, N.I.; Spitsyn, V.I.

    1983-01-01

    The exchange reaction between central ions in the NdD - Ln' 3+ systems, where Ln' 3+ is a substituting cation (Eu 3+ and Ho 3+ , D 4 =cyclohexanediaminetetraacetate) is studied and the electrophilic suhstitution mechanism is considered. To study the kinetic isotope effects, the reagents have been solVed in heavy water containing 99.9% D 2 O. The electrophilic substitution in the indicated systems proceeds through the dissociative mechanism catalyzed by protons and via the spontaneous dissociation mechanism. The exchange via the acid-catalyzed mechanism is limited by the intermediate protonated complex decay. The associative mechanism of the electrophilic exchange in the studied systems is not realized

  17. Surface modification of a proton exchange membrane and hydrogen storage in a metal hydride for fuel cells

    Science.gov (United States)

    Andrews, Lisa

    Interest in fuel cell technology is rising as a result of the need for more affordable and available fuel sources. Proton exchange membrane fuel cells involve the catalysis of a fuel to release protons and electrons. It requires the use of a polymer electrolyte membrane to transfer protons through the cell, while the electrons pass through an external circuit, producing electricity. The surface modification of the polymer, NafionRTM, commonly researched as a proton exchange membrane, may improve efficiency of a fuel cell. Surface modification can change the chemistry of the surface of a polymer while maintaining bulk properties. Plasma modification techniques such as microwave discharge of an argon and oxygen gas mixture as well as vacuum-ultraviolet (VUV) photolysis may cause favorable chemical and physical changes on the surface of Nafion for improved fuel cell function. A possible increase in hydrophilicity as a result of microwave discharge experiments may increase proton conductivity. Grafting of acrylic acid from the surface of modified Nafion may decrease the permeation of methanol in a direct methanol fuel cell, a process which can decrease efficiency. Modification of the surface of Nafion samples were carried out using: 1) An indirect Ar/O2 gas mixture plasma investigating the reaction of oxygen radicals with the surface, 2) A direct Ar/O2 gas mixture plasma investigating the reaction of oxygen radicals and VUV radiation with the surface and, 3) VUV photolysis investigating exclusively the interaction of VUV radiation with the surface and any possible oxidation upon exposure to air. Acrylic acid was grafted from the VUV photolysed Nafion samples. All treated surfaces were analyzed using X-ray photoelectron spectroscopy (XPS). Fourier transform infrared spectroscopy (FTIR) was used to analyze the grafted Nafion samples. Scanning electron microscopy (SEM) and contact angle measurements were used to analyze experiments 2 and 3. Using hydrogen as fuel is a

  18. In situ spectroscopy of ligand exchange reactions at the surface of colloidal gold and silver nanoparticles

    International Nuclear Information System (INIS)

    Dinkel, Rebecca; Peukert, Wolfgang; Braunschweig, Björn

    2017-01-01

    Gold and silver nanoparticles with their tunable optical and electronic properties are of great interest for a wide range of applications. Often the ligands at the surface of the nanoparticles have to be exchanged in a second step after particle formation in order to obtain a desired surface functionalization. For many techniques, this process is not accessible in situ . In this review, we present second-harmonic scattering (SHS) as an inherently surface sensitive and label-free optical technique to probe the ligand exchange at the surface of colloidal gold and silver nanoparticles in situ and in real time. First, a brief introduction to SHS and basic features of the SHS of nanoparticles are given. After that, we demonstrate how the SHS intensity decrease can be correlated to the thiol coverage which allows for the determination of the Gibbs free energy of adsorption and the surface coverage. (topical review)

  19. CFD Modeling of Flow and Ion Exchange Kinetics in a Rotating Bed Reactor System

    DEFF Research Database (Denmark)

    Larsson, Hilde Kristina; Schjøtt Andersen, Patrick Alexander; Byström, Emil

    2017-01-01

    A rotating bed reactor (RBR) has been modeled using computational fluid dynamics (CFD). The flow pattern in the RBR was investigated and the flow through the porous material in it was quantified. A simplified geometry representing the more complex RBR geometry was introduced and the simplified...... model was able to reproduce the main characteristics of the flow. Alternating reactor shapes were investigated, and it was concluded that the use of baffles has a very large impact on the flows through the porous material. The simulations suggested, therefore, that even faster reaction rates could...... be achieved by making the baffles deeper. Two-phase simulations were performed, which managed to reproduce the deflection of the gas–liquid interface in an unbaffled system. A chemical reaction was implemented in the model, describing the ion-exchange phenomena in the porous material using four different...

  20. Kinetic ion exchange studies in ultramarines by the radioactive tracer method; Etudes cinetiques d'echanges d'ions dans les outremers par la technique des traceurs radioactifs

    Energy Technology Data Exchange (ETDEWEB)

    May, S; Goenvec, H; Pinte, G [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1960-07-01

    The possibility of ion exchanges in various ultramarines has been studied in the aqueous phase. The kinetics of the exchange reactions is followed by studying the behaviour of a radioactive ion, either in the solution of the exchanging salt or in the ultramarine itself. The sodium in the make-up of the ultramarine, is found to exchange with various ions in solution. The reaction speeds appear to be governed by a diffusion process inside the grains of ultramarine. The diffusion coefficients and the activation energies are determined for the exchanges studied. Several exchange studies were carried out in an organic medium. The kinetics of ion exchange is also investigated in ultramarines from which most of the constituent sulphur has been eliminated. The results obtained in these ultramarines are compared with the exchange kinetics of the same ions in ordinary ultramarine. (author) [French] Nous avons etudie la possibilite d'echanges ioniques dans differents outremers, en phase aqueuse. L'etude cinetique des reactions d'echanges est suivie en etudiant le comportement d'ion radioactif, soit dans la solution du sel echangeant, soit dans l'outremer lui-meme. C'est le sodium de constitution de l'outremer qui s'echange avec differents ions en solution. Les vitesses de reactions semblent etre controlees par un processus de diffusion a l'interieur des grains d'outremer. Les coefficients de diffusion et les energies d'activation sont determines pour les echanges etudies. Quelques etudes sont realisees en milieu organique ou quelques echanges ont ete etudies. La cinetique d'echange d'ions est egalement etudie dans des outremers dans lesquels la majorite du soufre de constitution a ete eliminee. On compare les resultats obtenus dans ces outremers avec les cinetiques d'echanges des memes ions dans l'outremer ordinaire. (auteur)

  1. In situ studies of the kinetics of surface topography development during ion irradiation

    International Nuclear Information System (INIS)

    Levinskas, R.; Pranevicius, L.

    1996-01-01

    Studies of the mechanical properties of the materials affected by 25-200 keV H + , He + , Ne + and Ar + ion irradiation in the range of fluences up to 2 · 10 17 cm -2 based on the analysis of acoustic emission signals, kinetics of the surface deformations measured by laser interferometric technique and the variations of the surface acoustic waves propagation velocity are conducted. The acoustic emissions source mechanisms under various ion irradiation conditions are discussed and relative contribution various possible mechanism are indicated. The correlation of experimental results obtained by different methods of analysis is done. (author). 11 refs, 5 figs

  2. Final Report: Mechanisms of sputter ripple formation: coupling among energetic ions, surface kinetics, stress and composition

    Energy Technology Data Exchange (ETDEWEB)

    Chason, Eric; Shenoy, Vivek

    2013-01-22

    Self-organized pattern formation enables the creation of nanoscale surface structures over large areas based on fundamental physical processes rather than an applied template. Low energy ion bombardment is one such method that induces the spontaneous formation of a wide variety of interesting morphological features (e.g., sputter ripples and/or quantum dots). This program focused on the processes controlling sputter ripple formation and the kinetics controlling the evolution of surfaces and nanostructures in high flux environments. This was done by using systematic, quantitative experiments to measure ripple formation under a variety of processing conditions coupled with modeling to interpret the results.

  3. Scratching the surface of ice: Interfacial phase transitions and their kinetic implications

    Science.gov (United States)

    Limmer, David

    The surface structure of ice maintains a high degree of disorder down to surprisingly low temperatures. This is due to a number of underlying interfacial phase transitions that are associated with incremental changes in broken symmetry relative to the bulk crystal. In this talk I summarize recent work attempting to establish the nature and locations of these different phase transitions as well as how they depend on external conditions and nonequilibrium driving. The implications of this surface disorder is discussed in the context of simple kinetic processes that occur at these interfaces. Recent experimental work on the roughening transition is highlighted.

  4. Effect of fluoride on ion exchange, remineralization and acid resistance of surface enamel

    Energy Technology Data Exchange (ETDEWEB)

    Aponte-Merced, L A; Feagin, F F [Alabama Univ., Birmingham (USA)

    1979-01-01

    In a system of constant ion activities the rates of F/sup -/ exchange in enamel, under conditions of exchange alone and remineralization, depended on the concentration of F/sup -/ in solutions. Acid resistance of surface minerals resulted from exchange of F/sup -/ for OH/sup -/ in the enamel at pH 7.0 and 4.5. The level of 0.5 mM NaF, compared to 0.05 and 5.0 mM, caused maximum rates of isotopic exchange of /sup 45/Ca and maximum acid resistance of enamel. Similarly low levels of F/sup -/ may be feasible for use in caries prevention in the absence and presence of remineralization.

  5. Non-equilibrium Thermodynamic Dissolution Theory for Multi-Component Solid/Liquid Surfaces Involving Surface Adsorption and Radiolysis Kinetics

    International Nuclear Information System (INIS)

    Stout, R B

    2001-01-01

    A theoretical expression is developed for the dissolution rate response for multi-component radioactive materials that have surface adsorption kinetics and radiolysis kinetics when wetted by a multi-component aqueous solution. An application for this type of dissolution response is the performance evaluation of multi-component spent nuclear fuels (SNFs) for long term interim storage and for geological disposition. Typically, SNF compositions depend on initial composition, uranium oxide and metal alloys being most common, and on reactor burnup which results in a wide range of fission product and actinide concentrations that decay by alpha, beta, and gamma radiation. These compositional/burnup ranges of SNFs, whether placed in interim storage or emplaced in a geologic repository, will potentially be wetted by multi-component aqueous solutions, and these solutions may be further altered by radiolytic aqueous species due to three radiation fields. The solid states of the SNFs are not thermodynamically stable when wetted and will dissolve, with or without radiolysis. The following development of a dissolution theory is based on a non-equilibrium thermodynamic analysis of energy reactions and energy transport across a solid-liquid phase change discontinuity that propagates at a quasi-steady, dissolution velocity. The integral form of the energy balance equation is used for this spatial surface discontinuity analysis. The integral formulation contains internal energy functional of classical thermodynamics for both the SNFs' solid state and surface adsorption species, and the adjacent liquid state, which includes radiolytic chemical species. The steady-state concentrations of radiolytic chemical species are expressed by an approximate analysis of the decay radiation transport equation. For purposes of illustration a modified Temkin adsorption isotherm was assumed for the surface adsorption kinetics on an arbitrary, finite area of the solid-liquid dissolution interface. For

  6. Kinetic effects on the propagation of surface waves and their relevance to the heating of the solar corona

    International Nuclear Information System (INIS)

    Kuperus, M.; Heyvaerts, J.

    1980-01-01

    The MHD oscillations of the Alfven type running along surfaces of discontinuity generate motions in the discontinuity region which come rapidly out of phase. It is shown how the mathematical theory of this phase detuning predicts that surface wave should suffer dissipationless damping. Real damping is actually achieved by viscosity or kinetic effects. When detuning has grown to a large enough level, however, oscillations must be described by kinetic theory. Kinetic Alfven waves differ from perfect MHD Alfven waves in that they are able to propagate across the field. A theory of kinetic type oscillations in a finite thickness boundary is described, which predicts that surface waves generate intense kinetic Alfven waves in this boundary. The subsequent dissipation of these waves may be a powerful heating mechanism [fr

  7. Bubble extinction in Hele-Shaw flow with surface tension and kinetic undercooling regularization

    International Nuclear Information System (INIS)

    Dallaston, Michael C; McCue, Scott W

    2013-01-01

    We perform an analytic and numerical study of an inviscid contracting bubble in a two-dimensional Hele-Shaw cell, where the effects of both surface tension and kinetic undercooling on the moving bubble boundary are not neglected. In contrast to expanding bubbles, in which both boundary effects regularize the ill-posedness arising from the viscous (Saffman–Taylor) instability, we show that in contracting bubbles the two boundary effects are in competition, with surface tension stabilizing the boundary, and kinetic undercooling destabilizing it. This competition leads to interesting bifurcation behaviour in the asymptotic shape of the bubble in the limit it approaches extinction. In this limit, the boundary may tend to become either circular, or approach a line or ‘slit’ of zero thickness, depending on the initial condition and the value of a nondimensional surface tension parameter. We show that over a critical range of surface tension values, both these asymptotic shapes are stable. In this regime there exists a third, unstable branch of limiting self-similar bubble shapes, with an asymptotic aspect ratio (dependent on the surface tension) between zero and one. We support our asymptotic analysis with a numerical scheme that utilizes the applicability of complex variable theory to Hele-Shaw flow. (paper)

  8. Effect of Ingredient Loading on Surface Migration Kinetics of Additives in Vulcanized Natural Rubber Compounds

    Directory of Open Access Journals (Sweden)

    Bryan B. Pajarito

    2014-12-01

    Full Text Available Surface migration kinetics of chemical additives in vulcanized natural rubber compounds were studied as function of ingredient loading. Rubber sheets were compounded according to a 212-8 fractional factorial design of experiment, where ingredients were treated as factors varied at two levels of loading. Amount of migrated additives in surface of rubber sheets was monitored through time at ambient conditions. The maximum amount and estimated rate of additive migration were determined from weight loss kinetic curves. Attenuated total reflection–Fourier transform infrared (ATR-FTIR spectroscopy and optical microscopy were used to characterize the chemical structure and surface morphology of sheet specimens during additive migration. ANOVA results showed that increased loading of reclaimed rubber, CaCO3, and paraffin wax signif icantly decreased the maximum amount of additive migration; by contrast, increased loading of used oil, asphalt, and mercaptobenzothiazole disulphide (MBTS increased the maximum amount. Increased loading of sulfur, diphenylguanidine (DPG, and paraffin wax significantly decreased the additive migration rate; increased loading of used oil, asphalt, and stearic acid elicited an opposite effect. Comparison of ATRFTIR spectra of migrated and cleaned rubber surfaces showed signif icant variation in intensity of specif ic absorbance bands that are also present in infrared spectra of migrating chemicals. Paraffin wax, used oil, stearic acid, MBTS, asphalt, and zinc stearate were identified to bloom and bleed in the rubber sheets. Optical micrographs of migrated rubber surfaces revealed formation of white precipitates due to blooming and of semi-transparent wet patches due to bleeding.

  9. Plasma surface functionalization and dyeing kinetics of Pan-Pmma copolymers

    Science.gov (United States)

    Labay, C.; Canal, C.; Rodríguez, C.; Caballero, G.; Canal, J. M.

    2013-10-01

    Fiber surface modification with air corona plasma has been studied through dyeing kinetics under isothermal conditions at 30 °C on an acrylic-fiber fabric with a cationic dye (CI Basic Blue 3) analyzing the absorption, desorption and fixing on the surface of molecules having defined cationic character. The initial dyeing rate in the first 60 s indicates an increase of 58.3% in the dyeing rate due to the effect of corona plasma on the acrylic fiber surface. At the end of the dyeing process, the plasma-treated fabrics absorb 24.7% more dye, and the K/S value of the acrylic fabric increases by 8.8%. With selected dyestuff molecules, new techniques can be designed to amplify the knowledge about plasma-treated surface modifications of macromolecules.

  10. Surface kinetic roughening caused by dental erosion: An atomic force microscopy study

    Science.gov (United States)

    Quartarone, Eliana; Mustarelli, Piercarlo; Poggio, Claudio; Lombardini, Marco

    2008-05-01

    Surface kinetic roughening takes place both in case of growth and erosion processes. Teeth surfaces are eroded by contact with acid drinks, such as those used to supplement mineral salts during sporting activities. Calcium-phosphate based (CPP-ACP) pastes are known to reduce the erosion process, and to favour the enamel remineralization. In this study we used atomic force microscopy (AFM) to investigate the surface roughening during dental erosion, and the mechanisms at the basis of the protection role exerted by a commercial CPP-ACP paste. We found a statistically significant difference (p<0.01) in the roughness of surfaces exposed and not exposed to the acid solutions. The treatment with the CPP-ACP paste determined a statistically significant reduction of the roughness values. By interpreting the AFM results in terms of fractal scaling concepts and continuum stochastic equations, we showed that the protection mechanism of the paste depends on the chemical properties of the acid solution.

  11. Kinetic and equilibrium properties of regulatory Ca(2+)-binding domains in sodium-calcium exchangers 2 and 3.

    Science.gov (United States)

    Tal, Inbal; Kozlovsky, Tom; Brisker, Dafna; Giladi, Moshe; Khananshvili, Daniel

    2016-04-01

    In mammals, three sodium-calcium exchanger (NCX) protein isoforms (NCX1, NCX2, and NCX3) mediate Ca(2+) fluxes across the membrane to maintain cellular Ca(2+) homeostasis. NCX isoforms and their splice variants are expressed in a tissue-specific manner to meet physiological demands. NCX1 is ubiquitously expressed, NCX2 is expressed in the brain and spinal cord, and NCX3 is expressed in the brain and skeletal muscle. Eukaryotic NCXs contain two cytosolic regulatory Ca(2+)-binding domains, CBD1 and CBD2, which form a two-domain tandem (CBD12) through a short linker. Ca(2+) binding to the CBDs underlies allosteric regulation of NCX. Previous structural and functional studies in NCX1 have shown that the CBDs synergistically interact, where their interactions are modulated in a splice variant-specific manner by splicing segment at CBD2. Here, we analyze the equilibrium and kinetic properties of Ca(2+) binding to purified preparations of CBD1, CBD2, and CBD12 from NCX2 and from NCX3 splice variants. We show that CBD1 interacts with CBD2 in the context of the CBD12 tandem in all NCX isoforms, where these interactions specifically modulate Ca(2+) sensing at the primary sensor of CBD1 to meet the physiological requirements. For example, the rate-limiting slow dissociation of "occluded" Ca(2+) from the primary allosteric sensor of variants expressed in skeletal muscle is ∼10-fold slower than that of variants expressed in the brain. Notably, these kinetic differences between NCX variants occur while maintaining a similar Ca(2+) affinity of the primary sensor, since the resting [Ca(2+)]i levels are similar among different cell types. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Hanzhong, E-mail: jiahz@ms.xjb.ac.cn [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Li, Li [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Chen, Hongxia; Zhao, Yue [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); School of Geology and Mining Engineering, Xinjiang University, Urumqi 830046 (China); Li, Xiyou [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Wang, Chuanyi, E-mail: cywang@ms.xjb.ac.cn [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China)

    2015-04-28

    Graphical abstract: Roles of exchangeable cations in PAHs photodegradation on clay surafces under visible light. - Highlights: • Photolysis rate are strongly dependent on the type of cations on clay surface. • The strength of “cation–π” interactions governs the photodegradation rate of PAHs. • Several exchangeable cations could cause a shift in the absorption spectrum of PAHs. • Exchangeable cations influence the type and amount of reactive intermediates. - Abstract: Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe{sup 3+} > Al{sup 3+} > Cu{sup 2+} >> Ca{sup 2+} > K{sup +} > Na{sup +}, which is consistent with the binding energy of cation–π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation–π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na{sup +}-smectite and K{sup +}-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe{sup 3+}, Al{sup 3+}, and Cu{sup 2+} are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O{sub 2}{sup −}· , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation.

  13. Investigation and optimization of the depth of flue gas heat recovery in surface heat exchangers

    Science.gov (United States)

    Bespalov, V. V.; Bespalov, V. I.; Melnikov, D. V.

    2017-09-01

    Economic issues associated with designing deep flue gas heat recovery units for natural gas-fired boilers are examined. The governing parameter affecting the performance and cost of surface-type condensing heat recovery heat exchangers is the heat transfer surface area. When firing natural gas, the heat recovery depth depends on the flue gas temperature at the condenser outlet and determines the amount of condensed water vapor. The effect of the outlet flue gas temperature in a heat recovery heat exchanger on the additionally recovered heat power is studied. A correlation has been derived enabling one to determine the best heat recovery depth (or the final cooling temperature) maximizing the anticipated reduced annual profit of a power enterprise from implementation of energy-saving measures. Results of optimization are presented for a surface-type condensing gas-air plate heat recovery heat exchanger for the climatic conditions and the economic situation in Tomsk. The predictions demonstrate that it is economically feasible to design similar heat recovery heat exchangers for a flue gas outlet temperature of 10°C. In this case, the payback period for the investment in the heat recovery heat exchanger will be 1.5 years. The effect of various factors on the optimal outlet flue gas temperature was analyzed. Most climatic, economical, or technological factors have a minor effect on the best outlet temperature, which remains between 5 and 20°C when varying the affecting factors. The derived correlation enables us to preliminary estimate the outlet (final) flue gas temperature that should be used in designing the heat transfer surface of a heat recovery heat exchanger for a gas-fired boiler as applied to the specific climatic conditions.

  14. Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light

    International Nuclear Information System (INIS)

    Jia, Hanzhong; Li, Li; Chen, Hongxia; Zhao, Yue; Li, Xiyou; Wang, Chuanyi

    2015-01-01

    Graphical abstract: Roles of exchangeable cations in PAHs photodegradation on clay surafces under visible light. - Highlights: • Photolysis rate are strongly dependent on the type of cations on clay surface. • The strength of “cation–π” interactions governs the photodegradation rate of PAHs. • Several exchangeable cations could cause a shift in the absorption spectrum of PAHs. • Exchangeable cations influence the type and amount of reactive intermediates. - Abstract: Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe 3+ > Al 3+ > Cu 2+ >> Ca 2+ > K + > Na + , which is consistent with the binding energy of cation–π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation–π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na + -smectite and K + -smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe 3+ , Al 3+ , and Cu 2+ are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O 2 − · , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation

  15. Preliminary findings of the Viking gas exchange experiment and a model for Martian surface chemistry

    International Nuclear Information System (INIS)

    Oyama, V.I.; Berdahl, B.J.; Carle, G.C.

    1977-01-01

    It is stated that O 2 and CO 2 were evolved from humidified Martian soil in the gas exchange experiment on Viking Lander 1. Small changes in N 2 gas were also recorded. A model of the morphology and a hypothesis of the mechanistics of the Martian surface are proposed. (author)

  16. Processes of Ammonia Air-Surface Exchange in a Fertilized Zea Mays Canopy

    Science.gov (United States)

    Recent incorporation of coupled soil biogeochemical and bi-directional NH3 air-surface exchange algorithms into regional air quality models holds promise for further reducing uncertainty in estimates of NH3 emissions from fertilized soils. While this advancement represents a sig...

  17. GROUNDWATER-SURFACE WATER EXCHANGE AND IMPLICATIONS FOR LARGE RIVER RESTORATION

    Science.gov (United States)

    Movement of river water into and out of high-porosity alluvial deposits can have an important influence on surface water quality and aquatic habitat. In our study of a 60-km reach of the Willamette River in Oregon, USA, we: 1) used tracers to estimate the rate of exchange betw...

  18. Energy exchange in thermal energy atom-surface scattering: impulsive models

    International Nuclear Information System (INIS)

    Barker, J.A.; Auerbach, D.J.

    1979-01-01

    Energy exchange in thermal energy atom surface collisions is studied using impulsive ('hard cube' and 'hard sphere') models. Both models reproduce the observed nearly linear relation between outgoing and incoming energies. In addition, the hard-sphere model accounts for the widths of the outcoming energy distributions. (Auth.)

  19. Kinetics of interaction from low-energy-ion bombardment of surfaces

    International Nuclear Information System (INIS)

    Horton, C.C.

    1988-01-01

    The kinetics of interaction from low energy oxygen ion bombardment of carbon and Teflon surfaces have been investigated. The surfaces were bombarded with 4.5 to 93 eV oxygen ions and emitted species were observed with a mass spectrometer. To obtain the kinetic information, the ion beam was square pulse modulated and reaction products were observed as a function of time. The kinetic information is contained in the response of the emitted species to the pulsed ion beam. Oxygen bombardment of carbon produced CO in three parallel branches with each following an adsorption-desorption process. The fast branch, with a rate constants of 12,000/sec, appeared to be sputter induced an was absent below about 19 eV. The medium and slow branches, with rate constants of 850/sec and 45/sec respectively, has little energy dependence and appeared to be due to chemical sputtering from two sites. The ratio of the fraction of the medium branch to that of the slow was constant at 1:3. The bombardment of Teflon produced CF in two parallel branches, with one following a series process and the other an adsorb-desorb process. The rate constant of the other branch were 22,000/sec and 7,000/sec and the rate constant of the other branch was 90/sec. The total signal fell monotonically with decreasing ion energy with the fraction for each branch holding constant at 71% for the series and 29% for the adsorb-desorb

  20. Quantitative kinetics of proteolytic enzymes determined by a surface concentration-based assay using peptide arrays.

    Science.gov (United States)

    Jung, Se-Hui; Kong, Deok-Hoon; Park, Seoung-Woo; Kim, Young-Myeong; Ha, Kwon-Soo

    2012-08-21

    Peptide arrays have emerged as a key technology for drug discovery, diagnosis, and cell biology. Despite the promise of these arrays, applications of peptide arrays to quantitative analysis of enzyme kinetics have been limited due to the difficulty in obtaining quantitative information of enzymatic reaction products. In this study, we developed a new approach for the quantitative kinetics analysis of proteases using fluorescence-conjugated peptide arrays, a surface concentration-based assay with solid-phase peptide standards using dry-off measurements, and compared it with an applied concentration-based assay. For fabrication of the peptide arrays, substrate peptides of cMMP-3, caspase-3, caspase-9, and calpain-1 were functionalized with TAMRA and cysteine, and were immobilized onto amine-functionalized arrays using a heterobifunctional linker, N-[γ-maleimidobutyloxy]succinimide ester. The proteolytic activities of the four enzymes were quantitatively analyzed by calculating changes induced by enzymatic reactions in the concentrations of peptides bound to array surfaces. In addition, this assay was successfully applied for calculating the Michaelis constant (K(m,surf)) for the four enzymes. Thus, this new assay has a strong potential for use in the quantitative evaluation of proteases, and for drug discovery through kinetics studies including the determination of K(m) and V(max).

  1. Comparison of skating kinetics and kinematics on ice and on a synthetic surface.

    Science.gov (United States)

    Stidwill, T J; Pearsall, David; Turcotte, Rene

    2010-03-01

    The recent popularization and technological improvements of synthetic or artificial ice surfaces provide an attractive alternative to real ice in venues where the latter is impractical to install. Potentially, synthetic ice (SI) may be installed in controlled laboratory settings to permit detailed biomechanical analysis of skating manoeuvres. Unknown, however, is the extent to which skating on SI replicates skating on traditional ice (ICE). Hence, the purpose of this study was to compare kinetic and kinematic forward skating parameters between SI and ICE surfaces. With 11 male hockey players, a portable strain gauge system adhered to the outside of the skate blade holder was used to measure skate propulsive force synchronized with electrogoniometers for tracking dynamic knee and ankle movements during forward skating acceleration. In general, the kinetic and kinematic variables investigated in this study showed minimal differences between the two surfaces (P > 0.06), and no individual variable differences were identified between the two surfaces (P > or = 0.1) with the exception of greater knee extension on SI than ICE (15.2 degrees to 11.0 degrees; P skating, and thus offer the potential for valid analogous conditions for in-lab testing and training.

  2. Kinetic model for electric-field induced point defect redistribution near semiconductor surfaces

    Science.gov (United States)

    Gorai, Prashun; Seebauer, Edmund G.

    2014-07-01

    The spatial distribution of point defects near semiconductor surfaces affects the efficiency of devices. Near-surface band bending generates electric fields that influence the spatial redistribution of charged mobile defects that exchange infrequently with the lattice, as recently demonstrated for pile-up of isotopic oxygen near rutile TiO2 (110). The present work derives a mathematical model to describe such redistribution and establishes its temporal dependence on defect injection rate and band bending. The model shows that band bending of only a few meV induces significant redistribution, and that the direction of the electric field governs formation of either a valley or a pile-up.

  3. Kinetic model for electric-field induced point defect redistribution near semiconductor surfaces

    International Nuclear Information System (INIS)

    Gorai, Prashun; Seebauer, Edmund G.

    2014-01-01

    The spatial distribution of point defects near semiconductor surfaces affects the efficiency of devices. Near-surface band bending generates electric fields that influence the spatial redistribution of charged mobile defects that exchange infrequently with the lattice, as recently demonstrated for pile-up of isotopic oxygen near rutile TiO 2 (110). The present work derives a mathematical model to describe such redistribution and establishes its temporal dependence on defect injection rate and band bending. The model shows that band bending of only a few meV induces significant redistribution, and that the direction of the electric field governs formation of either a valley or a pile-up.

  4. Comprehensive Study of the Solubility, Thermochemistry, Ion Exchange, and Precipitation Kinetics of NO3 Cancrinite and NO3 Sodalite

    International Nuclear Information System (INIS)

    Navrotsky, Alexandra; Liu, Qinyuan

    2004-01-01

    The precipitation of aluminosilicate phases from caustic nuclear wastes has proven to be problematic in a number of processes including radionuclide separations (cementation of columns by aluminosilicate phases), tank emptying (aluminosilicate tank heels), and condensation of wastes in evaporators (aluminosilicate precipitates in the evaporators, providing nucleation sites for growth of critical masses of radioactive actinide salts). In a collaboration between SNL and UCD, we have investigated why and how these phases form, and which conditions favor the formation of which phases. These studies have involved synthesis and characterization of aluminosilicate phases formed using a variety of synthesis techniques, kinetics of precipitation, structural investigations of aluminosilicate phases, thermodynamic calculations of aluminosilicate solubility, calorimetric studies of aluminosilicate precipitation, and a limited investigation of radionuclide partitioning and ion exchange processes (involving typical tank fluid chemistries and these materials). The predominant phases that are observed in the aluminosilicate precipitates from basic tanks wastes (i.e. Hanford, Savannah River Site ''SRS'' wastes) are the salt enclathrated zeolites: sodium nitrate, sodium carbonate and sodium hydroxide sodalite and cancrinite. These phases precipitate readily from the high ionic strength, highly basic solutions at ambient temperatures as well as at elevated temperatures, with or without the presence of an external Al and Si source (both are contained in the waste solutions), and upon interactions with reactive soil components such as clays

  5. Kinetic bottlenecks to chemical exchange rates for deep-sea animals - Part 2: Carbon Dioxide

    Science.gov (United States)

    Hofmann, A. F.; Peltzer, E. T.; Brewer, P. G.

    2013-04-01

    Increased ocean acidification from fossil fuel CO2 invasion, from temperature-driven changes in respiration, and from possible leakage from sub-seabed geologic CO2 disposal has aroused concern over the impacts of elevated CO2 concentrations on marine life. Discussion of these impacts has so far focused only on changes in the oceanic bulk fluid properties (ΔpH, Δ[∑ CO2], etc.) as the critical variable and with a major focus on carbonate shell formation. Here we describe the rate problem for animals that must export CO2 at about the same rate at which O2 is consumed. We analyse the basic properties controlling CO2 export within the diffusive boundary layer around marine animals in an ocean changing in temperature (T) and CO2 concentration in order to compare the challenges posed by O2 uptake under stress with the equivalent problem of CO2 expulsion. The problem is more complex than that for a non-reactive gas, since with CO2 the influence of the seawater carbonate acid-base system needs to be considered. These reactions significantly facilitate CO2 efflux compared to O2 intake at equal temperature, pressure and fluid flow rate under typical oceanic concentrations. The effect of these reactions can be described by an enhancement factor, similar to that widely used for CO2 invasion at the sea surface. While organisms do need to actively regulate flow over their surface to thin the boundary layer to take up enough O2, this seems to be not necessary to facilitate CO2 efflux. Instead, the main impacts of rising oceanic CO2 will most likely be those associated with classical ocean acidification science. Regionally, as with O2, the combination of T, P and pH/pCO2 creates a zone of maximum CO2 stress at around 1000 m depth.

  6. Kinetic bottlenecks to chemical exchange rates for deep-sea animals – Part 2: Carbon Dioxide

    Directory of Open Access Journals (Sweden)

    A. F. Hofmann

    2013-04-01

    Full Text Available Increased ocean acidification from fossil fuel CO2 invasion, from temperature-driven changes in respiration, and from possible leakage from sub-seabed geologic CO2 disposal has aroused concern over the impacts of elevated CO2 concentrations on marine life. Discussion of these impacts has so far focused only on changes in the oceanic bulk fluid properties (ΔpH, Δ[∑ CO2], etc. as the critical variable and with a major focus on carbonate shell formation. Here we describe the rate problem for animals that must export CO2 at about the same rate at which O2 is consumed. We analyse the basic properties controlling CO2 export within the diffusive boundary layer around marine animals in an ocean changing in temperature (T and CO2 concentration in order to compare the challenges posed by O2 uptake under stress with the equivalent problem of CO2 expulsion. The problem is more complex than that for a non-reactive gas, since with CO2 the influence of the seawater carbonate acid-base system needs to be considered. These reactions significantly facilitate CO2 efflux compared to O2 intake at equal temperature, pressure and fluid flow rate under typical oceanic concentrations. The effect of these reactions can be described by an enhancement factor, similar to that widely used for CO2 invasion at the sea surface. While organisms do need to actively regulate flow over their surface to thin the boundary layer to take up enough O2, this seems to be not necessary to facilitate CO2 efflux. Instead, the main impacts of rising oceanic CO2 will most likely be those associated with classical ocean acidification science. Regionally, as with O2, the combination of T, P and pH/pCO2 creates a zone of maximum CO2 stress at around 1000 m depth.

  7. New insights into proton surface mobility processes in PEMFC catalysts using isotopic exchange methods.

    Science.gov (United States)

    Ferreira-Aparicio, Paloma

    2009-09-01

    The surface chemistry and the adsorption/desorption/exchange behavior of a proton-exchange membrane fuel cell catalyst are analyzed as a case study for the development of tailor-made support materials of enhanced performance and stability. By using H2, D2, and CO as probe molecules, the relevance of some surface functional groups of the catalyst support on several diffusion processes taking place during the adsorption is shown. Sulfonic groups associated with the vulcanized carbon black surface have been detected by means of spectroscopic techniques (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy) and by analysis of the desorbed products during temperature-programmed desorption tests by mass spectrometry. Such hydrophilic species have been observed to favor proton surface mobility and exchange with Pt-adsorbed deuterium even in the presence of adsorbed CO. This behavior is relevant both for the proper characterization of these kinds of catalysts using adsorption probes and for the design of new surface-modified carbon supports, enabling alternative proton-transfer pathways throughout the catalytic layers toward the membrane.

  8. Global observations and modeling of atmosphere-surface exchange of elemental mercury: a critical review

    Science.gov (United States)

    Zhu, Wei; Lin, Che-Jen; Wang, Xun; Sommar, Jonas; Fu, Xuewu; Feng, Xinbin

    2016-04-01

    Reliable quantification of air-surface fluxes of elemental Hg vapor (Hg0) is crucial for understanding mercury (Hg) global biogeochemical cycles. There have been extensive measurements and modeling efforts devoted to estimating the exchange fluxes between the atmosphere and various surfaces (e.g., soil, canopies, water, snow, etc.) in the past three decades. However, large uncertainties remain due to the complexity of Hg0 bidirectional exchange, limitations of flux quantification techniques and challenges in model parameterization. In this study, we provide a critical review on the state of science in the atmosphere-surface exchange of Hg0. Specifically, the advancement of flux quantification techniques, mechanisms in driving the air-surface Hg exchange and modeling efforts are presented. Due to the semi-volatile nature of Hg0 and redox transformation of Hg in environmental media, Hg deposition and evasion are influenced by multiple environmental variables including seasonality, vegetative coverage and its life cycle, temperature, light, moisture, atmospheric turbulence and the presence of reactants (e.g., O3, radicals, etc.). However, the effects of these processes on flux have not been fundamentally and quantitatively determined, which limits the accuracy of flux modeling. We compile an up-to-date global observational flux database and discuss the implication of flux data on the global Hg budget. Mean Hg0 fluxes obtained by micrometeorological measurements do not appear to be significantly greater than the fluxes measured by dynamic flux chamber methods over unpolluted surfaces (p = 0.16, one-tailed, Mann-Whitney U test). The spatiotemporal coverage of existing Hg0 flux measurements is highly heterogeneous with large data gaps existing in multiple continents (Africa, South Asia, Middle East, South America and Australia). The magnitude of the evasion flux is strongly enhanced by human activities, particularly at contaminated sites. Hg0 flux observations in East

  9. Global observations and modeling of atmosphere–surface exchange of elemental mercury: a critical review

    Directory of Open Access Journals (Sweden)

    W. Zhu

    2016-04-01

    Full Text Available Reliable quantification of air–surface fluxes of elemental Hg vapor (Hg0 is crucial for understanding mercury (Hg global biogeochemical cycles. There have been extensive measurements and modeling efforts devoted to estimating the exchange fluxes between the atmosphere and various surfaces (e.g., soil, canopies, water, snow, etc. in the past three decades. However, large uncertainties remain due to the complexity of Hg0 bidirectional exchange, limitations of flux quantification techniques and challenges in model parameterization. In this study, we provide a critical review on the state of science in the atmosphere–surface exchange of Hg0. Specifically, the advancement of flux quantification techniques, mechanisms in driving the air–surface Hg exchange and modeling efforts are presented. Due to the semi-volatile nature of Hg0 and redox transformation of Hg in environmental media, Hg deposition and evasion are influenced by multiple environmental variables including seasonality, vegetative coverage and its life cycle, temperature, light, moisture, atmospheric turbulence and the presence of reactants (e.g., O3, radicals, etc.. However, the effects of these processes on flux have not been fundamentally and quantitatively determined, which limits the accuracy of flux modeling. We compile an up-to-date global observational flux database and discuss the implication of flux data on the global Hg budget. Mean Hg0 fluxes obtained by micrometeorological measurements do not appear to be significantly greater than the fluxes measured by dynamic flux chamber methods over unpolluted surfaces (p = 0.16, one-tailed, Mann–Whitney U test. The spatiotemporal coverage of existing Hg0 flux measurements is highly heterogeneous with large data gaps existing in multiple continents (Africa, South Asia, Middle East, South America and Australia. The magnitude of the evasion flux is strongly enhanced by human activities, particularly at contaminated sites. Hg0

  10. The surface blistering kinetics and the H-platelet evolution in H-implanted germanium

    International Nuclear Information System (INIS)

    Yang Fan; Zhang Xuanxiong; Ye Tianchun; Zhuang Songlin

    2012-01-01

    The surface blistering phenomenon produced in H-implanted Ge by a series of low temperature annealing processes was investigated. The kinetic plot of the onset of blistering contains a break point that separates the straight-line plot into two parts, with two distinct slopes based on the calculated activation energy from the different temperature regions for 3×10 16 cm -2 and 5×10 16 cm -2 H-implanted doses. This plot indicates the existence of distinct, temperature dependent mechanisms, probably caused by the release of different types of H-platelets. The turning direction (from low to high temperature) of the Arrhenius plot with the break point is contrary to that of other known materials. The formation and evolution of the H-platelets under the Ge surface was revealed by TEM (transmission electron microscopy). The TEM results demonstrate that the 〈0 0 1〉 platelets parallel to the sample surface are first produced by a low H implantation dose; however, the vertical 〈0 1 0〉 platelets perpendicular to the sample surface form later as the H implantation dose increases. The H-platelets combine with each other, becoming micro-cracks. The {1 1 1} and {3 1 1} micro-cracks serve as interconnections between the 〈0 0 1〉-oriented micro-cracks below the substrate surface. Finally, the accumulated H 2 pressure in the cracks deforms the surface to generate Ge surface exfoliation.

  11. Adsorption/desorption kinetics of Na atoms on reconstructed Si (111)-7 x 7 surface

    International Nuclear Information System (INIS)

    Chauhan, Amit Kumar Singh; Govind; Shivaprasad, S.M.

    2010-01-01

    Self-assembled nanostructures on a periodic template are fundamentally and technologically important as they put forward the possibility to fabricate and pattern micro/nano-electronics for sensors, ultra high-density memories and nanocatalysts. Alkali-metal (AM) nanostructure grown on a semiconductor surface has received considerable attention because of their simple hydrogen like electronic structure. However, little efforts have been made to understand the fundamental aspects of the growth mechanism of self-assembled nanostructures of AM on semiconductor surfaces. In this paper, we report organized investigation of kinetically controlled room-temperature (RT) adsorption/desorption of sodium (Na) metal atoms on clean reconstructed Si (111)-7 x 7 surface, by X-ray photoelectron spectroscopy (XPS). The RT uptake curve shows a layer-by-layer growth (Frank-vander Merve growth) mode of Na on Si (111)-7 x 7 surfaces and a shift is observed in the binding energy position of Na (1s) spectra. The thermal stability of the Na/Si (111) system was inspected by annealing the system to higher substrate temperatures. Within a temperature range from RT to 350 o C, the temperature induced mobility to the excess Na atoms sitting on top of the bilayer, allowing to arrange themselves. Na atoms desorbed over a wide temperature range of 370 o C, before depleting the Si (111) surface at temperature 720 o C. The acquired valence-band (VB) spectra during Na growth revealed the development of new electronic-states near the Fermi level and desorption leads the termination of these. For Na adsorption up to 2 monolayers, decrease in work function (-1.35 eV) was observed, whereas work function of the system monotonically increases with Na desorption from the Si surface as observed by other studies also. This kinetic and thermodynamic study of Na adsorbed Si (111)-7 x 7 system can be utilized in fabrication of sensors used in night vision devices.

  12. Analyzing the Molecular Kinetics of Water Spreading on Hydrophobic Surfaces via Molecular Dynamics Simulation.

    Science.gov (United States)

    Zhao, Lei; Cheng, Jiangtao

    2017-09-07

    In this paper, we report molecular kinetic analyses of water spreading on hydrophobic surfaces via molecular dynamics simulation. The hydrophobic surfaces are composed of amorphous polytetrafluoroethylene (PTFE) with a static contact angle of ~112.4° for water. On the basis of the molecular kinetic theory (MKT), the influences of both viscous damping and solid-liquid retarding were analyzed in evaluating contact line friction, which characterizes the frictional force on the contact line. The unit displacement length on PTFE was estimated to be ~0.621 nm and is ~4 times as long as the bond length of C-C backbone. The static friction coefficient was found to be ~[Formula: see text] Pa·s, which is on the same order of magnitude as the dynamic viscosity of water, and increases with the droplet size. A nondimensional number defined by the ratio of the standard deviation of wetting velocity to the characteristic wetting velocity was put forward to signify the strength of the inherent contact line fluctuation and unveil the mechanism of enhanced energy dissipation in nanoscale, whereas such effect would become insignificant in macroscale. Moreover, regarding a liquid droplet on hydrophobic or superhydrophobic surfaces, an approximate solution to the base radius development was derived by an asymptotic expansion approach.

  13. The role of surface oxides on hydrogen sorption kinetics in titanium thin films

    Science.gov (United States)

    Hadjixenophontos, Efi; Michalek, Lukas; Roussel, Manuel; Hirscher, Michael; Schmitz, Guido

    2018-05-01

    Titanium is presently discussed as a catalyst to accelerate the hydrogenation kinetics of hydrogen storage materials. It is however known that H absorption in Ti decisively depends on the surface conditions (presence or absence of the natural surface oxide). In this work, we use Ti thin films of controlled thickness (50-800 nm) as a convenient tool for quantifying the atomic transport. XRD and TEM investigations allow us to follow the hydrogenation progress inside the film. Hydrogenation of TiO2/Ti bi-layers is studied at 300 °C, for different durations (10 s to 600 min) and at varying pressures of pure H2 atmosphere. Under these conditions, the hydrogenation is found to be linear in time. By comparing films with and without TiO2, as well as by studying the pressure dependence of hydrogenation, it is demonstrated that hydrogen transport across the oxide represents the decisive kinetic barrier rather than the splitting of H2 molecules at the surface. Hydrogenation appears by a layer-like reaction initiated by heterogeneous nucleation at the backside interface to the substrate. The linear growth constant and the H diffusion coefficient inside the oxide are quantified, as well as a reliable lower bound to the hydrogen diffusion coefficient in Ti is derived. The pressure dependence of hydrogen absorption is quantitatively modelled.

  14. Murmanite and lomonosovite as Ag-selective ionites: kinetics and products of ion exchange in aqueous AgNO3 solutions

    Science.gov (United States)

    Lykova, Inna S.; Chukanov, Nikita V.; Kazakov, Anatoliy I.; Tarasov, Viktor P.; Pekov, Igor V.; Yapaskurt, Vasiliy O.; Chervonnaya, Nadezhda A.

    2013-09-01

    Products and kinetics of ion exchange of heterophyllosilicate minerals lomonosovite and murmanite with aqueous AgNO3 solutions under low-temperature conditions have been studied using scanning electron microscopy, electron microprobe analysis, single-crystal X-ray diffraction, infrared spectroscopy, 23Na nuclear magnetic resonance spectroscopy and dynamic calorimetry. Both minerals show strong affinity for silver in cation exchange. Simplified formulae of Ag-exchanged forms of murmanite and lomonosovite are (Ag3.0Ca0.5Na0.5) (Ti,Nb,Mn,Fe)3.7-4 (Si2O7)2O4·4(H2O,OH) and (Ag8.2Na1.2Ca0.3) (Ti,Nb,Mn,Fe)3.9-4 (Si2O7)2 (PO4)1.9O4· xH2O, respectively. The reaction of ion exchange for murmanite follows the first-order kinetic model up to ca. 70-80 % conversion. The rate of the process is described by the equation k(h-1) = 107.64±0.60 exp[-(12.2 ± 0.9)·103/RT]. The average heat release value in the temperature range 39.4-72 °C is 230 J g-1. The cation exchange is limited by processes in solid state, most probably binding of silver.

  15. Cortical surface-based analysis reduces bias and variance in kinetic modeling of brain PET data

    DEFF Research Database (Denmark)

    Greve, Douglas N; Svarer, Claus; Fisher, Patrick M

    2014-01-01

    Exploratory (i.e., voxelwise) spatial methods are commonly used in neuroimaging to identify areas that show an effect when a region-of-interest (ROI) analysis cannot be performed because no strong a priori anatomical hypothesis exists. However, noise at a single voxel is much higher than noise...... in a ROI making noise management critical to successful exploratory analysis. This work explores how preprocessing choices affect the bias and variability of voxelwise kinetic modeling analysis of brain positron emission tomography (PET) data. These choices include the use of volume- or cortical surface...

  16. Wetting kinetics of nanodroplets on lyophilic nanopillar-arrayed surfaces: A molecular dynamics study

    Science.gov (United States)

    Zong, Diyuan; Yang, Zhen; Duan, Yuanyuan

    2017-10-01

    Wetting kinetics of water droplets on substrates with lyophilic nanopillars was investigated using molecular dynamics simulations. Early spreading of the droplet is hindered by the nanopillars because of the penetration of the liquid which induce an extra dissipation in the droplet. Droplet spreading is mainly controlled by liquid viscosity and surface tension and not dependent on solid wettability. Propagation of the fringe film is hindered by the enhanced solid wettability because of the energy barrier introduced by the interaction between water molecules and nanopillars which increase with solid wettability.

  17. Finite size effects in phase transformation kinetics in thin films and surface layers

    International Nuclear Information System (INIS)

    Trofimov, Vladimir I.; Trofimov, Ilya V.; Kim, Jong-Il

    2004-01-01

    In studies of phase transformation kinetics in thin films, e.g. crystallization of amorphous films, until recent time is widely used familiar Kolmogorov-Johnson-Mehl-Avrami (KJMA) statistical model of crystallization despite it is applicable only to an infinite medium. In this paper a model of transformation kinetics in thin films based on a concept of the survival probability for randomly chosen point during transformation process is presented. Two model versions: volume induced transformation (VIT) when the second-phase grains nucleate over a whole film volume and surface induced transformation (SIT) when they form on an interface with two nucleation mode: instantaneous nucleation at transformation onset and continuous one during all the process are studied. At VIT-process due to the finite film thickness effects the transformation profile has a maximum in a film middle, whereas that of the grains population reaches a minimum inhere, the grains density is always higher than in a volume material, and the thinner film the slower it transforms. The transformation kinetics in a thin film obeys a generalized KJMA equation with parameters depending on a film thickness and in limiting cases of extremely thin and thick film it reduces to classical KJMA equation for 2D- and 3D-system, respectively

  18. Ozone kinetics in low-pressure discharges: vibrationally excited ozone and molecule formation on surfaces

    Science.gov (United States)

    Marinov, Daniil; Guerra, Vasco; Guaitella, Olivier; Booth, Jean-Paul; Rousseau, Antoine

    2013-10-01

    A combined experimental and modeling investigation of the ozone kinetics in the afterglow of pulsed direct current discharges in oxygen is carried out. The discharge is generated in a cylindrical silica tube of radius 1 cm, with short pulse durations between 0.5 and 2 ms, pressures in the range 1-5 Torr and discharge currents ˜40-120 mA. Time-resolved absolute concentrations of ground-state atoms and ozone molecules were measured simultaneously in situ, by two-photon absorption laser-induced fluorescence and ultraviolet absorption, respectively. The experiments were complemented by a self-consistent model developed to interpret the results and, in particular, to evaluate the roles of vibrationally excited ozone and of ozone formation on surfaces. It is found that vibrationally excited ozone, O_3^{*} , plays an important role in the ozone kinetics, leading to a decrease in the ozone concentration and an increase in its formation time. In turn, the kinetics of O_3^{*} is strongly coupled with those of atomic oxygen and O2(a 1Δg) metastables. Ozone formation at the wall does not contribute significantly to the total ozone production under the present conditions. Upper limits for the effective heterogeneous recombination probability of O atoms into ozone are established.

  19. Ozone kinetics in low-pressure discharges: vibrationally excited ozone and molecule formation on surfaces

    International Nuclear Information System (INIS)

    Marinov, Daniil; Guaitella, Olivier; Booth, Jean-Paul; Rousseau, Antoine; Guerra, Vasco

    2013-01-01

    A combined experimental and modeling investigation of the ozone kinetics in the afterglow of pulsed direct current discharges in oxygen is carried out. The discharge is generated in a cylindrical silica tube of radius 1 cm, with short pulse durations between 0.5 and 2 ms, pressures in the range 1–5 Torr and discharge currents ∼40–120 mA. Time-resolved absolute concentrations of ground-state atoms and ozone molecules were measured simultaneously in situ, by two-photon absorption laser-induced fluorescence and ultraviolet absorption, respectively. The experiments were complemented by a self-consistent model developed to interpret the results and, in particular, to evaluate the roles of vibrationally excited ozone and of ozone formation on surfaces. It is found that vibrationally excited ozone, O 3 * , plays an important role in the ozone kinetics, leading to a decrease in the ozone concentration and an increase in its formation time. In turn, the kinetics of O 3 * is strongly coupled with those of atomic oxygen and O 2 (a 1 Δ g ) metastables. Ozone formation at the wall does not contribute significantly to the total ozone production under the present conditions. Upper limits for the effective heterogeneous recombination probability of O atoms into ozone are established. (paper)

  20. Uncertainty quantification of surface-water/groundwater exchange estimates in large wetland systems using Python

    Science.gov (United States)

    Hughes, J. D.; Metz, P. A.

    2014-12-01

    Most watershed studies include observation-based water budget analyses to develop first-order estimates of significant flow terms. Surface-water/groundwater (SWGW) exchange is typically assumed to be equal to the residual of the sum of inflows and outflows in a watershed. These estimates of SWGW exchange, however, are highly uncertain as a result of the propagation of uncertainty inherent in the calculation or processing of the other terms of the water budget, such as stage-area-volume relations, and uncertainties associated with land-cover based evapotranspiration (ET) rate estimates. Furthermore, the uncertainty of estimated SWGW exchanges can be magnified in large wetland systems that transition from dry to wet during wet periods. Although it is well understood that observation-based estimates of SWGW exchange are uncertain it is uncommon for the uncertainty of these estimates to be directly quantified. High-level programming languages like Python can greatly reduce the effort required to (1) quantify the uncertainty of estimated SWGW exchange in large wetland systems and (2) evaluate how different approaches for partitioning land-cover data in a watershed may affect the water-budget uncertainty. We have used Python with the Numpy, Scipy.stats, and pyDOE packages to implement an unconstrained Monte Carlo approach with Latin Hypercube sampling to quantify the uncertainty of monthly estimates of SWGW exchange in the Floral City watershed of the Tsala Apopka wetland system in west-central Florida, USA. Possible sources of uncertainty in the water budget analysis include rainfall, ET, canal discharge, and land/bathymetric surface elevations. Each of these input variables was assigned a probability distribution based on observation error or spanning the range of probable values. The Monte Carlo integration process exposes the uncertainties in land-cover based ET rate estimates as the dominant contributor to the uncertainty in SWGW exchange estimates. We will discuss

  1. Kinetic energy of ions produced with first-, second-, and multi-shot femtosecond laser ablation on a solid surface

    International Nuclear Information System (INIS)

    Kobayashi, Tohru; Kato, Toshiyuki; Kurata-Nishimura, Mizuki; Matsuo, Yukari; Kawai, Jun; Motobayashi, Tohru; Hayashizaki, Yoshihide

    2007-01-01

    We report that the kinetic energy of samarium (Sm) atom and Sm + ion produced by femtosecond laser ablation of solid samarium is strongly dependent on the number of ablation laser shots in the range from 1 to 10. By ablating the fresh surface (i.e. 1st shot), we find the kinetic energy of both Sm and Sm + ion to be the largest (24 and 250 eV, respectively). Almost 10 times larger kinetic energy of Sm + ion than that of Sm clearly indicates the contribution of Coulomb explosion in the acceleration process. From the second shot, kinetic energies of Sm and Sm + ion are lower than those of the first shot and almost constant (ca. 12 and 80 eV, respectively). This behaviour suggests the change in the nature of the solid surface after femtosecond laser ablation, which can be explained by the amorphization of ablated sample surface reported in recent studies

  2. Implied and Local Volatility Surfaces for South African Index and Foreign Exchange Options

    Directory of Open Access Journals (Sweden)

    Antonie Kotzé

    2015-01-01

    Full Text Available Certain exotic options cannot be valued using closed-form solutions or even by numerical methods assuming constant volatility. Many exotics are priced in a local volatility framework. Pricing under local volatility has become a field of extensive research in finance, and various models are proposed in order to overcome the shortcomings of the Black-Scholes model that assumes a constant volatility. The Johannesburg Stock Exchange (JSE lists exotic options on its Can-Do platform. Most exotic options listed on the JSE’s derivative exchanges are valued by local volatility models. These models needs a local volatility surface. Dupire derived a mapping from implied volatilities to local volatilities. The JSE uses this mapping in generating the relevant local volatility surfaces and further uses Monte Carlo and Finite Difference methods when pricing exotic options. In this document we discuss various practical issues that influence the successful construction of implied and local volatility surfaces such that pricing engines can be implemented successfully. We focus on arbitrage-free conditions and the choice of calibrating functionals. We illustrate our methodologies by studying the implied and local volatility surfaces of South African equity index and foreign exchange options.

  3. Spin-wave resonance frequency in ferromagnetic thin film with interlayer exchange coupling and surface anisotropy

    Science.gov (United States)

    Zhang, Shuhui; Rong, Jianhong; Wang, Huan; Wang, Dong; Zhang, Lei

    2018-01-01

    We have investigated the dependence of spin-wave resonance(SWR) frequency on the surface anisotropy, the interlayer exchange coupling, the ferromagnetic layer thickness, the mode number and the external magnetic field in a ferromagnetic superlattice film by means of the linear spin-wave approximation and Green's function technique. The SWR frequency of the ferromagnetic thin film is shifted to higher values corresponding to those of above factors, respectively. It is found that the linear behavior of SWR frequency curves of all modes in the system is observed as the external magnetic field is increasing, however, SWR frequency curves are nonlinear with the lower and the higher modes for different surface anisotropy and interlayer exchange coupling in the system. In addition, the SWR frequency of the lowest (highest) mode is shifted to higher (lower) values when the film thickness is thinner. The interlayer exchange coupling is more important for the energetically higher modes than for the energetically lower modes. The surface anisotropy has a little effect on the SWR frequency of the highest mode, when the surface anisotropy field is further increased.

  4. Flow-Induced New Channels of Energy Exchange in Multi-Scale Plasma Dynamics - Revisiting Perturbative Hybrid Kinetic-MHD Theory.

    Science.gov (United States)

    Shiraishi, Junya; Miyato, Naoaki; Matsunaga, Go

    2016-05-10

    It is found that new channels of energy exchange between macro- and microscopic dynamics exist in plasmas. They are induced by macroscopic plasma flow. This finding is based on the kinetic-magnetohydrodynamic (MHD) theory, which analyses interaction between macroscopic (MHD-scale) motion and microscopic (particle-scale) dynamics. The kinetic-MHD theory is extended to include effects of macroscopic plasma flow self-consistently. The extension is realised by generalising an energy exchange term due to wave-particle resonance, denoted by δ WK. The first extension is generalisation of the particle's Lagrangian, and the second one stems from modification to the particle distribution function due to flow. These extensions lead to a generalised expression of δ WK, which affects the MHD stability of plasmas.

  5. Applied research for profilometric testing of the state of interior surfaces in heat exchanger tubes

    International Nuclear Information System (INIS)

    Gyongyosi, Tiberiu; Panaitescu, Valeriu Nicolae

    2009-01-01

    Generally, the surface flaws identified at heat exchangers tubing are characteristic for the heat secondary systems, located on the external surfaces of the heat exchanger tubes and are mostly the results of the ageing phenomena in systems operation. The tests performed, with the impressing replicating device confirmed the applicability of the technique, functionality of the device and resulted in replicas on metal support, these being the hard copy of the negative of the test tube surface, allowing the profile measurement. The visual inspection of the replicas on the metallic support gives information about the surface geometry replicated, pointing out the marks, which belong to the same area under observation. The minimum and maximum values for the depth of the channel worked out in the inner test tube wall have been determined by profile graphic measurement on the replicas. The paper presents the structural and functional description of the experimental devices. The first results and some conclusions are also included. Two patent applications were submitted at State Office for Inventions and Trademarks (OSIM) covering the original data to protect royalty: 'The local pit flaws, scratches, incipient micro-cracks replicating device on inner cylindrical surfaces', under no. A/00299/17.04.2008 and 'The annular local flaw, incipient micro-cracks replicating device on inner cylindrical surface' under no. A/00300/17.04.2008

  6. Kinetic Behaviors of Catalysis-Driven Growth of Three-Species Aggregates on Base of Exchange-Driven Aggregations

    International Nuclear Information System (INIS)

    Sun Yunfei; Chen Dan; Lin Zhenquan; Ke Jianhong

    2009-01-01

    We propose a solvable aggregation model to mimic the evolution of population A, asset B, and the quantifiable resource C in a society. In this system, the population and asset aggregates themselves grow through self-exchanges with the rate kernels K 1 (k, j) = K 1 kj and K 2 (k, j) = K 2 kj, respectively. The actions of the population and asset aggregations on the aggregation evolution of resource aggregates are described by the population-catalyzed monomer death of resource aggregates and asset-catalyzed monomer birth of resource aggregates with the rate kernels J 1 (k, j) = J 1 k and J 2 (k, j) = J 2 k, respectively. Meanwhile, the asset and resource aggregates conjunctly catalyze the monomer birth of population aggregates with the rate kernel I 1 (k, i, j) = I 1 ki μ j η , and population and resource aggregates conjunctly catalyze the monomer birth of asset aggregates with the rate kernel I 2 (k, i, j) = I 2 ki v j η . The kinetic behaviors of species A, B, and C are investigated by means of the mean-field rate equation approach. The effects of the population-catalyzed death and asset-catalyzed birth on the evolution of resource aggregates based on the self-exchanges of population and asset appear in effective forms. The coefficients of the effective population-catalyzed death and the asset-catalyzed birth are expressed as J 1e = J 1 /K 1 and J 2e = J 2 /K 2 , respectively. The aggregate size distribution of C species is found to be crucially dominated by the competition between the effective death and the effective birth. It satisfies the conventional scaling form, generalized scaling form, and modified scaling form in the cases of J 1e 2e , J 1e = J 2e , and J 1e > J 2e , respectively. Meanwhile, we also find the aggregate size distributions of populations and assets both fall into two distinct categories for different parameters μ, ν, and η: (i) When μ = ν = η = 0 and μ = ν = 0, η = 1, the population and asset aggregates obey the generalized

  7. GENERAL: Kinetic Behaviors of Catalysis-Driven Growth of Three-Species Aggregates on Base of Exchange-Driven Aggregations

    Science.gov (United States)

    Sun, Yun-Fei; Chen, Dan; Lin, Zhen-Quan; Ke, Jian-Hong

    2009-06-01

    We propose a solvable aggregation model to mimic the evolution of population A, asset B, and the quantifiable resource C in a society. In this system, the population and asset aggregates themselves grow through self-exchanges with the rate kernels K1(k, j) = K1kj and K2(k, j) = K2kj, respectively. The actions of the population and asset aggregations on the aggregation evolution of resource aggregates are described by the population-catalyzed monomer death of resource aggregates and asset-catalyzed monomer birth of resource aggregates with the rate kernels J1(k, j) = J1k and J2(k, j) = J2k, respectively. Meanwhile, the asset and resource aggregates conjunctly catalyze the monomer birth of population aggregates with the rate kernel I1(k, i, j) = I1kiμjη, and population and resource aggregates conjunctly catalyze the monomer birth of asset aggregates with the rate kernel I2(k, i, j) = I2kivjη. The kinetic behaviors of species A, B, and C are investigated by means of the mean-field rate equation approach. The effects of the population-catalyzed death and asset-catalyzed birth on the evolution of resource aggregates based on the self-exchanges of population and asset appear in effective forms. The coefficients of the effective population-catalyzed death and the asset-catalyzed birth are expressed as J1e = J1/K1 and J2e = J2/K2, respectively. The aggregate size distribution of C species is found to be crucially dominated by the competition between the effective death and the effective birth. It satisfies the conventional scaling form, generalized scaling form, and modified scaling form in the cases of J1e J2e, respectively. Meanwhile, we also find the aggregate size distributions of populations and assets both fall into two distinct categories for different parameters μ, ν, and η: (i) When μ = ν = η = 0 and μ = ν = 0, η = 1, the population and asset aggregates obey the generalized scaling forms; and (ii) When μ = ν = 1, η = 0, and μ = ν = η = 1, the

  8. Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation

    DEFF Research Database (Denmark)

    Wellendorff, Jess; Lundgård, Keld Troen; Møgelhøj, Andreas

    2012-01-01

    A methodology for semiempirical density functional optimization, using regularization and cross-validation methods from machine learning, is developed. We demonstrate that such methods enable well-behaved exchange-correlation approximations in very flexible model spaces, thus avoiding the overfit......A methodology for semiempirical density functional optimization, using regularization and cross-validation methods from machine learning, is developed. We demonstrate that such methods enable well-behaved exchange-correlation approximations in very flexible model spaces, thus avoiding...... the energetics of intramolecular and intermolecular, bulk solid, and surface chemical bonding, and the developed optimization method explicitly handles making the compromise based on the directions in model space favored by different materials properties. The approach is applied to designing the Bayesian error...... sets validates the applicability of BEEF-vdW to studies in chemistry and condensed matter physics. Applications of the approximation and its Bayesian ensemble error estimate to two intricate surface science problems support this....

  9. Impulse exchange at the surface of the ocean and the fractal dimension of drifter trajectories

    Directory of Open Access Journals (Sweden)

    D. M. Summers

    2002-01-01

    Full Text Available An impulse-based model is developed to represent a coupling between turbulent flow in the atmosphere and turbulent flow in the ocean. In particular, it is argued that the atmosphere flowing horizontally over the ocean surface generates a velocity fluctuation field in the latter's near-surface flow. The mechanism for this can be understood kinematically in terms of an exchange of tangentially-oriented fluid impulse at the air-sea interface. We represent this exchange numerically through the creation of Lagrangian elements of impulse density. An indication of the efficacy of such a model would lie in its ability to predict the observed fractal dimension of lateral trajectories of submerged floats set adrift in the ocean. To this end, we examine the geometry of lateral tracer-paths determined from the present model.

  10. Monte Carlo simulation of heavy ion induced kinetic electron emission from an Al surface

    CERN Document Server

    Ohya, K

    2002-01-01

    A Monte Carlo simulation is performed in order to study heavy ion induced kinetic electron emission from an Al surface. In the simulation, excitation of conduction band electrons by the projectile ion and recoiling target atoms is treated on the basis of the partial wave expansion method, and the cascade multiplication process of the excited electrons is simulated as well as collision cascade of the recoiling target atoms. Experimental electron yields near conventional threshold energies of heavy ions are simulated by an assumption of a lowering in the apparent surface barrier for the electrons. The present calculation derives components for electron excitations by the projectile ion, the recoiling target atoms and the electron cascades, from the calculated total electron yield. The component from the recoiling target atoms increases with increasing projectile mass, whereas the component from the electron cascade decreases. Although the components from the projectile ion and the electron cascade increase with...

  11. Enhanced charging kinetics of porous electrodes: surface conduction as a short-circuit mechanism.

    Science.gov (United States)

    Mirzadeh, Mohammad; Gibou, Frederic; Squires, Todd M

    2014-08-29

    We use direct numerical simulations of the Poisson-Nernst-Planck equations to study the charging kinetics of porous electrodes and to evaluate the predictive capabilities of effective circuit models, both linear and nonlinear. The classic transmission line theory of de Levie holds for general electrode morphologies, but only at low applied potentials. Charging dynamics are slowed appreciably at high potentials, yet not as significantly as predicted by the nonlinear transmission line model of Biesheuvel and Bazant. We identify surface conduction as a mechanism which can effectively "short circuit" the high-resistance electrolyte in the bulk of the pores, thus accelerating the charging dynamics and boosting power densities. Notably, the boost in power density holds only for electrode morphologies with continuous conducting surfaces in the charging direction.

  12. Tuning the metal-insulator transition in manganite films through surface exchange coupling with magnetic nanodots.

    Science.gov (United States)

    Ward, T Z; Gai, Z; Xu, X Y; Guo, H W; Yin, L F; Shen, J

    2011-04-15

    In strongly correlated electronic systems, the global transport behavior depends sensitively on spin ordering. We show that spin ordering in manganites can be controlled by depositing isolated ferromagnetic nanodots at the surface. The exchange field at the interface is tunable with nanodot density and makes it possible to overcome dimensionality and strain effects in frustrated systems to greatly increasing the metal-insulator transition and magnetoresistance. These findings indicate that electronic phase separation can be controlled by the presence of magnetic nanodots.

  13. Adsorption of surfactants on sand surface in enhanced oil recovery: Isotherms, kinetics and thermodynamic studies

    Energy Technology Data Exchange (ETDEWEB)

    Bera, Achinta; Kumar, T.; Ojha, Keka; Mandal, Ajay, E-mail: mandal_ajay@hotmail.com

    2013-11-01

    Adsorption of surfactants onto reservoir rock surface may result in the loss and reduction of their concentrations in surfactant flooding, which may render them less efficient or ineffective in practical applications of enhanced oil recovery (EOR) techniques. Surfactant flooding for EOR received attraction due to its ability to increase the displacement efficiency by lowering the interfacial tension between oil and water and mobilizing the residual oil. This article highlights the adsorption of surfactants onto sand surface with variation of different influencing factors. It has been experimentally found that adsorption of cationic surfactant on sand surface is more and less for anionic surfactant, while non-ionic surfactant shows intermediate behaviour. X-ray diffraction (XRD) study of clean sand particles has been made to determine the main component present in the sand particles. The interaction between sand particles and surfactant has been studied by Fourier Transform Infrared (FTIR) Spectroscopy of the sand particles before and after aging with surfactant. Salinity plays an important role in adsorption of anionic surfactant. Batch experiments were also performed to understand the effects of pH and adsorbent dose on the sorption efficiency. The sand particles exhibited high adsorption efficiency at low pH for anionic and nonionic surfactants. But opposite trend was found for cationic surfactant. Adsorption data were analyzed by fitting with Langmuir, Freundlich, Redlich-Peterson, and Sips isotherm models. Results show that the Langmuir isotherm and pseudo-second order kinetics models suit the equilibrium and kinetics of adsorption on sand surface. Thermodynamics feasibility of the adsorption process was also studied to verify the spontaneity of the process.

  14. Effects of airway surface liquid height on the kinetics of extracellular nucleotides in airway epithelia.

    Science.gov (United States)

    Amarante, Tauanne D; da Silva, Jafferson K L; Garcia, Guilherme J M

    2014-12-21

    Experimental techniques aimed at measuring the concentration of signaling molecules in the airway surface liquid (ASL) often require an unrealistically large ASL volume to facilitate sampling. This experimental limitation, prompted by the difficulty of pipetting liquid from a very shallow layer (~15 μm), leads to dilution and the under-prediction of physiologic concentrations of signaling molecules that are vital to the regulation of mucociliary clearance. Here, we use a computational model to describe the effect of liquid height on the kinetics of extracellular nucleotides in the airway surface liquid coating respiratory epithelia. The model consists of a reaction-diffusion equation with boundary conditions that represent the enzymatic reactions occurring on the epithelial surface. The simulations reproduce successfully the kinetics of extracellular ATP following hypotonic challenge for ASL volumes ranging from 25 μl to 500 μl in a 12-mm diameter cell culture. The model reveals that [ATP] and [ADO] reach 1200 nM and 2200 nM at the epithelial surface, respectively, while their volumetric averages remain less than 200 nM at all times in experiments with a large ASL volume (500 μl). These findings imply that activation of P2Y2 and A2B receptors is robust after hypotonic challenge, in contrast to what could be concluded based on experimental measurements of volumetric concentrations in large ASL volumes. Finally, given the central role that ATP and ADO play in regulating mucociliary clearance, we investigated which enzymes, when inhibited, provide the greatest increase in ATP and ADO concentrations. Our findings suggest that inhibition of NTPDase1/highTNAP would cause the greatest increase in [ATP] after hypotonic challenge, while inhibition of the transporter CNT3 would provide the greatest increase in [ADO]. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. Load-dependent surface diffusion model for analyzing the kinetics of protein adsorption onto mesoporous materials.

    Science.gov (United States)

    Marbán, Gregorio; Ramírez-Montoya, Luis A; García, Héctor; Menéndez, J Ángel; Arenillas, Ana; Montes-Morán, Miguel A

    2018-02-01

    The adsorption of cytochrome c in water onto organic and carbon xerogels with narrow pore size distributions has been studied by carrying out transient and equilibrium batch adsorption experiments. It was found that equilibrium adsorption exhibits a quasi-Langmuirian behavior (a g coefficient in the Redlich-Peterson isotherms of over 0.95) involving the formation of a monolayer of cyt c with a depth of ∼4nm on the surface of all xerogels for a packing density of the protein inside the pores of 0.29gcm -3 . A load-dependent surface diffusion model (LDSDM) has been developed and numerically solved to fit the experimental kinetic adsorption curves. The results of the LDSDM show better fittings than the standard homogeneous surface diffusion model. The value of the external mass transfer coefficient obtained by numerical optimization confirms that the process is controlled by the intraparticle surface diffusion of cyt c. The surface diffusion coefficients decrease with increasing protein load down to zero for the maximum possible load. The decrease is steeper in the case of the xerogels with the smallest average pore diameter (∼15nm), the limit at which the zero-load diffusion coefficient of cyt c also begins to be negatively affected by interactions with the opposite wall of the pore. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. Assessment of surface reactivity of thorium oxide in conditions close to chemical equilibrium by isotope exchange {sup 229}Th/{sup 232}Th method

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki-Muresan, Tomo; Perrigaud, Katy; Vandenborre, Johan; Ribet, Solange; Grambow, Bernd [Nantes Univ., CNRS/IN2P3 (France). SUBATECH Unite Mixte de Recherche 6457; Takamasa, Inai [TOKAI Univ., Kanagawa (Japan)

    2017-08-01

    This work aims to assess the solubility and the surface reactivity of crystallized thorium at pH 3.0 in presence of three types of solids: synthesized powder at 1300 C, crushed kernel, and intact kernel. In this study, the kernel is composed by the core solid from high temperature reactors (HTR) sphere particles. The originality of this work consisted in following in a sequential order the kinetic of dissolution, the surface reactivity in presence of isotope tracer {sup 229}Th, and its desorption process. Long time experiments (634 days) allowed to get deeper understanding on the behavior of the surface reactivity in contact with the solution. Solubility values are ranging from 0.3 x 10{sup -7} mol.L{sup -1} to 3 x 10{sup -7} mol.L{sup -1} with a dissolution rate of 10{sup -6}-10{sup -4} g.m{sup -2} day{sup -1}. PHREEQC modeling showed that crystallized ThO{sub 2}(cr, 20 nm) phase controls the equilibrium in solution. Isotope exchange between {sup 229}Th and {sup 232}Th indicated that well-crystallized phase exist as an inert surface regarding to the absence of exchange between surface solid and solution.

  17. Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light.

    Science.gov (United States)

    Jia, Hanzhong; Li, Li; Chen, Hongxia; Zhao, Yue; Li, Xiyou; Wang, Chuanyi

    2015-04-28

    Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe(3+)>Al(3+)>Cu(2+)>Ca(2+)>K(+)>Na(+), which is consistent with the binding energy of cation-π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation-π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na(+)-smectite and K(+)-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe(3+), Al(3+), and Cu(2+) are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O2(-) , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Solvent effects on the kinetics of the chlorine isotopic exchange reaction between chloride ion and O,O-diphenyl phosphorochloridate or O,O-diphenyl phosphorchloridothioate

    International Nuclear Information System (INIS)

    Mikolajczyk, M.; Slebocka-Tilk, H.; Reimschussel, W.

    1982-01-01

    The effect of solvent on the kinetics of the chlorine isotopic exchange reaction between 36 Cl- ions and O,O-diphenyl phosphorochloridate or O,O-diphenyl phosphorochloridothioate has been investigated in nitromethane, acetonitrile, propylene carbonate, benzonitrile, nitrobenzene, and hexamethyl-phosphoric triamide. The rate constants decrease with increasing electrophilicity of the solvent. A good correlation between the logarithm of the rate constants and acceptor number (AN) of the solvent was obtained with identical slopes for reactions with phosphoryl and thiophosporyl compounds. The slopes for the dependence of ΔH or TΔS vs. AN for chlorine isotopic exchange in (PHO) 2 pace are opposite those for the exchange reaction in (PHO) 2 PSCl, so a constant ratio of k/sub p=O//k/sub p=s/ is observed, resulting from compensation of ΔH by ΔS. The effect of solvent on the initial state (from solubility measurements) and the transition state of the reaction between (PhO) 2 PSCl and the Cl- ion was evaluated. Changes of solvation of (PHO) 2 PSCE have practically no effect on the kinetics of the reactions. Changes of solvation of the chloride ion and of the transition state primarily influence the rate constants and activation parameters of the investigated isotopic-exchange reaction

  19. THE SURFACE-MEDIATED UNFOLDING KINETICS OF GLOBULAR PROTEINS IS DEPENDENT ON MOLECULAR WEIGHT AND TEMPERATURE

    Energy Technology Data Exchange (ETDEWEB)

    Patananan, A.N.; Goheen, S.C.

    2008-01-01

    The adsorption and unfolding pathways of proteins on rigid surfaces are essential in numerous complex processes associated with biomedical engineering, nanotechnology, and chromatography. It is now well accepted that the kinetics of unfolding are characterized by chemical and physical interactions dependent on protein deformability and structure, as well as environmental pH, temperature, and surface chemistry. Although this fundamental process has broad implications in medicine and industry, little is known about the mechanism because of the atomic lengths and rapid time scales involved. Therefore, the unfolding kinetics of myoglobin, β-glucosidase, and ovalbumin were investigated by adsorbing the globular proteins to non-porous cationic polymer beads. The protein fractions were adsorbed at different residence times (0, 9, 10, 20, and 30 min) at near-physiological conditions using a gradient elution system similar to that in high-performance liquid chromatography. The elution profi les and retention times were obtained by ultraviolet/visible spectrophotometry. A decrease in recovery was observed with time for almost all proteins and was attributed to irreversible protein unfolding on the non-porous surfaces. These data, and those of previous studies, fi t a positively increasing linear trend between percent unfolding after a fi xed (9 min) residence time (71.8%, 31.1%, and 32.1% of myoglobin, β-glucosidase, and ovalbumin, respectively) and molecular weight. Of all the proteins examined so far, only myoglobin deviated from this trend with higher than predicted unfolding rates. Myoglobin also exhibited an increase in retention time over a wide temperature range (0°C and 55°C, 4.39 min and 5.74 min, respectively) whereas ovalbumin and β-glucosidase did not. Further studies using a larger set of proteins are required to better understand the physiological and physiochemical implications of protein unfolding kinetics. This study confi rms that surface

  20. Surface Reaction Kinetics of Ga(1-x)In(x)P Growth During Pulsed Chemical Beam Epitaxy

    National Research Council Canada - National Science Library

    Dietz, N; Beeler, S. C; Schmidt, J. W; Tran, H. T

    2000-01-01

    ... into the surface reaction kinetics during an organometallic deposition process. These insights will allow us to move the control point closer to the point where the growth occurs, which in a chemical been epitaxy process is a surface reaction layer (SRL...

  1. Kinetic study on ligand exchange reaction between ethylenedicysteine and 99mTc- glucoheptonate (99mTc-GH)

    International Nuclear Information System (INIS)

    Wu, C.Y.; Ji, S.R.; Lu, C.X.; Ding, S.Y.; Chen, Z.P.; Lin, X.T.

    2002-01-01

    Aim: 99m Tc-L,L-ethylenedicysteine( 99m Tc-EC)is a new type of renal imaging agent. It can be labeled very easily and efficiently at room temperature through direct labeling at pH 12. The need for direct labeling at pH 12 does not compromise the simplicity and ease of preparation of 99m Tc-EC and its practical usefulness in daily routine. On the basis of the labeling experiments, we developed a ligand exchange labeling method, in which the labeling EC with 99m Tc can be performed at pH 8. In order to provide a theoretic basis, a detailed kinetic study of ligand exchange reaction between 99m Tc- glucoheptonate( 99m Tc-GH) and EC was carried out. Materials and Methods: 99m Tc-EC is prepared as follows: 99m Tc-GH + EC → 99m Tc-EC + GH, labeling can be easily performed by adding 99m TcO 4 - (2∼6ml generator elute) to glucoheptonate solution containing SnCl 2 .2H 2 O solution to form 99m Tc-GH, then freshly prepared 99m Tc-GH is transferred to the aqueous solution of different concentrations of EC at different pH value, after being shaken, 99m Tc-EC was formed. Radiolabeling yield(RLY) and radiochemical purity(RCP) of 99m Tc-GH and 99m Tc-EC were measured by Xinhua No.1 paper with developing system of Me 2 CO/H 2 O/con.NH 3 .H 2 O=9/3/1(V/V). 99m Tc-GH(RCP must be over 98%, 80ul, 3.6∼7.4MBq) was added to 1ml of 0.5mol/L phosphate buffer(pH 12) containing different amount of EC(150, 75, 50 and 15ug), the sample was taken out at different time intervals and RCP was determined. The solution of EC(30ul, 5g/L) was added to 1ml of 0.5mol/L phosphate buffer at different pH value(pH11, 10, 9, 8, 7), after completely vortexed, 99m Tc-GH(RCP must be over 98%, 80ul, 3.6∼7.4MBq) was then added, the sample was taken out and RCP was determined as above. The rate constant(k) of ligand exchange reaction at different concentrations of EC and different reaction pH values were calculated out by integrating. Plot ln[1/(1-RLY)] vs t(time) showed a liner relationship, and the rate

  2. Characterization of photosynthetic gas exchange in leaves under simulated adaxial and abaxial surfaces alternant irradiation.

    Science.gov (United States)

    Zhang, Zi-Shan; Li, Yu-Ting; Gao, Hui-Yuan; Yang, Cheng; Meng, Qing-Wei

    2016-07-05

    Previous investigations on photosynthesis have been performed on leaves irradiated from the adaxial surface. However, leaves usually sway because of wind. This action results in the alternating exposure of both the adaxial and abaxial surfaces to bright sunlight. To simulate adaxial and abaxial surfaces alternant irradiation (ad-ab-alt irradiation), the adaxial or abaxial surface of leaves were exposed to light regimes that fluctuated between 100 and 1,000 μmol m(-2) s(-1). Compared with constant adaxial irradiation, simulated ad-ab-alt irradiation suppressed net photosynthetic rate (Pn) and transpiration (E) but not water use efficiency. These suppressions were aggravated by an increase in alternant frequency of the light intensity. When leaves were transferred from constant light to simulated ad-ab-alt irradiation, the maximum Pn and E during the high light period decreased, but the rate of photosynthetic induction during this period remained constant. The sensitivity of photosynthetic gas exchange to simulated ad-ab-alt irradiation was lower on abaxial surface than adaxial surface. Under simulated ad-ab-alt irradiation, higher Pn and E were measured on abaxial surface compared with adaxial surface. Therefore, bifacial leaves can fix more carbon than leaves with two "sun-leaf-like" surfaces under ad-ab-alt irradiation. Photosynthetic research should be conducted under dynamic conditions that better mimic nature.

  3. Influence of ionic conductivity of the nano-particulate coating phase on oxygen surface exchange of La0.58Sr0.4Co0.2Fe0.8O3-δ

    NARCIS (Netherlands)

    Saher, S.; Naqash, S.; Boukamp, Bernard A.; Hu, Bobing; Xia, Changrong; Bouwmeester, Henricus J.M.

    2017-01-01

    The oxygen surface exchange kinetics of mixed-conducting perovskite La0.58Sr0.4Co0.2Fe0.8O3 d (LSCF) ceramics coated with a porous nano-particulate layer of either gadolinea (Gd2O3), ceria (CeO2) or 20 mol% Gd-doped ceria (GCO) was determined by electrical conductivity relaxation (ECR). The

  4. A review of measurement and modelling results of particle atmosphere-surface exchange

    DEFF Research Database (Denmark)

    Pryor, Sara; Gallagher, M.; Sievering, H.

    2008-01-01

    Atmosphere-surface exchange represents one mechanism by which atmospheric particle mass and number size distributions are modified. Deposition velocities (upsilon(d)) exhibit a pronounced dependence on surface type, due in part to turbulence structure (as manifest in friction velocity), with minima...... agreement between models and observations is found over less-rough surfaces though those data also imply substantially higher surface collection efficiencies than were originally proposed and are manifest in current models. We review theorized dependencies for particle fluxes, describe and critique model...... of approximately 0.01 and 0.2 cm s(-1) over grasslands and 0.1-1 cm s(-1) over forests. However, as noted over 20 yr ago, observations over forests generally do not support the pronounced minimum of deposition velocity (upsilon(d)) for particle diameters of 0.1-2 mu m as manifest in theoretical predictions. Closer...

  5. Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden-Popper phases?

    Science.gov (United States)

    Tomkiewicz, Alex C; Tamimi, Mazin A; Huq, Ashfia; McIntosh, Steven

    2015-01-01

    The possible link between oxygen surface exchange rate and bulk oxygen anion diffusivity in mixed ionic and electronic conducting oxides is a topic of great interest and debate. While a large body of experimental evidence and theoretical analyses support a link, observed differences between bulk and surface composition of these materials are hard to reconcile with this observation. This is further compounded by potential problems with simultaneous measurement of both parameters. Here we utilize separate techniques, in situ neutron diffraction and pulsed isotopic surface exchange, to examine bulk ion mobility and surface oxygen exchange rates of three Ruddlesden-Popper phases, general form A(n-1)A(2)'B(n)O(3n+1), A(n-1)A(2)'B(n)X(3n+1); LaSrCo(0.5)Fe(0.5)O(4-δ) (n = 1), La(0.3)Sr(2.7)CoFeO(7-δ) (n = 2) and LaSr3Co(1.5)Fe(1.5)O(10-δ) (n = 3). These measurements are complemented by surface composition determination via high sensitivity-low energy ion scattering. We observe a correlation between bulk ion mobility and surface exchange rate between materials. The surface exchange rates vary by more than one order of magnitude with high anion mobility in the bulk of an oxygen vacancy-rich n = 2 Ruddlesden-Popper material correlating with rapid oxygen exchange. This is in contrast with the similar surface exchange rates which we may expect due to similar surface compositions across all three samples. We conclude that experimental limitations lead to inherent convolution of surface and bulk rates, and that surface exchange steps are not likely to be rate limiting in oxygen incorporation.

  6. Surface coverage of Pt atoms on PtCo nanoparticles and catalytic kinetics for oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Jiang Rongzhong, E-mail: rongzhong.jiang@us.army.mi [Sensors and Electron Devices Directorate, U.S. Army Research Laboratory, 2800 Powder Mill Road, Adelphi, MD 20783-1197 (United States); Rong, Charles; Chu, Deryn [Sensors and Electron Devices Directorate, U.S. Army Research Laboratory, 2800 Powder Mill Road, Adelphi, MD 20783-1197 (United States)

    2011-02-01

    The surface coverage of Pt atoms on PtCo nanoparticles and its effect on catalytic kinetics for oxygen reduction were investigated. The PtCo nanoparticles with different surface coverage of Pt atoms were synthesized with various methods, including normal chemical method, microemulsion synthesis, and ultrasound-assisted microemulsion. A model of Pt atoms filling into a spherical nanoparticle was proposed to explain the relationship of surface metal atoms and nanoparticle size. The catalytic activity of the PtCo nano-particles is highly dependent on the synthetic methods, even if they have the same chemical composition. The PtCo nano-particles synthesized with ultrasound-assisted microemulsion showed the highest activity, which is attributed to an increase of active surface coverage of Pt atoms on the metal nanoparticles. The rate of oxygen reduction at 0.5 V (vs. SCE) catalyzed by the PtCo synthesized with ultrasound-assisted micro-emulsion was about four times higher than that of the PtCo synthesized with normal chemical method. As demonstrated with rotating-ring disk electrode measurement, the PtCo nano-particles can catalyze oxygen 4-electron reduction to water without intermediate H{sub 2}O{sub 2} detected.

  7. Thermal performance of a spirally coiled finned tube heat exchanger under wet-surface conditions

    International Nuclear Information System (INIS)

    Wongwises, Somchai; Naphon, Paisarn

    2006-01-01

    This paper is a continuation of the author's previous work on spiral coil heat exchangers. In the present study, the heat transfer characteristics and the performance of a spirally coiled finned tube heat exchanger under wet-surface conditions are theoretically and experimentally investigated. The test section is a spiral-coil heat exchanger which consists of a steel shell and a spirally coiled tube unit. The spiral-coil unit consists of six layers of concentric spirally coiled finned tubes. Each tube is fabricated by bending a 9.6 mm diameter straight copper tube into a spiral-coil of four turns. The innermost and outermost diameters of each spiral-coil are 145.0 and 350.4 mm, respectively. Aluminium crimped spiral fins with thickness of 0.6 mm and outer diameter of 28.4 mm are placed around the tube. The edge of fin at the inner diameter is corrugated. Air and water are used as working fluids in shell side and tube side, respectively. The experiments are done under dehumidifying conditions. A mathematical model based on the conservation of mass and energy is developed to simulate the flow and heat transfer characteristics of working fluids flowing through the heat exchanger. The results obtained from the present model show reasonable agreement with the experimental data

  8. Kinetics of isotope exchange reactions involving intra- and intermolecular reactions: 1. Rate law for a system with two chemical compounds and three exchangeable atoms

    International Nuclear Information System (INIS)

    Xuelei Chu; Ohmoto, Hiroshi

    1991-01-01

    For an isotopic exchange reaction between two compounds (X and AB) in a homogeneous system, such as a gaseous or aqueous system, where one (AB) of them possesses two exchangeable atoms in non-equivalent positions and where one intramolecular isotope exchange (A ↔ B) and two intermolecular isotope exchange reactions (X ↔ A and X ↔ B) may occur, its rate law no longer obeys a pseudo-first order rate equation described for simple two-component systems by many previous investigators. The change with time of the δ value of each of the three components (X, A, and B) in a closed and homogeneous system is a complicated function of the initial δ values of the three components, the chemical concentrations of the two compounds, and the overall rate constants of the forward and reverse reactions involving the two intermolecular and one intramolecular reactions of isotope exchanges. Also, for some one of the three components, the change of its δ value with time may not be monotonic, and the relationship of 1n (1 - F) with time may be non-linear in a plot of 1n (1 - F) vs. t. In addition, the rate law of the isotope exchange reaction in this system also provides a quantitative method to estimate the overall rate constants for the one-intra-and two intermolecular isotope exchanges and the equilibrium isotopic fractionation factors among the three components

  9. Scaling properties of fracture surfaces on glass strengthened by ionic exchange

    International Nuclear Information System (INIS)

    Garza-Mendez, F.J.; Hinojosa-Rivera, M.; Gomez, I.; Sanchez, E.M.

    2007-01-01

    In this work the results of the statistical topometric analysis of fracture surfaces of soda-lime-silica glass with and without ionic exchange treatment are reported. In this case, the mechanism of substitution is K + -Na + . atomic force microscopy (AFM) was employed to record the topometric data from the fracture surface. The roughness exponent (ζ) and the correlation length (ξ) were calculated by the variable bandwidth method. The analysis for both glasses (subjected and non-subjected to ionic exchange) for ζ shows a value ∼0.8, this value agrees well with that reported in the literature for rapid crack propagation in a variety of materials. The correlation length shows different values for each condition. These results, along with those of microhardness indentations suggest that the self-affine correlation length is influenced by the complex interactions of the stress field of microcracks with that resulting from the collective behavior of the point defects introduced by the strengthening mechanism of ionic exchange

  10. Air-side performance of a micro-channel heat exchanger in wet surface conditions

    Directory of Open Access Journals (Sweden)

    Srisomba Raviwat

    2017-01-01

    Full Text Available The effects of operating conditions on the air-side heat transfer, and pressure drop of a micro-channel heat exchanger under wet surface conditions were studied experimentally. The test section was an aluminum micro-channel heat exchanger, consisting of a multi-louvered fin and multi-port mini-channels. Experiments were conducted to study the effects of inlet relative humidity, air frontal velocity, air inlet temperature, and refrigerant temperature on air-side performance. The experimental data were analyzed using the mean enthalpy difference method. The test run was performed at relative air humidities ranging between 45% and 80%; air inlet temperature ranges of 27, 30, and 33°C; refrigerant-saturated temperatures ranging from 18 to 22°C; and Reynolds numbers between 128 and 166. The results show that the inlet relative humidity, air inlet temperature, and the refrigerant temperature had significant effects on heat transfer performance and air-side pressure drop. The heat transfer coefficient and pressure drop for the micro-channel heat exchanger under wet surface conditions are proposed in terms of the Colburn j factor and Fanning f factor.

  11. Surface modification of cation exchange membranes by graft polymerization of PAA-co-PANI/MWCNTs nanoparticles

    International Nuclear Information System (INIS)

    Nemati, Mahsa; Hosseini, Sayed Mohsen; Bagheripour, Ehsan; Madaeni, Sayed Siavash

    2016-01-01

    Surface modification of polyvinylchloride based heterogeneous cation exchange membrane was performed by graft polymerization of PAA and PAA-co-PANI/MWCNTs nanoparticles. The ion exchange membranes were prepared by solution casting technique. Spectra analysis confirmed graft polymerization clearly. SEM images illustrated that graft polymerization covers the membranes by simple gel network entanglement. The membrane water content was decreased by graft polymerization of PAA-co-PANI/MWCNTs nanoparticles on membrane surface. Membrane transport number and selectivity declined initially by PAA graft polymerization and then began to increase by utilizing of composite nanoparticles in modifier solution. The sodium and barium flux was improved sharply by PAA and PAAco- 0.01%wt PANI/MWCNTs graft polymerization on membrane surface and then decreased again by more increase of PANI/MWCNTs nanoparticles content ratio in modifier solution. The electrodialysis experiment results in laboratory scale showed higher dialytic rate in heavy metals removal for grafted-PAA and grafted-PAA-co-PANI/MWCNTs modified membrane compared to pristine one. Membrane areal electrical resistance was also decreased by introducing graft polymerization of PAA and PAA-co-PANI/MWCNTs NPs on membrane surface.

  12. Static and kinetic friction force and surface roughness of different archwire-bracket sliding contacts.

    Science.gov (United States)

    Carrion-Vilches, Francisco J; Bermudez, María-Dolores; Fructuoso, Paula

    2015-01-01

    The aim of this study was to determine the static and kinetic friction forces of the contact bracket-archwire with different dental material compositions in order to select those materials with lower resistance to sliding. We carried out sliding friction tests by means of a universal testing machine following an experimental procedure as described in ASTM D1894 standard. We determined the static and kinetic friction forces under dry and lubricating conditions using an artificial saliva solution at 36.5ºC. The bracket-archwire pairs studied were: stainless steel-stainless steel; stainless steel-glass fiber composite; stainless steel-Nitinol 60; sapphire-stainless steel; sapphire-glass fiber composite; and sapphire-Nitinol 60. The best performance is obtained for Nitinol 60 archwire sliding against a stainless steel bracket, both under dry and lubricated conditions. These results are in agreement with the low surface roughness of Nitinol 60 with respect to the glass fiber composite archwire. The results described here contribute to establishing selection criteria for materials for dental archwire-brackets.

  13. Drying Kinetics and Optimisation of Pectin Extraction from Banana Peels via Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    Bee Lin Chua

    2018-01-01

    Full Text Available Banana peels which are the waste in abundance, are used to extract valuable pectin. The gelling ability of the pectin has gained attention in food and pharmaceutical industries. This research aims to select the best drying kinetic model for banana peels and also optimize the pectin extraction process using Box-Behnken response surface design (BBD. Determination of pectin gelling mechanism using degree of esterification (DE is also focused in this research. In this study, oven drying with temperature 50°C was chosen as the best drying temperature due to highest extraction yield. Furthermore, Page-Two-term model was selected as the best model to describe the drying kinetics of banana peels due to highest R2 value (0.9991 and lowest RMSE value (0.001. The optimal extraction conditions given by BBD were 75°C extraction temperature, 23 min extraction time and 1:33.3 g/ml solid-liquid ratio. Likewise, the DE for both pectins extracted using unoptimised and optimised conditions were 71.92±1.38% and 76.1±2.07% respectively. Both of the pectins were classified as high-methoxyl pectins. The pectin with higher DE also indicated that the rate of gel formation is higher. The results showed that the pectin yield and gelling time has successfully improved after optimised the pectin extraction process.

  14. Variation in surface water-groundwater exchange with land use in an urban stream

    Science.gov (United States)

    Ryan, Robert J.; Welty, Claire; Larson, Philip C.

    2010-10-01

    SummaryA suite of methods is being utilized in the Baltimore metropolitan area to develop an understanding of the interaction between groundwater and surface water at multiple space and time scales. As part of this effort, bromide tracer experiments were conducted over two 10-day periods in August 2007 and May 2008 along two sections (each approximately 900 m long) of Dead Run, a small urban stream located in Baltimore County, Maryland, to investigate the influence of distinct zones of riparian land cover on surface-subsurface exchange and transient storage under low and high baseflow conditions. Riparian land cover varied by reach along a gradient of land use spanning parkland, suburban/residential, commercial, institutional, and transportation, and included wooded, meadow, turf grass, and impervious cover. Under summer low baseflow conditions, surface water-groundwater exchange, defined by gross inflow and gross outflow, was larger and net inflow (gross inflow minus gross outflow) had greater spatial variability, than was observed under spring high baseflow conditions. In addition, the fraction of nominal travel time attributable to transient storage ( Fmed) was lower and was more spatially variable under high baseflow conditions than under low baseflow conditions. The influence of baseflow condition on surface water-ground water exchange and transient storage was most evident in the subreaches with the least riparian forest cover and these effects are attributed to a lack of shading in reaches with little riparian forest cover. We suggest that under summer low baseflow conditions, the lack of shading allowed excess in-channel vegetation growth which acted as a transient storage zone and a conduit for outflow (i.e. uptake and evapotranspiration). Under spring high baseflow conditions the transient storage capacity of the channel was reduced because there was little in-channel vegetation.

  15. Local antiferromagnetic exchange and collaborative Fermi surface as key ingredients of high temperature superconductors

    Science.gov (United States)

    Hu, Jiangping; Ding, Hong

    2012-01-01

    Cuprates, ferropnictides and ferrochalcogenides are three classes of unconventional high temperature superconductors, who share similar phase diagrams in which superconductivity develops after a magnetic order is suppressed, suggesting a strong interplay between superconductivity and magnetism, although the exact picture of this interplay remains elusive. Here we show that there is a direct bridge connecting antiferromagnetic exchange interactions determined in the parent compounds of these materials to the superconducting gap functions observed in the corresponding superconducting materials: in all high temperature superconductors, the Fermi surface topology matches the form factor of the pairing symmetry favored by local magnetic exchange interactions. We suggest that this match offers a principle guide to search for new high temperature superconductors. PMID:22536479

  16. Solid oxide electrode kinetics in light of in situ surface studies

    DEFF Research Database (Denmark)

    Mogensen, Mogens Bjerg

    2014-01-01

    The combination of in situ and in particular in operando characterization methods such as electrochemical impedance spectroscopy (EIS) on both technical and model electrode are well known ways to gain some practical insight in electrode reaction kinetics. Yet, is has become clear that in spite...... of the strengths it is not sufficient to reveal much details of the electrode mechanisms mainly because it provide average values only. Therefore it has to be combined with surface science methods in order to reveal the interface structure and composition. Ex situ methods have been very useful over the latest....... Furthermore, it seems that detailed mathematical modeling using new tools like COMSOL is necessary for the synthesis of the large amount of data for a well-characterized electrode into one physical meaningful picture. A brief review of literature an own data will be presented with a practical example of SOFC...

  17. Thermodynamic and kinetic aspects on the selective surface oxidation of binary, ternary and quarternary model alloys

    International Nuclear Information System (INIS)

    Swaminathan, Srinivasan; Spiegel, Michael

    2007-01-01

    Segregation and selective oxidation phenomena of minor alloying elements during annealing of steel sheets lead to the formation of bare spots after hot dip galvanizing. In order to understand the influence of common alloying elements on the surface chemistry after annealing, model alloys of binary (Fe-2Si, Fe-2Mn and Fe-0.8Cr), ternary (Fe-2Mn-2Si, Fe-2Mn-0.8Cr and Fe-2Si-0.8Cr) and quarternary (Fe-2Mn-2Si-0.8Cr) systems were investigated. The specimens were annealed for 60 s at 820 deg. C in N 2 -5% H 2 gas atmospheres with different dew points -80 and -40 deg. C, respectively. Surface chemistry of the annealed specimens was obtained by using X-ray photoelectron spectroscopy (XPS). The field emission scanning electron microscopy (FE-SEM) was used to view surface morphology. At low dew point -80 deg. C, apart from the thermodynamical calculations such as solubility product of oxides and their critical solute concentrations, kinetics play a decisive role on the selective oxidation, i.e. oxygen competition. As expected, the amount of external selective oxidation of alloying elements are well pronounced at higher dew point -40 deg. C. An attempt has been made to explain the dominant process of Si and Mn on Cr-oxidation and segregation. It is observed that annealing of quarternary system at higher dew point shifts the Cr-oxidation from external to internal

  18. Thermodynamic and kinetic aspects on the selective surface oxidation of binary, ternary and quarternary model alloys

    Energy Technology Data Exchange (ETDEWEB)

    Swaminathan, Srinivasan [High Temperature Reactions Group, Department of Interface Chemistry and Surface Engineering, Max-Planck-Institut fuer Eisenforschung GmbH, Max-Planck-Str. 1, D-40237 Duesseldorf (Germany)]. E-mail: s.swaminathan@mpie.de; Spiegel, Michael [High Temperature Reactions Group, Department of Interface Chemistry and Surface Engineering, Max-Planck-Institut fuer Eisenforschung GmbH, Max-Planck-Str. 1, D-40237 Duesseldorf (Germany)

    2007-03-15

    Segregation and selective oxidation phenomena of minor alloying elements during annealing of steel sheets lead to the formation of bare spots after hot dip galvanizing. In order to understand the influence of common alloying elements on the surface chemistry after annealing, model alloys of binary (Fe-2Si, Fe-2Mn and Fe-0.8Cr), ternary (Fe-2Mn-2Si, Fe-2Mn-0.8Cr and Fe-2Si-0.8Cr) and quarternary (Fe-2Mn-2Si-0.8Cr) systems were investigated. The specimens were annealed for 60 s at 820 deg. C in N{sub 2}-5% H{sub 2} gas atmospheres with different dew points -80 and -40 deg. C, respectively. Surface chemistry of the annealed specimens was obtained by using X-ray photoelectron spectroscopy (XPS). The field emission scanning electron microscopy (FE-SEM) was used to view surface morphology. At low dew point -80 deg. C, apart from the thermodynamical calculations such as solubility product of oxides and their critical solute concentrations, kinetics play a decisive role on the selective oxidation, i.e. oxygen competition. As expected, the amount of external selective oxidation of alloying elements are well pronounced at higher dew point -40 deg. C. An attempt has been made to explain the dominant process of Si and Mn on Cr-oxidation and segregation. It is observed that annealing of quarternary system at higher dew point shifts the Cr-oxidation from external to internal.

  19. Kinetic model for hydroxyapatite precipitation on human enamel surface by electrolytic deposition

    International Nuclear Information System (INIS)

    Lei Caixia; Liao Yingmin; Feng Zude

    2009-01-01

    The electrolytic deposition (ELD) of hydroxyapatite (HAP) coating on human enamel surface for different loading times at varied temperatures (ranging from 37 deg. C to 85 deg. C) and varied current densities (ranging from 0.05 mA cm -2 to 10 mA cm -2 ) was investigated in this study. Thin film x-ray diffraction, Fourier transform infrared and micro-Raman spectra analysis, as well as an environmental scanning electron microscope, were used to characterize the coating. The results showed that only the HAP phase occurred on the enamel surface after ELD experiments. The contents of HAP deposits on the enamel surface linearly changed proportional to the square root of the loading time, which was in good agreement with the kinetic model of ELD of HAP coating based on one-dimensional diffusion. The induction periods were observed on all the regression lines, and the rate of the HAP coating formation on enamel showed a linear relationship with the current density. It was implied that the diffusion process was the rate-determining step in the ELD of the HAP coating on human enamel.

  20. Kinetic model for hydroxyapatite precipitation on human enamel surface by electrolytic deposition

    Energy Technology Data Exchange (ETDEWEB)

    Lei Caixia; Liao Yingmin; Feng Zude, E-mail: zdfeng@xmu.edu.c [College of Materials, Xiamen University, Xiamen 361005 (China)

    2009-06-15

    The electrolytic deposition (ELD) of hydroxyapatite (HAP) coating on human enamel surface for different loading times at varied temperatures (ranging from 37 deg. C to 85 deg. C) and varied current densities (ranging from 0.05 mA cm{sup -2} to 10 mA cm{sup -2}) was investigated in this study. Thin film x-ray diffraction, Fourier transform infrared and micro-Raman spectra analysis, as well as an environmental scanning electron microscope, were used to characterize the coating. The results showed that only the HAP phase occurred on the enamel surface after ELD experiments. The contents of HAP deposits on the enamel surface linearly changed proportional to the square root of the loading time, which was in good agreement with the kinetic model of ELD of HAP coating based on one-dimensional diffusion. The induction periods were observed on all the regression lines, and the rate of the HAP coating formation on enamel showed a linear relationship with the current density. It was implied that the diffusion process was the rate-determining step in the ELD of the HAP coating on human enamel.

  1. Ge(001):B gas-source molecular beam epitaxy: B surface segregation, hydrogen desorption, and film growth kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Kim, H.; Greene, J.E. [Materials Science Department, the Coordinated Science Laboratory and the Materials Research Laboratory, University of Illinois, Urbana, Illinois 61801 (United States)

    1999-03-01

    Ultrahigh B-doped Ge(001) layers, with concentrations C{sub B} up to 8{times}10{sup 21} cm{sup {minus}3}, were grown by gas-source molecular beam epitaxy from Ge{sub 2}H{sub 6} and B{sub 2}H{sub 6} at temperatures T{sub s}=325{degree}C (in the surface-reaction-limited regime) and 600{degree}C (in the flux-limited regime). The samples were quenched, D site exchanged for H, and D{sub 2} temperature-programed desorption (TPD) used to determine B coverages {theta}{sub B} as a function of C{sub B} and T{sub s} by comparison with B-adsorbed Ge(001) reference samples with known {theta}{sub B} values. During Ge(001):B film growth, strong surface B segregation to the second layer was observed with surface-to-bulk B concentration ratios ranging up to 6000. The TPD spectra exhibited {alpha}{sub 2} and {alpha}{sub 1} peaks associated with dideuteride and monodeuteride desorption as well as lower-temperature B-induced {alpha}{sub 2}{sup {asterisk}} and {alpha}{sub 1}{sup {asterisk}} peaks associated with deuterium desorption from Ge{sup {asterisk}} surface atoms with B backbonds. Increasing {theta}{sub B} expanded the area under {alpha}{sub 2}{sup {asterisk}} and {alpha}{sub 1}{sup {asterisk}} at the expense of {alpha}{sub 2} and {alpha}{sub 1} and decreased the total D coverage {theta}{sub D}. The TPD results were used to determine the B segregation enthalpy, {minus}0.64 eV, and to explain and model the effects of high B coverages on Ge(001) growth kinetics. At T{sub s}=325{degree}C, where B segregation is kinetically hindered, film deposition rates R{sub Ge} are not a strong function of C{sub B}, exhibiting only a small decrease at C{sub B}{approx_gt}5{times}10{sup 18} cm{sup {minus}3}. However, at T{sub s}=600{degree}C, R{sub Ge} decreases by up to 40{percent} with increasing C{sub B}{approx_gt}1{times}10{sup 18} cm{sup {minus}3}. This is due primarily to the combination of B-induced Ge dimer vacancies and the deactivation of surface dangling bonds caused by charge transfer

  2. The fractal geometry of nutrient exchange surfaces does not provide an explanation for 3/4-power metabolic scaling

    Directory of Open Access Journals (Sweden)

    Painter Page R

    2005-08-01

    Full Text Available Abstract Background A prominent theoretical explanation for 3/4-power allometric scaling of metabolism proposes that the nutrient exchange surface of capillaries has properties of a space-filling fractal. The theory assumes that nutrient exchange surface area has a fractal dimension equal to or greater than 2 and less than or equal to 3 and that the volume filled by the exchange surface area has a fractal dimension equal to or greater than 3 and less than or equal to 4. Results It is shown that contradicting predictions can be derived from the assumptions of the model. When errors in the model are corrected, it is shown to predict that metabolic rate is proportional to body mass (proportional scaling. Conclusion The presence of space-filling fractal nutrient exchange surfaces does not provide a satisfactory explanation for 3/4-power metabolic rate scaling.

  3. Preparation of Two-Layer Anion-Exchange Poly(ethersulfone Based Membrane: Effect of Surface Modification

    Directory of Open Access Journals (Sweden)

    Lucie Zarybnicka

    2016-01-01

    Full Text Available The present work deals with the surface modification of a commercial microfiltration poly(ethersulfone membrane by graft polymerization technique. Poly(styrene-co-divinylbenzene-co-4-vinylbenzylchloride surface layer was covalently attached onto the poly(ethersulfone support layer to improve the membrane electrochemical properties. Followed by amination, a two-layer anion-exchange membrane was prepared. The effect of surface layer treatment using the extraction in various solvents on membrane morphological and electrochemical characteristics was studied. The membranes were tested from the point of view of water content, ion-exchange capacity, specific resistance, permselectivity, FT-IR spectroscopy, and SEM analysis. It was found that the two-layer anion-exchange membranes after the extraction using tetrahydrofuran or toluene exhibited smooth and porous surface layer, which resulted in improved ion-exchange capacity, electrical resistance, and permselectivity of the membranes.

  4. A Monte Carlo simulation of the exchange reaction between gaseous molecules and the atoms on a heterogeneous solid surface

    International Nuclear Information System (INIS)

    Imai, Hisao

    1980-01-01

    A method of the Monte Carlo simulation of the isotopic exchange reaction between gaseous molecules and the atoms on an arbitrarily heterogeneous solid surface is described by employing hydrogen as an example. (author)

  5. Kinetic Monte Carlo simulations of the effect of the exchange control layer thickness in CoPtCrB/CoPtCrSiO granular media

    Science.gov (United States)

    Almudallal, Ahmad M.; Mercer, J. I.; Whitehead, J. P.; Plumer, M. L.; van Ek, J.

    2018-05-01

    A hybrid Landau Lifshitz Gilbert/kinetic Monte Carlo algorithm is used to simulate experimental magnetic hysteresis loops for dual layer exchange coupled composite media. The calculation of the rate coefficients and difficulties arising from low energy barriers, a fundamental problem of the kinetic Monte Carlo method, are discussed and the methodology used to treat them in the present work is described. The results from simulations are compared with experimental vibrating sample magnetometer measurements on dual layer CoPtCrB/CoPtCrSiO media and a quantitative relationship between the thickness of the exchange control layer separating the layers and the effective exchange constant between the layers is obtained. Estimates of the energy barriers separating magnetically reversed states of the individual grains in zero applied field as well as the saturation field at sweep rates relevant to the bit write speeds in magnetic recording are also presented. The significance of this comparison between simulations and experiment and the estimates of the material parameters obtained from it are discussed in relation to optimizing the performance of magnetic storage media.

  6. A study of charge transfer kinetics in dye-sensitized surface conductivity solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Friedrich, Dennis

    2011-05-15

    The efficiency of the quasi-solid-state dye-sensitized solar cell developed by Junghaenel and Tributsch, the so-called Nano Surface Conductivity Solar Cell (NSCSC), was improved from 2% to 3.5% introducing a compact TiO{sub 2} underlayer, modifying the surface of the mesoporous TiO{sub 2} electrode, optimizing the deposition process of the electrolyte film, and replacing the platinum counter electrode by a carbon layer. Space-resolved photocurrent images revealed the importance of a homogeneous distribution of the electrolyte film. An uneven dispersion led to localized areas of high and low photocurrents, whereas the latter were attributed to an insufficient concentration of the redox couple. Impedance spectroscopy was performed on cells containing different concentrations of the redox couple. By modeling the spectra using an equivalent circuit with a transmission line of resistive and capacitive elements, the characteristic parameters of electron transport in the TiO{sub 2}, such as diffusion length and electron lifetime were obtained. The measurements indicated that the transport of the positive charge to the counter electrode is the main process limiting the efficiency of the cells. Excess charge carrier decay in functioning devices was analyzed by contactless transient photoconductance measurements in the microwave frequency range (TRMC). The lifetime of the photogenerated charge carriers was observed to decrease with increasing applied potential, reaching its maximum close to the opencircuit potential of the cell, where the photocurrent density was minimal, i.e. the potential dependent decay observed was limited by the injection of electrons into the front contact. The functioning of this NSCSC indicated that the transport of the positive charge occurs by solid-state diffusion at the surface of the TiO{sub 2} particles. TRMC measurements on subset devices in the form of sensitized TiO{sub 2} layers revealed charge carrier kinetics strongly dependent on the

  7. Fingerprints of surface magnetism in Cr2O3 based exchange bias heterostructures

    Science.gov (United States)

    He, Xi; Wang, Yi; Binek, Ch.

    2009-03-01

    Magnetoelectric materials experienced a recent revival as promising components of novel spintronic devices [1, 2, 3]. Since the magnetoelectric (ME) effect is relativistically small in traditional antiferromagnetic (AF) compounds like Cr2O3 (max. αzz 4ps/m) and also cross-coupling between ferroic order parameters is typically small in the modern multiferroics, it is a challenge to electrically induce sufficient magnetization required for the envisioned device applications. In exchange bias systems the bias field depends critically on the AF interface magnetization. Hence, a strong relation between the latter and the surface magnetization of the free Cr2O3 pinning layer can be expected. Our recent research indicates that there are surface magnetic phase transitions in free Cr2O3 (111) films accompanying surface structural phase transitions. Well defined AF interface magnetization is initialized through ME annealing to T=20K. Subsequently, the interface magnetization is thermally driven through phase transitions at T=120 and 210K. Their effects on the exchange bias are studied in Cr2O3 (111)/CoPt films with the help of polar Kerr and SQUID magnetometry. [1] P. Borisov et al. Phys. Rev. Lett. 94, 117203 (2005). [2] Ch. Binek, B.Doudin, J. Phys. Condens. Matter 17, L39 (2005). [3] R. Ramesh et al. 2007 Nature Materials 6 21. Financial support by NSF through Career DMR-0547887, MRSEC DMR-0820521 and the NRI.

  8. Effect of nanofluids on the performance of a miniature plate heat exchanger with modulated surface

    International Nuclear Information System (INIS)

    Pantzali, M.N.; Kanaris, A.G.; Antoniadis, K.D.; Mouza, A.A.; Paras, S.V.

    2009-01-01

    In the present work, the effect of the use of a nanofluid in a miniature plate heat exchanger (PHE) with modulated surface has been studied both experimentally and numerically. First, the thermophysical properties (i.e., thermal conductivity, heat capacity, viscosity, density and surface tension) of a typical nanofluid (CuO in water, 4% v/v) were systematically measured. The effect of surface modulation on heat transfer augmentation and friction losses was then investigated by simulating the existing miniature PHE as well as a notional similar PHE with flat plate using a CFD code. Finally, the effect of the nanofluid on the PHE performance was studied and compared to that of a conventional cooling fluid (i.e., water). The results suggest that, for a given heat duty, the nanofluid volumetric flow rate required is lower than that of water causing lower pressure drop. As a result, smaller equipment and less pumping power are required. In conclusion, the use of the nanofluids seems to be a promising solution towards designing efficient heat exchanging systems, especially when the total volume of the equipment is the main issue. The only drawbacks so far are the high price and the possible instability of the nanoparticle suspensions.

  9. Iron oxidation kinetics and phosphorus immobilization at the groundwater-surface water interface

    Science.gov (United States)

    van der Grift, Bas; Rozemeijer, Joachim; Griffioen, Jasper; van der Velde, Ype

    2014-05-01

    Eutrophication of freshwater environments following diffuse nutrient loads is a widely recognized water quality problem in catchments. Fluxes of non-point P sources to surface waters originate from surface runoff and flow from soil water and groundwater into surface water. The availability of P in surface waters is controlled strongly by biogeochemical nutrient cycling processes at the soil-water interface. The mechanisms and rates of the iron oxidation process with associated binding of phosphate during exfiltration of anaerobic Fe(II) bearing groundwater are among the key unknowns in P retention processes in surface waters in delta areas where the shallow groundwater is typically pH-neutral to slightly acid, anoxic, iron-rich. We developed an experimental field set-up to study the dynamics in Fe(II) oxidation and mechanisms of P immobilization at the groundwater-surface water interface in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. The exfiltrating groundwater was captured in in-stream reservoirs constructed in the ditch. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we quantified Fe(II) oxidation kinetics and P immobilization processes across the seasons. This study showed that seasonal changes in climatic conditions affect the Fe(II) oxidation process. In winter time the dissolved iron concentrations in the in-stream reservoirs reached the levels of the anaerobic groundwater. In summer time, the dissolved iron concentrations of the water in the reservoirs are low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into the reservoirs. Higher discharges, lower temperatures and lower pH of the exfiltrated groundwater in winter compared to summer shifts the location of the redox transition zone

  10. Silver-Ion-Exchanged Nanostructured Zeolite X as Antibacterial Agent with Superior Ion Release Kinetics and Efficacy against Methicillin-Resistant Staphylococcus aureus.

    Science.gov (United States)

    Chen, Shaojiang; Popovich, John; Iannuzo, Natalie; Haydel, Shelley E; Seo, Dong-Kyun

    2017-11-15

    As antibiotic resistance continues to be a major public health problem, antimicrobial alternatives have become critically important. Nanostructured zeolites have been considered as an ideal host for improving popular antimicrobial silver-ion-exchanged zeolites, because with very short diffusion path lengths they offer advantages in ion diffusion and release over their conventional microsized zeolite counterparts. Herein, comprehensive studies are reported on materials characteristics, silver-ion release kinetics, and antibacterial properties of silver-ion-exchanged nanostructured zeolite X with comparisons to conventional microsized silver-ion-exchanged zeolite (∼2 μm) as a reference. The nanostructured zeolites are submicrometer-sized aggregates (100-700 nm) made up of primary zeolite particles with an average primary particle size of 24 nm. The silver-ion-exchanged nanostructured zeolite released twice the concentration of silver ions at a rate approximately three times faster than the reference. The material exhibited rapid antimicrobial activity against methicillin-resistant Staphylococcus aureus (MRSA) with minimum inhibitory concentration (MIC) values ranging from 4 to 16 μg/mL after 24 h exposure in various growth media and a minimum bactericidal concentration (MBC; >99.9% population reduction) of 1 μg/mL after 2 h in water. While high concentrations of silver-ion-exchanged nanostructured zeolite X were ineffective at reducing MRSA biofilm cell viability, efficacy increased at lower concentrations. In consideration of potential medical applications, cytotoxicity of the silver-ion-exchanged nanostructured zeolite X was also investigated. After 4 days of incubation, significant reduction in eukaryotic cell viability was observed only at concentrations 4-16-fold greater than the 24 h MIC, indicating low cytotoxicity of the material. Our results establish silver-ion-exchanged nanostructured zeolites as an effective antibacterial material against dangerous

  11. Reaction kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers

    International Nuclear Information System (INIS)

    Gokcen, Dincer; Bae, Sang-Eun; Brankovic, Stanko R.

    2011-01-01

    The study of the kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers is presented. The model system was Pt submonolayer deposition on Au(1 1 1) via red-ox replacement of Pb and Cu UPD monolayers on Au(1 1 1). The kinetics of a single replacement reaction was studied using the formalism of the comprehensive analytical model developed to fit the open circuit potential transients from deposition experiments. The practical reaction kinetics parameters like reaction half life, reaction order and reaction rate constant are determined and discussed with their relevance to design and control of deposition experiments. The effects of transport limitation and the role of the anions/electrolyte on deposition kinetics are investigated and their significance to design of effective deposition process is discussed.

  12. Fouling of heat exchanger surfaces by dust particles from flue gases of glass furnaces

    Energy Technology Data Exchange (ETDEWEB)

    Mutsaers, P.L.M.; Beerkens, R.G.C.; Waal, H. de (Nederlandse Centrale Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek, Delft. Inst. of Applied Physics)

    1989-08-01

    Fouling by dust particles generally leads to a reduction of the heat transfer and causes corrosion of secondary heat exchangers. A deposition model, including thermodynamic equilibrium calculations, has been derived and applied to describe the deposition (i.e. fouling) process and the nature of the deposition products in a secondary heat exchanger. The deposition model has been verified by means of laboratory experiments, for the case of flue gases from soda-lime glass furnaces. Corrosion of iron-containing metallic materials, caused by the deposition products, has been briefly investigated with the same equipment. There is a close similarity between the experimental results and model calculations. The largest deposition rates from flue gases on cylindrical tubes in cross-flow configuration, are predicted and measured at the upstream stagnation point. The lowest deposition rates are determined at downstream stagnation point locations. At tube surface temperatures of approximately 520 to 550 K, the fouling rate on the tube reaches a maximum. In this temperature region NaHSO{sub 4} is the most important deposition product. This component is mainly formed at temperatures from 470 up to 540 K. The compound Na{sub 3}H(SO{sub 4}){sub 2} seems to be stable up to 570 K, for even higher temperatures Na{sub 2}SO{sub 4} has been found. These deposition products react with iron, SO{sub 3}, oxygen and water vapour forming the complex corrosion product Na{sub 3}Fe(SO{sub 4}){sub 3}. NaHSO{sub 4}, which is formed at tube surface temperatures below 540 K, causes more severe corrosion of iron-containing materials than Na{sub 2}SO{sub 4}. Maintaining temperatures of the heat exchanger surfaces above 550 to 600 K reduces the fouling tendency and corrosion in case of flue gases from oil-fired soda-lime glass furnaces. (orig.).

  13. Speciation of uranium in surface-modified, hydrothermally treated, (UO2)2+-exchanged smectite clays

    International Nuclear Information System (INIS)

    Giaquinta, D.M.; Soderholm, L.; Yuchs, S.E.; Wasserman, S.R.

    1997-01-01

    A successful solution to the problem of disposal and permanent storage of water soluble radioactive species must address two issues: exclusion of the radionuclides from the environment and the prevention of leaching from the storage media into the environment. Immobilization of radionuclides in clay minerals has been studied. In addition to the use of clays as potential waste forms, information about the interactions of radionuclides with clays and how such interactions affect their speciations is crucial for successful modeling of actinide-migration. X-ray absorption spectroscopy (XAS) is used to determine the uranium speciation in exchanged and surface-modified clays. The XAS data from uranyl-loaded bentonite clay are compared with those obtained after the particle surfaces have been coated with alkylsilanes. These silane films, which render the surface of the clay hydrophobic, are added in order to minimize the ability of external water to exchange with the water in the clay interlayer, thereby decreasing the release rate of the exchanged-uranium species. Mild hydrothermal conditions are used in an effort to mimic potential geologic conditions that may occur during long-term radioactive waste storage. The XAS spectra indicate that the uranyl monomer species remain unchanged in most samples, except in those samples that were both coated with an alkylsilane and hydrothermally treated. When the clay was coated with an organic film, formed by the acidic deposition of octadecyltrimethoxysilane, hydrothermal treatment results in the formation of aggregated uranium species in which the uranium is reduced from U VI to U IV

  14. Towards hot electron mediated charge exchange in hyperthermal energy ion-surface interactions

    DEFF Research Database (Denmark)

    Ray, M. P.; Lake, R. E.; Thomsen, Lasse Bjørchmar

    2010-01-01

    shows that the primary energy loss mechanism is the atomic displacement of Au atoms in the thin film of the metal–oxide–semiconductor device. We propose that neutral particle detection of the scattered flux from a biased device could be a route to hot electron mediated charge exchange.......We have made Na + and He + ions incident on the surface of solid state tunnel junctions and measured the energy loss due to atomic displacement and electronic excitations. Each tunnel junction consists of an ultrathin film metal–oxide–semiconductor device which can be biased to create a band of hot...

  15. Modeling heat efficiency, flow and scale-up in the corotating disc scraped surface heat exchanger

    DEFF Research Database (Denmark)

    Friis, Alan; Szabo, Peter; Karlson, Torben

    2002-01-01

    A comparison of two different scale corotating disc scraped surface heat exchangers (CDHE) was performed experimentally. The findings were compared to predictions from a finite element model. We find that the model predicts well the flow pattern of the two CDHE's investigated. The heat transfer...... performance predicted by the model agrees well with experimental observations for the laboratory scale CDHE whereas the overall heat transfer in the scaled-up version was not in equally good agreement. The lack of the model to predict the heat transfer performance in scale-up leads us to identify the key...

  16. Kinetics and mechanisms of thiol-disulfide exchange covering direct substitution and thiol oxidation-mediated pathways.

    Science.gov (United States)

    Nagy, Péter

    2013-05-01

    Disulfides are important building blocks in the secondary and tertiary structures of proteins, serving as inter- and intra-subunit cross links. Disulfides are also the major products of thiol oxidation, a process that has primary roles in defense mechanisms against oxidative stress and in redox regulation of cell signaling. Although disulfides are relatively stable, their reduction, isomerisation, and interconversion as well as their production reactions are catalyzed by delicate enzyme machineries, providing a dynamic system in biology. Redox homeostasis, a thermodynamic parameter that determines which reactions can occur in cellular compartments, is also balanced by the thiol-disulfide pool. However, it is the kinetic properties of the reactions that best represent cell dynamics, because the partitioning of the possible reactions depends on kinetic parameters. This review is focused on the kinetics and mechanisms of thiol-disulfide substitution and redox reactions. It summarizes the challenges and advances that are associated with kinetic investigations in small molecular and enzymatic systems from a rigorous chemical perspective using biological examples. The most important parameters that influence reaction rates are discussed in detail. Kinetic studies of proteins are more challenging than small molecules, and quite often investigators are forced to sacrifice the rigor of the experimental approach to obtain the important kinetic and mechanistic information. However, recent technological advances allow a more comprehensive analysis of enzymatic systems via using the systematic kinetics apparatus that was developed for small molecule reactions, which is expected to provide further insight into the cell's machinery.

  17. Oxygen isotope exchange kinetics of mineral pairs in closed and open systems: Applications to problems of hydrothermal alteration of igneous rocks and Precambrian iron formations

    Science.gov (United States)

    Gregory, R.T.; Criss, R.E.; Taylor, H.P.

    1989-01-01

    The systematics of stable-isotope exchange between minerals and fluids are examined in the context of modal mineralogical variations and mass-balance considerations, both in closed and in open systems. On mineral-pair ??18O plots, samples from terranes that have exchanged with large amounts of fluid typically map out steep positively-sloped non-equilibrium arrays. Analytical models are derived to explain these effects; these models allow for different exchange rates between the various minerals and the external fluids, as well as different fluid fluxes. The steep arrays are adequately modelled by calculated isochron lines that involve the whole family of possible exchange trajectories. These isochrons have initially-steep near-vertical positive slopes that rotate toward a 45?? equilibrium slope as the exchange process proceeds to completion. The actual data-point array is thus analogous to the hand of an "isotopic clock" that measures the duration of the hydrothermal episode. The dimensionless ratio of the volumetric fluid flux to the kinetic rate parameter ( u k) determines the shape of each individual exchange trajectory. In a fluid-buffered system ( u k ??? 1), the solutions to the equations: (1) are independent of the mole fractions of the solid phases; (2) correspond to Taylor's open-system water/rock equation; and (3) yield straight-line isochrons that have slopes that approach 1 f, where f is the fraction reacted of the more sluggishly exchanging mineral. The isochrons for this simple exchange model are closely congruent with the isochrons calculated for all of the more complex models, thereby simplifying the application of theory to actual hydrothermal systems in nature. In all of the models an order of magnitude of time (in units of kt) separates steep non-equilibrium arrays (e.g., slope ??? 10) from arrays approaching an equilibrium slope of unity on a ??-?? diagram. Because we know the approximate lifetimes of many hydrothermal systems from geologic and

  18. Surface roughness effect on the metallic bipolar plates of a proton exchange membrane fuel cell

    International Nuclear Information System (INIS)

    Lin, Chien-Hung

    2013-01-01

    Highlights: ► Various degrees of roughness are caused by the sandblasting method. ► An improper surface modification depletes the PEMFC performance severely. ► The AC impedance are used to assess the fuel gas transfer effect. ► The Warburg resistance form in the coarse flow channel surface. - Abstract: Proton exchange membrane fuel cells (PEMFCs) is a promising candidate as energy systems. However, the stability and lifetime of cells are still important issues. The effect of surface roughness on metallic bipolar plate is discussed in this paper. Various roughness on the bulk surface are obtained by the sandblasting method. The grain sizes of sand are selected as 50, 100 and 200 μm. The Ac impedance experiment results show that the bipolar plate roughness and carbon paper porosity are well matched when the surface roughness is within 1–2 μm. Superior condition decreases the contact resistance loss in the fuel cell. The high frequency resistance of the coarse surface was larger than that of the substrate by around 5 mΩ. Furthermore, a new arc was formed at the low frequency region. Hence, the unmatch roughness condition of the bipolar plate significantly increases the contact resistance and mass transfer resistance. This paper develops a sequential approach to study an optimum surface roughness by combining the whole performance (I–V) curve and AC impedance result. It benefits us to quantify the contact and mass transfer resistance exists in the PEMFC. The proposed surface treatment improves the surface effect and promotes the implement of potential metallic bipolar plate in near future

  19. Synthesis of Prebiotic Caramels Catalyzed by Ion-Exchange Resin Particles: Kinetic Model for the Formation of Di-d-fructose Dianhydrides.

    Science.gov (United States)

    Ortiz Cerda, Imelda-Elizabeth; Thammavong, Phahath; Caqueret, Vincent; Porte, Catherine; Mabille, Isabelle; Garcia Fernandez, José Manuel; Moscosa Santillan, Mario; Havet, Jean-Louis

    2018-02-21

    Caramel enriched in di-d-fructose dianhydrides (DFAs, a family of prebiotic cyclic fructodisaccharides) is a functional food with beneficial properties for health. The aim of this work was to study the conversion of fructose into DFAs catalyzed by acid ion-exchange resin, in order to establish a simplified mechanism of the caramelization reaction and a kinetic model for DFA formation. Batch reactor experiments were carried out in a 250 mL spherical glass flask and afforded up to 50% DFA yields. The mechanism proposed entails order 2 reactions that describe fructose conversion on DFAs or formation of byproducts such as HMF or melanoidines. A third order 1 reaction defines DFA transformation into fructosyl-DFAs or fructo-oligosaccharides. The influence of fructose concentration, resin loading and temperature was studied to calculate the kinetic parameters necessary to scale up the process.

  20. Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells

    KAUST Repository

    Crumlin, Ethan J.

    2010-11-04

    Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of ∼85 nm thick La0.8Sr0.2CoO3-δ (LSC113) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced (∼3-4 orders of magnitude above bulk LSC113) by surface decorations of (La 0.5Sr0.5)2CoO4±δ (LSC214) with coverage in the range from ∼0.1 to ∼15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC113/LSC214 regions, which were shown to be atomically sharp. © 2010 American Chemical Society.

  1. Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells

    KAUST Repository

    Crumlin, Ethan J.; Mutoro, Eva; Ahn, Sung-Jin; la O’ , Gerardo Jose; Leonard, Donovan N.; Borisevich, Albina; Biegalski, Michael D.; Christen, Hans M.; Shao-Horn, Yang

    2010-01-01

    Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of ∼85 nm thick La0.8Sr0.2CoO3-δ (LSC113) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced (∼3-4 orders of magnitude above bulk LSC113) by surface decorations of (La 0.5Sr0.5)2CoO4±δ (LSC214) with coverage in the range from ∼0.1 to ∼15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC113/LSC214 regions, which were shown to be atomically sharp. © 2010 American Chemical Society.

  2. Osteoclast cell-surface specializations and nuclear kinetics during egg-laying in Japanese quail

    International Nuclear Information System (INIS)

    Miller, S.C.

    1981-01-01

    Medullary bone deposits serve as a reservoir of labile calcium for egg-shell calcification in birds. Quantitative transmission-electron-microscope methods and light-microscope autoradiographic cell-population-kinetic analyses were used to determine changes in cell-surface specializations and population dynamics of medullary bone osteoclasts during egg-laying in Japanese quail. Prior to egg-shell formation, from 0 to about 8 hours after the previous oviposition, very few osteoclast profiles had ruffled borders. The appearance of ruffled borders coincided with the beginning of egg-shell calcification, about 9-10 hours after the previous oviposition. During egg-shell calcification, about 10-21 hours after the previous oviposition, most osteoclast profiles had ruffled borders. Ruffled borders disappeared at the completion of egg-shell calcification and commencement of egg-shell pigmentation. Thus, functional activities of medullary bone osteoclasts appear to be closely synchronized with egg-shell calcification during egg-laying. From 1 to 48 hours after a single injection of 3H-thymidine (3H-TdR), very few labeled osteoclast nuclei were seen during egg-laying. Following multiple injections of 3H-TdR, the percentage of labeled nuclei reached a peak at about 170 hours after the first injection. At this peak-labeling time, relatively few of the osteoclast profiles that had labeled nuclei had two or more; although the average number of nuclei per osteoclast profile was about 3.6. These kinetic data suggest that the medullary bone osteoclast population has a prolonged rate of turnover compared to rapid changes in cell activities associated with each 24-hour egg-laying cycle; and collectively they would suggest that rapid changes in osteoclast functions occur independently of changes in cell-population dynamics

  3. Potential for Small Unmanned Aircraft Systems Applications for Identifying Groundwater-Surface Water Exchange in a Meandering River Reach

    Science.gov (United States)

    Pai, H.; Malenda, H. F.; Briggs, M. A.; Singha, K.; González-Pinzón, R.; Gooseff, M. N.; Tyler, S. W.

    2017-12-01

    The exchange of groundwater and surface water (GW-SW), including dissolved constituents and energy, represents a critical yet challenging characterization problem for hydrogeologists and stream ecologists. Here we describe the use of a suite of high spatial resolution remote sensing techniques, collected using a small unmanned aircraft system (sUAS), to provide novel and complementary data to analyze GW-SW exchange. sUAS provided centimeter-scale resolution topography and water surface elevations, which are often drivers of exchange along the river corridor. Additionally, sUAS-based vegetation imagery, vegetation-top elevation, and normalized difference vegetation index mapping indicated GW-SW exchange patterns that are difficult to characterize from the land surface and may not be resolved from coarser satellite-based imagery. We combined these data with estimates of sediment hydraulic conductivity to provide a direct estimate of GW "shortcutting" through meander necks, which was corroborated by temperature data at the riverbed interface.

  4. A Novel RFID Sensing System Using Enhanced Surface Wave Technology for Battery Exchange Stations

    Directory of Open Access Journals (Sweden)

    Yeong-Lin Lai

    2014-01-01

    Full Text Available This paper presents a novel radio-frequency identification (RFID sensing system using enhanced surface wave technology for battery exchange stations (BESs of electric motorcycles. Ultrahigh-frequency (UHF RFID technology is utilized to automatically track and manage battery and user information without manual operation. The system includes readers, enhanced surface wave leaky cable antennas (ESWLCAs, coupling cable lines (CCLs, and small radiation patches (SRPs. The RFID sensing system overcomes the electromagnetic interference in the metallic environment of a BES cabinet. The developed RFID sensing system can effectively increase the efficiency of BES operation and promote the development of electric vehicles which solve the problem of air pollution as well as protect the environment of the Earth.

  5. Experimental study on fouling in the heat exchangers of surface water heat pumps

    International Nuclear Information System (INIS)

    Bai, Xuelian; Luo, Te; Cheng, Kehui; Chai, Feng

    2014-01-01

    Fouling in the heat exchangers plays a key role on the performance of surface water heat pumps. It is also the basement for the system design criteria and operation energy efficiency. In this paper, experimental measurements are performed both in the field and the laboratory with different water qualities, temperatures and velocities. The research will focus on the dynamic growth characteristics of fouling and its main components. By studying the variation rules of fouling resistance, the fouling resistance allowance for certain water condition is recommended. Furthermore, a fouling prediction model in surface water heat pump will be developed and validated based on elaborating with fouling principle under specified water conditions. - Highlights: • Field and laboratory experiments are taken to measure the fouling variation. • Fouling growth process can be divided into four stages. • We recommend fouling resistance allowances for certain conditions. • A fouling prdiction model is developed and validated

  6. Regime-Dependent Differences in Surface Freshwater Exchange Estimates Over the Ocean

    Science.gov (United States)

    Wong, Sun; Behrangi, Ali

    2018-01-01

    Differences in gridded precipitation (P), surface evaporation (E), and the resultant surface freshwater exchange (P - E) among different products over the ocean are diagnosed as functions of moisture advection (Qadvt) and moisture tendency by dynamical convergence (Qcnvg). Compared to the GPCP product, the TRMM3B42 product captures higher frequency of precipitation with larger extreme precipitation rates in regimes of deep convection and more light rain detections in regimes of frequent occurrence of boundary layer clouds. Discrepancies in E depend on moisture flux divergence, with the OAFlux product having the largest E in regimes of divergence. Discrepancies in mean P - E in deep convective regimes are highly influenced by differences in precipitation, with the TRMM3B42 product yielding P - E histograms closer to those inferred from the reanalysis moisture flux convergence. In nonconvergent regimes, observation-based P - E histograms skew toward positive values while the inferred reanalysis histograms are symmetric about the means.

  7. Influence of the adhesion force crystal/heat exchanger surface on fouling mitigation

    International Nuclear Information System (INIS)

    Forster, M.; Augustin, W.; Bohnet, M.

    1999-01-01

    The accumulation of unwanted crystalline deposits (fouling) reduces the efficiency of heat exchangers considerably. In order to decrease the cost of fouling two strategies have been developed. The first fouling mitigation strategy is based on the modification of energy-and-geometry-related characteristics of the heat transfer surface to realize an increased duration of the induction period. By means of a drop-shape-analysis measurement device the interaction at the interface crystal/heat transfer surface is determined. The deployment of the fracture energy model and the interfacial defect model relates wetting characteristics to the adhesion phenomenon. Hence, a first estimation of the optimal choice of surface material is realized. Furthermore, the influence of surface topography on interfacial interactions has been analyzed. The second fouling mitigation strategy is based on the adjustment of the hydrodynamic flow conditions using a pulsation technique. Here, single strokes of higher velocity are superimposed on the stationary flow. These strokes shift the equilibrium of forces to an improved removal process. Fouling experiments have proved that pulsation is a powerful tool to mitigate the built-up of fouling layers on heat transfer surfaces. (author)

  8. How important is getting the land surface energy exchange correct in WRF for wind energy forecasting?

    Science.gov (United States)

    Wharton, S.; Simpson, M.; Osuna, J. L.; Newman, J. F.; Biraud, S.

    2013-12-01

    Wind power forecasting is plagued with difficulties in accurately predicting the occurrence and intensity of atmospheric conditions at the heights spanned by industrial-scale turbines (~ 40 to 200 m above ground level). Better simulation of the relevant physics would enable operational practices such as integration of large fractions of wind power into power grids, scheduling maintenance on wind energy facilities, and deciding design criteria based on complex loads for next-generation turbines and siting. Accurately simulating the surface energy processes in numerical models may be critically important for wind energy forecasting as energy exchange at the surface strongly drives atmospheric mixing (i.e., stability) in the lower layers of the planetary boundary layer (PBL), which in turn largely determines wind shear and turbulence at heights found in the turbine rotor-disk. We hypothesize that simulating accurate a surface-atmosphere energy coupling should lead to more accurate predictions of wind speed and turbulence at heights within the turbine rotor-disk. Here, we tested 10 different land surface model configurations in the Weather Research and Forecasting (WRF) model including Noah, Noah-MP, SSiB, Pleim-Xiu, RUC, and others to evaluate (1) the accuracy of simulated surface energy fluxes to flux tower measurements, (2) the accuracy of forecasted wind speeds to observations at rotor-disk heights, and (3) the sensitivity of forecasting hub-height rotor disk wind speed to the choice of land surface model. WRF was run for four, two-week periods covering both summer and winter periods over the Southern Great Plains ARM site in Oklahoma. Continuous measurements of surface energy fluxes and lidar-based wind speed, direction and turbulence were also available. The SGP ARM site provided an ideal location for this evaluation as it centrally located in the wind-rich Great Plains and multi-MW wind farms are rapidly expanding in the area. We found significant differences in

  9. Guided asteroid deflection by kinetic impact: Mapping keyholes to an asteroid's surface

    Science.gov (United States)

    Chesley, S.; Farnocchia, D.

    2014-07-01

    The kinetic impactor deflection approach is likely to be the optimal deflection strategy in most real-world cases, given the likelihood of decades of warning time provided by asteroid search programs and the probable small size of the next confirmed asteroid impact that would require deflection. However, despite its straightforward implementation, the kinetic impactor approach can have its effectiveness limited by the astrodynamics that govern the impactor spacecraft trajectory. First, the deflection from an impact is maximized when the asteroid is at perihelion, while an impact near perihelion can in some cases be energetically difficult to implement. Additionally, the asteroid change in velocity Δ V should aligned with the target's heliocentric velocity vector in order to maximize the deflection at a potential impact some years in the future. Thus the relative velocity should be aligned with or against the heliocentric velocity, which implies that the impactor and asteroid orbits should be tangent at the point of impact. However, for natural bodies such as meteorites colliding with the Earth, the relative velocity vectors tend to cluster near the sunward or anti- sunward directions, far from the desired direction. This is because there is generally a significant crossing angle between the orbits of the impactor and target and an impact at tangency is unusual. The point is that hitting the asteroid is not enough, but rather we desire to hit the asteroid at a point when the asteroid and spacecraft orbits are nearly tangent and when the asteroid is near perihelion. However, complicating the analysis is the fact that the impact of a spacecraft on an asteroid would create an ejecta plume that is roughly normal to the surface at the point of impact. This escaping ejecta provides additional momentum transfer that generally adds to the effectiveness of a kinetic deflection. The ratio β between the ejecta momentum and the total momentum (ejecta plus spacecraft) can

  10. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

    Science.gov (United States)

    van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

    2014-11-01

    The retention of phosphorus in surface waters through co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater into surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and surface water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than a week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilization of dissolved P during the initial stage of the Fe(II) oxidation process which results in P-depleted water before Fe(II) is completely depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients

  11. Porphyromonas gingivalis Uses Specific Domain Rearrangements and Allelic Exchange to Generate Diversity in Surface Virulence Factors.

    Science.gov (United States)

    Dashper, Stuart G; Mitchell, Helen L; Seers, Christine A; Gladman, Simon L; Seemann, Torsten; Bulach, Dieter M; Chandry, P Scott; Cross, Keith J; Cleal, Steven M; Reynolds, Eric C

    2017-01-01

    Porphyromonas gingivalis is a keystone pathogen of chronic periodontitis. The virulence of P. gingivalis is reported to be strain related and there are currently a number of strain typing schemes based on variation in capsular polysaccharide, the major and minor fimbriae and adhesin domains of Lys-gingipain (Kgp), amongst other surface proteins. P. gingivalis can exchange chromosomal DNA between strains by natural competence and conjugation. The aim of this study was to determine the genetic variability of P. gingivalis strains sourced from international locations over a 25-year period and to determine if variability in surface virulence factors has a phylogenetic basis. Whole genome sequencing was performed on 13 strains and comparison made to 10 previously sequenced strains. A single nucleotide polymorphism-based phylogenetic analysis demonstrated a shallow tri-lobed phylogeny. There was a high level of reticulation in the phylogenetic network, demonstrating extensive horizontal gene transfer between the strains. Two highly conserved variants of the catalytic domain of the major virulence factor the Kgp proteinase (Kgp cat I and Kgp cat II) were found. There were three variants of the fourth Kgp C-terminal cleaved adhesin domain. Specific variants of the cell surface proteins FimA, FimCDE, MfaI, RagAB, Tpr, and PrtT were also identified. The occurrence of all these variants in the P. gingivalis strains formed a mosaic that was not related to the SNP-based phylogeny. In conclusion P. gingivalis uses domain rearrangements and genetic exchange to generate diversity in specific surface virulence factors.

  12. Ozone-surface interactions: Investigations of mechanisms, kinetics, mass transport, and implications for indoor air quality

    Energy Technology Data Exchange (ETDEWEB)

    Morrison, Glenn Charles [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    In this dissertation, results are presented of laboratory investigations and mathematical modeling efforts designed to better understand the interactions of ozone with surfaces. In the laboratory, carpet and duct materials were exposed to ozone and measured ozone uptake kinetics and the ozone induced emissions of volatile organic compounds. To understand the results of the experiments, mathematical methods were developed to describe dynamic indoor aldehyde concentrations, mass transport of reactive species to smooth surfaces, the equivalent reaction probability of whole carpet due to the surface reactivity of fibers and carpet backing, and ozone aging of surfaces. Carpets, separated carpet fibers, and separated carpet backing all tended to release aldehydes when exposed to ozone. Secondary emissions were mostly n-nonanal and several other smaller aldehydes. The pattern of emissions suggested that vegetable oils may be precursors for these oxidized emissions. Several possible precursors and experiments in which linseed and tung oils were tested for their secondary emission potential were discussed. Dynamic emission rates of 2-nonenal from a residential carpet may indicate that intermediate species in the oxidation of conjugated olefins can significantly delay aldehyde emissions and act as reservoir for these compounds. The ozone induced emission rate of 2-nonenal, a very odorous compound, can result in odorous indoor concentrations for several years. Surface ozone reactivity is a key parameter in determining the flux of ozone to a surface, is parameterized by the reaction probability, which is simply the probability that an ozone molecule will be irreversibly consumed when it strikes a surface. In laboratory studies of two residential and two commercial carpets, the ozone reaction probability for carpet fibers, carpet backing and the equivalent reaction probability for whole carpet were determined. Typically reaction probability values for these materials were 10

  13. ULTRASOUND PRETREATMENT OF ELEMENTAL IRON: KINETIC STUDIES OF DEHALOGENATION REACTION ENHANCEMENT AND SURFACE EFFECTS. (R828598C743)

    Science.gov (United States)

    This work presents data showing the kinetic improvement afforded by ultrasound pretreatment and illustrates the physical and chemical changes that take place at the iron surface. First-order rate constants improved as much as 78% with 2 h of ultrasound pretreatment. Scann...

  14. Kinetics and mechanisms of the oxide film growth on the surface of α-Fe in transitional domains

    International Nuclear Information System (INIS)

    Mukhambetov, D.G.; Berber, N.N.; Kargin, D.B.; Chalaya, O.V.

    2003-01-01

    The object of this work was to study the kinetics of the α-Fe surface oxidation with prevailing cubic texture at temperatures of 450-500 deg. C. The basic conformity to natural laws and mechanisms of the two-phase thin oxide films grows are determined. (author)

  15. A kinetic analysis of manual wheelchair propulsion during start-up on select indoor and outdoor surfaces

    NARCIS (Netherlands)

    Koontz, AM; Cooper, RA; Boninger, ML; Yang, YS; Impink, BG; van der Woude, LHV

    2005-01-01

    The objective of this study was to conduct a kinetic analysis of manual wheelchair propulsion during start-LIP on select indoor and Outdoor surfaces. Eleven manual wheelchairs were fitted with a SMART(Wheel) and their users were asked to Push on a Course consisting of high- and low-pile carpet,

  16. Kinetic investigation of heterogeneous catalytic reactions by means of the kinetic isotope method

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, F; Dermietzel, J [Akademie der Wissenschaften der DDR, Leipzig. Zentralinstitut fuer Isotopen- und Strahlenforschung

    1978-09-01

    The application of the kinetic isotope method to heterogeneous catalytic processes is possible for surface compounds by using the steady-state relation. However, the characterization of intermediate products becomes ambiguous if sorption rates are of the same order of magnitude as surface reactions rates. The isotopic exchange reaction renders possible the estimation of sorption rates.

  17. Kinetics and Mechanisms of Thiol–Disulfide Exchange Covering Direct Substitution and Thiol Oxidation-Mediated Pathways

    Science.gov (United States)

    2013-01-01

    Abstract Significance: Disulfides are important building blocks in the secondary and tertiary structures of proteins, serving as inter- and intra-subunit cross links. Disulfides are also the major products of thiol oxidation, a process that has primary roles in defense mechanisms against oxidative stress and in redox regulation of cell signaling. Although disulfides are relatively stable, their reduction, isomerisation, and interconversion as well as their production reactions are catalyzed by delicate enzyme machineries, providing a dynamic system in biology. Redox homeostasis, a thermodynamic parameter that determines which reactions can occur in cellular compartments, is also balanced by the thiol–disulfide pool. However, it is the kinetic properties of the reactions that best represent cell dynamics, because the partitioning of the possible reactions depends on kinetic parameters. Critical Issues: This review is focused on the kinetics and mechanisms of thiol–disulfide substitution and redox reactions. It summarizes the challenges and advances that are associated with kinetic investigations in small molecular and enzymatic systems from a rigorous chemical perspective using biological examples. The most important parameters that influence reaction rates are discussed in detail. Recent Advances and Future Directions: Kinetic studies of proteins are more challenging than small molecules, and quite often investigators are forced to sacrifice the rigor of the experimental approach to obtain the important kinetic and mechanistic information. However, recent technological advances allow a more comprehensive analysis of enzymatic systems via using the systematic kinetics apparatus that was developed for small molecule reactions, which is expected to provide further insight into the cell's machinery. Antioxid. Redox Signal. 18, 1623–1641. PMID:23075118

  18. Surface controlled dissolution rates of gypsum in aqueous solutions exhibit nonlinear dissolution kinetics

    Science.gov (United States)

    Jeschke, Alexander A.; Vosbeck, Katrin; Dreybrodt, Wolfgang

    2001-01-01

    The effective dissolution rates of gypsum are determined by mixed kinetics, where the rate constants of dissolution at the surface and the transport constant of molecular diffusion of dissolved material are similar. To obtain the surface reaction rate law it is necessary to know the transport constant. We have determined the surface rate law for monocrystalline selenite by using a rotating disc set-up, where the transport coefficients are well known. As a result, up to a calcium concentration of 0.6 · ceq, we find a nearly linear rate law Rs = ksl (1- cs/ ceq) n1, where cs is the total calcium concentration at the surface and ceq the equilibrium concentration with respect to gypsum, n1 = 1.2 ± 0.2, and ksl = 1.1 · 10 -4 mmol cm -2 s -1 ± 15%. We also employed batch-experiments for selenite, alabaster and gypsum rock samples. The result of these experiments were interpreted by using a transport constant determined by NaCl dissolution experiments under similar physical conditions. The batch experiments reveal a dissolution rate law Rs = ksl (1- cs/ ceq) n1, ksl = 1.3 · 10 -4 mmol · cm -2 s -1, n1 = 1.2 ± 0.2 for c ≤ 0.94 · ceq. Close to equilibrium a nonlinear rate law, Rs = ks2 (1- cs/ ceq) n2, is observed, where ks2 is in the order of 10 mmol · cm -2 s -1 and n2 ≈ 4.5. The experimentally observed gypsum dissolution rates from the batch experiments could be accurately fitted, with only minor variations of the surface reaction constant obtained from the rotating disk experiment and the transport coefficient from the NaCl dissolution batch experiment. Batch experiments on pure synthetic gypsum, reveal a linear rate law up to equilibrium. This indicates inhibition of dissolution in natural samples close to equilibrium, as is known also for calcite minerals.

  19. Morphological evolution of dissolving feldspar particles with anisotropic surface kinetics and implications for dissolution rate normalization and grain size dependence: A kinetic modeling study

    Science.gov (United States)

    Zhang, Li; Lüttge, Andreas

    2009-11-01

    With previous two-dimensional (2D) simulations based on surface-specific feldspar dissolution succeeding in relating the macroscopic feldspar kinetics to the molecular-scale surface reactions of Si and Al atoms ( Zhang and Lüttge, 2008, 2009), we extended our modeling effort to three-dimensional (3D) feldspar particle dissolution simulations. Bearing on the same theoretical basis, the 3D feldspar particle dissolution simulations have verified the anisotropic surface kinetics observed in the 2D surface-specific simulations. The combined effect of saturation state, pH, and temperature on the surface kinetics anisotropy has been subsequently evaluated, found offering diverse options for morphological evolution of dissolving feldspar nanoparticles with varying grain sizes and starting shapes. Among the three primary faces on the simulated feldspar surface, the (1 0 0) face has the biggest dissolution rate across an extensively wide saturation state range and thus acquires a higher percentage of the surface area upon dissolution. The slowest dissolution occurs to either (0 0 1) or (0 1 0) faces depending on the bond energies of Si-(O)-Si ( ΦSi-O-Si/ kT) and Al-(O)-Si ( ΦAl-O-Si/ kT). When the ratio of ΦSi-O-Si/ kT to ΦAl-O-Si/ kT changes from 6:3 to 7:5, the dissolution rates of three primary faces change from the trend of (1 0 0) > (0 1 0) > (0 0 1) to the trend of (1 0 0) > (0 0 1) > (0 1 0). The rate difference between faces becomes more distinct and accordingly edge rounding becomes more significant. Feldspar nanoparticles also experience an increasing degree of edge rounding from far-from-equilibrium to close-to-equilibrium. Furthermore, we assessed the connection between the continuous morphological modification and the variation in the bulk dissolution rate during the dissolution of a single feldspar particle. Different normalization treatments equivalent to the commonly used mass, cube assumption, sphere assumption, geometric surface area, and reactive

  20. Kinetics of liquid-phase catalytic heterogeneous protium-tritium isotope exchange with participation of gaseous hydrogen

    International Nuclear Information System (INIS)

    Akulov, G.P.; Snetkova, E.V.; Kayumov, V.G.; Kaminskij, Yu.L.

    1990-01-01

    Reaction rate constants of catalytic (PdO/BaSO 4 (Al 2 O 3 ) catalyst) heterogeneous protium - tritium isotopic exchange D - [1- 3 H] of carbohydrates and gaseous oxygen have been measured. It is ascertained that the rate of isotopic exchange depends on the nature of carbohydrate, catalyst, buffer and medium acidity. The value of concentration of carbohydrate acyclic forms plays the determining role in the process

  1. Surface-Coating Regulated Lithiation Kinetics and Degradation in Silicon Nanowires for Lithium Ion Battery

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Langli; Yang, Hui; Yan, Pengfei; Travis, Jonathan J.; Lee, Younghee; Liu, Nian; Piper, Daniela M.; Lee, Se-Hee; Zhao, Peng; George, Steven M.; Zhang, Jiguang; Cui, Yi; Zhang, Sulin; Ban, Chunmei; Wang, Chong M.

    2015-05-26

    Silicon (Si)-based materials hold promise as the next-generation anodes for high-energy lithium (Li)-ion batteries. Enormous research efforts have been undertaken to mitigate the chemo-mechanical failure due to the large volume changes of Si during lithiation and delithiation cycles. It has been found nanostructured Si coated with carbon or other functional materials can lead to significantly improved cyclability. However, the underlying mechanism and comparative performance of different coatings remain poorly understood. Herein, using in situ transmission electron microscopy (TEM) through a nanoscale half-cell battery, in combination with chemo-mechanical simulation, we explored the effect of thin (~5 nm) alucone and Al2O3 coatings on the lithiation kinetics of Si nanowires (SiNWs). We observed that the alucone coating leads to a “V-shaped” lithiation front of the SiNWs , while the Al2O3 coating yields an “H-shaped” lithiation front. These observations indicate that the difference between the Li surface diffusivity and bulk diffusivity of the coatings dictates lithiation induced morphological evolution in the nanowires. Our experiments also indicate that the reaction rate in the coating layer can be the limiting step for lithiation and therefore critically influences the rate performance of the battery. Further, the failure mechanism of the Al2O3 coated SiNWs was also explored. Our studies shed light on the design of high capacity, high rate and long cycle life Li-ion batteries.

  2. Structure elucidation and degradation kinetic study of Ofloxacin using surface enhanced Raman spectroscopy

    Science.gov (United States)

    El-Zahry, Marwa R.; Lendl, Bernhard

    2018-03-01

    A simple, fast and sensitive surface enhanced Raman spectroscopy (SERS) method for quantitative determination of fluoroquinolone antibiotic Ofloxacin (OFX) is presented. Also the stability behavior of OFX was investigated by monitoring the SERS spectra of OFX after various degradation processes. Acidic, basic and oxidative force degradation processes were applied at different time intervals. The forced degradation conditions were conducted and followed using SERS method utilizing silver nanoparticles (Ag NPs) as a SERS substrate. The Ag NPs colloids were prepared by reduction of silver nitrate using polyethyelene glycol (PEG) as a reducing and stabilizing agent. Validation tests were done in accordance with International Conference on Harmonization (ICH) guidelines. The calibration curve with a correlation coefficient (R = 0.9992) was constructed as a relationship between the concentration range of OFX (100-500 ng/ml) and SERS intensity at 1394 cm- 1 band. LOD and LOQ values were calculated and found to be 23.5 ng/ml and 72.6 ng/ml, respectively. The developed method was applied successfully for quantitation of OFX in different pharmaceutical dosage forms. Kinetic parameters were calculated including rate constant of the degradation of the studied antibiotic.

  3. Simultaneous heat and mass transfer to air from a compact heat exchanger with water spray precooling and surface deluge cooling

    International Nuclear Information System (INIS)

    Zhang, Feini; Bock, Jessica; Jacobi, Anthony M.; Wu, Hailing

    2014-01-01

    Various methods are available to enhance heat exchanger performance with evaporative cooling. In this study, evaporative mist precooling, deluge cooling, and combined cooling schemes are examined experimentally and compared to model predictions. A flexible model of a compact, finned-tube heat exchanger with a wetted surface is developed by applying the governing conservation and rate equations and invoking the heat and mass transfer analogy. The model is applicable for dry, partially wet, or fully wet surface conditions and capable of predicting local heat/mass transfer, wetness condition, and pressure drop of the heat exchanger. Experimental data are obtained from wind tunnel experiments using a louver-fin flat-tube heat exchanger with single-phase tube-side flow. Total capacity, pressure drop, and water drainage behavior under various water usage rates and air face velocities are analyzed and compared to data for dry-surface conditions. A heat exchanger partitioning method for evaporative cooling is introduced to study partially wet surface conditions, as part of a consistent and general method for interpreting wet-surface performance data. The heat exchanger is partitioned into dry and wet portions by introducing a wet surface factor. For the wet part, the enthalpy potential method is used to determine the air-side sensible heat transfer coefficient. Thermal and hydraulic performance is compared to empirical correlations. Total capacity predictions from the model agree with the experimental results with an average deviation of 12.6%. The model is also exercised for four water augmentation schemes; results support operating under a combined mist precooling and deluge cooling scheme. -- Highlights: • A new spray-cooled heat exchanger model is presented and is validated with data. • Heat duty is shown to be asymptotic with spray flow rate. • Meaningful heat transfer coefficients for partially wet conditions are obtained. • Colburn j wet is lower than j dry

  4. Methodology to obtain exchange properties of the calcite surface-Application to major and trace elements: Ca(II), HCO3-, and Zn(II)

    International Nuclear Information System (INIS)

    Tertre, E.; Beaucaire, C.; Juery, A.; Ly, J.; Tertre, E.; Beaucaire, C.; Juery, A.; Ly, J.

    2010-01-01

    Sorption of inorganic elements onto carbonate minerals has been intensively described in the literature by two reaction steps: (1) a first one rapid and completed within a few hours and (2) a second one slower, eventually irreversible, and occurring at a constant rate. The first step is often attributed to an ion-exchange process, but its reversibility is rarely investigated. Consequently, discrimination of the global sorption phenomenon into two different mechanisms is not always justified. In this study, we investigated, by batch experiments, both sorption and desorption of Ca(II), HCO 3 - , and Zn(II), radiolabeled with isotopes 45 Ca(II), H 14 CO 3 - , and 65 Zn(II), respectively, onto synthetic pure calcite. Solutions were pre-equilibrated with atmospheric p(CO 2 ) and saturated with respect to calcite. Therefore, our purpose was to: (1) obtain experimental distribution coefficients of major elements (Ca(II) and HCO 3 - ) and a trace element (Zn(II)) onto calcite from sorption and desorption experiments, (2) test the validity of a first-occurring ion-exchange process generally noted in the literature, by calculating distribution coefficients for the 'sole' exchange process, and (3) quantify the amounts of Ca(II), HCO 3 - , and Zn(II) sorbed on the calcite surface by the sole 'exchange process' and compare them with surface crystallochemical data. Ca(II) or HCO 3 - sorption experimental data suggest that a significant fraction of these two elements was sorbed irreversibly onto or in the calcite. By using a method based on isotopic ratios, the Ca(II) or HCO 3 - concentrations, which are reversibly adsorbed on the calcite, have been quantified. These concentrations are respectively estimated at 4. 0 ± 2. 0 * 10 -4 and 7. 0 ± 1. 5 * 10 -4 mol/kg. The obtained Ca(II) surface concentration value is one order of magnitude lower than the one obtained from isotopic measurement by former authors [Geochim. Cosmochim. Acta 55 (1991) 1549; Geochim. Cosmochim. Acta 51

  5. Dissimilar kinetic behavior of electrically manipulated single- and double-stranded DNA tethered to a gold surface.

    Science.gov (United States)

    Rant, Ulrich; Arinaga, Kenji; Tornow, Marc; Kim, Yong Woon; Netz, Roland R; Fujita, Shozo; Yokoyama, Naoki; Abstreiter, Gerhard

    2006-05-15

    We report on the electrical manipulation of single- and double-stranded oligodeoxynucleotides that are end tethered to gold surfaces in electrolyte solution. The response to alternating repulsive and attractive electric surface fields is studied by time-resolved fluorescence measurements, revealing markedly distinct dynamics for the flexible single-stranded and stiff double-stranded DNA, respectively. Hydrodynamic simulations rationalize this finding and disclose two different kinetic mechanisms: stiff polymers undergo rotation around the anchoring pivot point; flexible polymers, on the other hand, are pulled onto the attracting surface segment by segment.

  6. Integrated assessment of groundwater - surface water exchange in the hillslope - riparian interface of a montane catchment

    Science.gov (United States)

    Scheliga, Bernhard; Tetzlaff, Doerthe; Nuetzmann, Gunnar; Soulsby, Chris

    2016-04-01

    Groundwater-surface water dynamics play an important role in runoff generation and the hydrologic connectivity between hillslopes and streams. Here, we present findings from a suite of integrated, empirical approaches to increase our understanding of groundwater-surface water interlinkages in a 3.2 km ^ 2 experimental catchment in the Scottish Highlands. The montane catchment is mainly underlain by granite and has extensive (70%) cover of glacial drift deposits which are up to 40 m deep and form the main aquifer in the catchment. Flat valley bottom areas fringe the stream channel and are characterised by peaty soils (0.5-4 m deep) which cover about 10% of the catchment and receive drainage from upslope areas. The transition between the hillslopes and riparian zone forms a critical interface for groundwater-surface water interactions that controls both the dynamics of riparian saturation and stream flow generation. We nested observations using wells to assess the groundwater - surface water transition, LiDAR surveys to explore the influence of micro-topography on shallow groundwater efflux and riparian wells to examine the magnitude and flux rates of deeper groundwater sources. We also used electrical resistivity surveys to assess the architecture and storage properties of drift aquifers. Finally, we used isotopic tracers to differentiate recharge sources and associated residence times as well as quantifying how groundwater dynamics affect stream flow. These new data have provided a novel conceptual framework for local groundwater - surface water exchange that is informing the development of new deterministic models for the site.

  7. The boundary condition for vertical velocity and its interdependence with surface gas exchange

    Science.gov (United States)

    Kowalski, Andrew S.

    2017-07-01

    The law of conservation of linear momentum is applied to surface gas exchanges, employing scale analysis to diagnose the vertical velocity (w) in the boundary layer. Net upward momentum in the surface layer is forced by evaporation (E) and defines non-zero vertical motion, with a magnitude defined by the ratio of E to the air density, as w = E/ρ. This is true even right down at the surface where the boundary condition is w|0 = E/ρ|0 (where w|0 and ρ|0 represent the vertical velocity and density of air at the surface). This Stefan flow velocity implies upward transport of a non-diffusive nature that is a general feature of the troposphere but is of particular importance at the surface, where it assists molecular diffusion with upward gas migration (of H2O, for example) but opposes that of downward-diffusing species like CO2 during daytime. The definition of flux-gradient relationships (eddy diffusivities) requires rectification to exclude non-diffusive transport, which does not depend on scalar gradients. At the microscopic scale, the role of non-diffusive transport in the process of evaporation from inside a narrow tube - with vapour transport into an overlying, horizontal airstream - was described long ago in classical mechanics and is routinely accounted for by chemical engineers, but has been neglected by scientists studying stomatal conductance. Correctly accounting for non-diffusive transport through stomata, which can appreciably reduce net CO2 transport and marginally boost that of water vapour, should improve characterisations of ecosystem and plant functioning.

  8. The boundary condition for vertical velocity and its interdependence with surface gas exchange

    Directory of Open Access Journals (Sweden)

    A. S. Kowalski

    2017-07-01

    Full Text Available The law of conservation of linear momentum is applied to surface gas exchanges, employing scale analysis to diagnose the vertical velocity (w in the boundary layer. Net upward momentum in the surface layer is forced by evaporation (E and defines non-zero vertical motion, with a magnitude defined by the ratio of E to the air density, as w = E/ρ. This is true even right down at the surface where the boundary condition is w|0 = E/ρ|0 (where w|0 and ρ|0 represent the vertical velocity and density of air at the surface. This Stefan flow velocity implies upward transport of a non-diffusive nature that is a general feature of the troposphere but is of particular importance at the surface, where it assists molecular diffusion with upward gas migration (of H2O, for example but opposes that of downward-diffusing species like CO2 during daytime. The definition of flux–gradient relationships (eddy diffusivities requires rectification to exclude non-diffusive transport, which does not depend on scalar gradients. At the microscopic scale, the role of non-diffusive transport in the process of evaporation from inside a narrow tube – with vapour transport into an overlying, horizontal airstream – was described long ago in classical mechanics and is routinely accounted for by chemical engineers, but has been neglected by scientists studying stomatal conductance. Correctly accounting for non-diffusive transport through stomata, which can appreciably reduce net CO2 transport and marginally boost that of water vapour, should improve characterisations of ecosystem and plant functioning.

  9. Frost behavior of a fin surface with temperature variation along heat exchanger fins

    International Nuclear Information System (INIS)

    Kim, Jung Soo; Kim, Min Soo; Lee, Kwan Soo; Kim, Ook Joong

    2007-01-01

    This paper presents a mathematical model for predicting the frost behavior formed on heat exchanger fins, considering fin heat conduction under frosting condition. The model is composed of air-side, the frost layer, and fin region, and they are coupled to the frost layer. The frost behavior is more accurately predicted with fin heat conduction considered (Case A) than with a constant fin surface temperature assumed (Case B). The results indicate that the frost thickness and heat transfer rate for Case B are over-predicted in most regions of the fin, as compared to those for Case A. Also, for Case A, the maximum frost thickness varies little with the fin length variations, and the extension of the fin length over 30 mm contributes insignificantly to heat transfer

  10. Rate of Isotope Exchange Reaction Between Tritiated Water in a Gas Phase and Water on the Surface of Piping Materials

    International Nuclear Information System (INIS)

    Nakashio, Nobuyuki; Yamaguchi, Junya; Kobayashi, Ryusuke; Nishikawa, Masabumi

    2001-01-01

    The system effect of tritium arises from the interaction of tritium in the gas phase with water on the surface of piping materials. It has been reported that the system effect can be quantified by applying the serial reactor model to the piping system and that adsorption and isotope exchange reactions play the main roles in the trapping of tritium. The isotope exchange reaction that occurs when the chemical form of tritium in the gas phase is in the molecular form, i.e., HT or T 2 , has been named isotope exchange reaction 1, and that which occurs when tritium in the gas phase is in water form, i.e., HTO or T 2 O, has been named isotope exchange reaction 2.The rate of isotope exchange reaction 2 is experimentally quantified, and the rate is observed to be about one-third of the rate of adsorption. The trapping and release behavior of tritium from the piping surface due to isotope exchange reaction 2 is also discussed. It is certified that swamping of water vapor to process gas is effective to release tritium from the surface contaminated with tritium

  11. Functionalization of Cadmium Selenide Quantum Dots with Poly(ethylene glycol): Ligand Exchange, Surface Coverage, and Dispersion Stability.

    Science.gov (United States)

    Wenger, Whitney Nowak; Bates, Frank S; Aydil, Eray S

    2017-08-22

    Semiconductor quantum dots synthesized using rapid mixing of precursors by injection into a hot solution of solvents and surfactants have surface ligands that sterically stabilize the dispersions in nonpolar solvents. Often, these ligands are exchanged to disperse the quantum dots in polar solvents, but quantitative studies of quantum dot surfaces before and after ligand exchange are scarce. We studied exchanging trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO) ligands on as-synthesized CdSe quantum dots dispersed in hexane with a 2000 g/mol thiolated poly(ethylene glycol) (PEG) polymer. Using infrared spectroscopy we quantify the absolute surface concentration of TOP/TOPO and PEG ligands per unit area before and after ligand exchange. While 50-85% of the TOP/TOPO ligands are removed upon ligand exchange, only a few are replaced with PEG. Surprisingly, the remaining TOP/TOPO ligands outnumber the PEG ligands, but these few PEG ligands are sufficient to disperse the quantum dots in polar solvents such as chloroform, tetrahydrofuran, and water. Moreover, as-synthesized quantum dots once easily dispersed in hexane are no longer dispersible in nonpolar solvents after ligand exchange. A subtle coverage-dependent balance between attractive PEG-solvent interactions and repulsive TOP/TOPO-solvent interactions determines the dispersion stability.

  12. Influence of some factors on kinetics of boron ions sorption by inorganic anion exchanger of MNG type

    International Nuclear Information System (INIS)

    Leont'eva, G.V.

    1991-01-01

    Consideration is given to the influence of particle size of anion exchanger and boron ion concentration on boron sorption from the solution of the following composition (kg/m 3 ): Na + -71.3; K + - 1.9; Ca 2+ - 43.8; Mg 2+ - 5.7; B 2 O 3 -0.32-1.50; Cl - - 204.6, SO 4 2- - 0.02, CO 3 2+ - 0.40; HCO 3 - - 1.74; pH=8.1; density - 1225 kg/m 3 . Increase of dispersivity of ion-exchange material promotes the elevation of sorption rate. Increase of boron ion concentration in the solution leads to exchange capacity growth and reduction of latent period of nucleation; this results to increase of sorption rate

  13. Endogenous minerals have influences on surface electrochemistry and ion exchange properties of biochar.

    Science.gov (United States)

    Zhao, Ling; Cao, Xinde; Zheng, Wei; Wang, Qun; Yang, Fan

    2015-10-01

    The feedstocks for biochar production are diverse and many of them contain various minerals in addition to being rich in carbon. Twelve types of biomass classified into 2 categories: plant-based and municipal waste, were employed to produce biochars under 350 °C and 500 °C. Their pH, point of zero net charge (PZNC), zeta potential, cation and anion exchange capacity (CEC and AEC) were analyzed. The municipal waste-based biochars (MW-BC) had higher mineral levels than the plant-based biochars (PB-BC). However, the water soluble mineral levels were lower in the MW-BCs due to the dominant presence of less soluble minerals, such as CaCO3 and (Ca,Mg)3(PO4)2. The higher total minerals in MW-BCs accounted for the higher PZNC (5.47-9.95) than in PB-BCs (1.91-8.18), though the PZNCs of the PB-BCs increased more than that of the MW-BCs as the production temperature rose. The minerals had influence on the zeta potentials via affecting the negative charges of biochars and the ionic strength of solution. The organic functional groups in PB-BCs such as -COOH and -OH had a greater effect on the CEC and AEC, while the minerals had a greater effect on that of MW-BCs. The measured CEC and AEC values had a strong positive correlation with the total amount of soluble cations and anions, respectively. Results indicated that biochar surface charges depend not only on the organic functional groups, but also on the minerals present and to some extent, minerals have more influences on the surface electrochemistry and ion exchange properties of biochar. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Kinetics of the metal exchange in Bis(salicylaldiminato)-copper(II)-complexes. Pt. 3. Influence of the electron density at the donor nitrogen

    Energy Technology Data Exchange (ETDEWEB)

    Winkler, H; Wannowius, K J; Elias, H [Technische Hochschule Darmstadt (Germany, F.R.). Fachbereich Anorganische Chemie und Kernchemie

    1977-01-01

    The kinetics of isotopic copper exchange between various (bis-(N-phenyl-salicylaldiminato))copper(II)complexes (= CuL/sub 2/) and mono(pyridine)copper(II)acetate (= CuAc/sub 2/py) was studied in dichloromethane as solvent in the temperature range -20 to +20/sup 0/C. The exchange follows the experimental rate law (5), which is simplified in certain cases due to k''((CuAc/sub 2/py)/sub 2/)/sup 1///sup 2/ < 1. The variation of substituents X on the salicylaldehyde ring and of substituents Y on the N-phenyl ring leads via Hammett plots to the conclusion that substituent effects become apparent as rate increasing or rate decreasing only in those cases, in which they cause an increase or decrease in electron density at the donor oxygen. Substituents Y in 2-position, and especially in 2.6-position, reduce the rate of exchange with increasing van der Waals radius of Y. The mechanistic implications of the results are discussed. (orig.) 891 HK.

  15. In Situ Tracking Kinetic Pathways of Li+/Na+ Substitution during Ion-Exchange Synthesis of LixNa1.5-xVOPO4F0.5.

    Science.gov (United States)

    Park, Young-Uk; Bai, Jianming; Wang, Liping; Yoon, Gabin; Zhang, Wei; Kim, Hyungsub; Lee, Seongsu; Kim, Sung-Wook; Looney, J Patrick; Kang, Kisuk; Wang, Feng

    2017-09-13

    Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials with metastable structure for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li + /Na + substitution during solvothermal ion-exchange synthesis of Li x Na 1.5-x VOPO 4 F 0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-time observation, corroborated by first-principles calculations, reveals a selective replacement of Na + by Li + , leading to peculiar Na + /Li + /vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.

  16. Stomatal kinetics and photosynthetic gas exchange along a continuum of isohydric to anisohydric regulation of plant water status

    Science.gov (United States)

    Frederick C. Meinzer; Duncan D. Smith; David R. Woodruff; Danielle E. Marias; Katherine A. McCulloh; Ava R. Howard; Alicia L. Magedman

    2017-01-01

    Species’ differences in the stringency of stomatal control of plant water potential represent a continuum of isohydric to anisohydric behaviours. However, little is known about how quasi-steady-state stomatal regulation of water potential may relate to dynamic behaviour of stomata and photosynthetic gas exchange in species operating at different positions along this...

  17. Kinetics of oxygen exchange between bisulfite ion and water as studied by oxygen-17 nuclear magnetic resonance spectroscopy

    International Nuclear Information System (INIS)

    Horner, D.A.

    1984-08-01

    The nuclear magnetic relaxation times of oxygen-17 have been measured in aqueous sodium bisulfite solutions in the pH range from 2.5 to 5 as a function of temperature, pH, and S(IV) concentration, at an ionic strength of 1.0 m. The rate law for oxygen exchange between bisulfite ion and water was obtained from an analysis of the data, and is consistent with oxygen exchange occurring via the reaction SO 2 + H 2 O right reversible H + + SHO 3 - . The value of k/sub -1/ is in agreement with relaxation measurements. Direct spectroscopic evidence was found for the existence of two isomers of bisulfite ion: one with the proton bonded to the sulfur (HSO 3 - ) and the other with the proton bonded to an oxygen (SO 3 H - ). (The symbol SHO 3 - in the above chemical equation refers to both isomeric forms of bisulfite ion.) The relative amounts of the two isomers were determined as a function of temperature, and the rate and mechanism of oxygen exchange between the two was investigated. One of the two isomers, presumably SO 3 H - , exchanges oxygens with water much more rapidly than does the other. A two-pulse sequence was developed which greatly diminished the solvent peak in the NMR spectrum

  18. Translational kinetic energy induced oxidation on Ti(0001) surfaces using a supersonic O2 beam

    International Nuclear Information System (INIS)

    Ogawa, Shuichi; Takakuwa, Yuji; Ishidzuka, Shinji; Yoshigoe, Akitaka; Teraoka, Yuden; Moritani, Kousuke; Mizuno, Yoshiyuki

    2007-01-01

    The initial sticking probability S 0 of O 2 molecules on a Ti(0001)1x1 surface at room temperature was measured as a function of translational kinetic energy E t by real-time photoelectron spectroscopy. The O 1s photoelectron spectra can be fitted well with three components A, B and C, where the chemical shift of component B and C are +0.7 and +1.6 eV relative to the binding energy of component A (528.8 eV). Upon exposing to the O 2 beam, component A and C appear dominantly and component B grows with an incubation time, indicating that two kinds of chemical adsorption states are concerned with dissociative adsorption of O 2 molecules at the initial stage. The E t dependences of S 0 show quite different behaviors between component A and C: S 0 of component C decreases monotonously with E t and is almost constant above 0.6 eV, while S 0 of component A shows a rapid decrease followed by a gradual increase with a minimum at ∼0.5 eV and then decreases two small maxima at ∼0.9 and ∼1.8 eV. The observed E t dependences of S 0 for component A and C are discussed in terms of a trapping-mediated adsorption and an activated adsorption process and the chemical adsorption state corresponding to component A and C is also considered. (author)

  19. Validation of a new device to quantify groundwater-surface water exchange

    Science.gov (United States)

    Cremeans, Mackenzie M.; Devlin, J. F.

    2017-11-01

    Distributions of flow across the groundwater-surface water interface should be expected to be as complex as the geologic deposits associated with stream or lake beds and their underlying aquifers. In these environments, the conventional Darcy-based method of characterizing flow systems (near streams) has significant limitations, including reliance on parameters with high uncertainties (e.g., hydraulic conductivity), the common use of drilled wells in the case of streambank investigations, and potentially lengthy measurement times for aquifer characterization and water level measurements. Less logistically demanding tools for quantifying exchanges across streambeds have been developed and include drive-point mini-piezometers, seepage meters, and temperature profiling tools. This project adds to that toolbox by introducing the Streambed Point Velocity Probe (SBPVP), a reusable tool designed to quantify groundwater-surface water interactions (GWSWI) at the interface with high density sampling, which can effectively, rapidly, and accurately complement conventional methods. The SBPVP is a direct push device that measures in situ water velocities at the GWSWI with a small-scale tracer test on the probe surface. Tracer tests do not rely on hydraulic conductivity or gradient information, nor do they require long equilibration times. Laboratory testing indicated that the SBPVP has an average accuracy of ± 3% and an average precision of ± 2%. Preliminary field testing, conducted in the Grindsted Å in Jutland, Denmark, yielded promising agreement between groundwater fluxes determined by conventional methods and those estimated from the SBPVP tests executed at similar scales. These results suggest the SBPVP is a viable tool to quantify groundwater-surface water interactions in high definition in sandy streambeds.

  20. Electro-Kinetic Pumping with Slip Irreversibility in Heat Exchange of CSP-Powered Bio-Digester Assemblies

    OpenAIRE

    Ogedengbe, Emmanuel; Rosen, Marc

    2012-01-01

    Parametric studies of the effects of slip irreversibility in concentrating solar power (CSP)-powered bio-digester assemblies are investigated. Complexities regarding the identification of the appropriate electro-kinetic phenomena for certain electrolyte phases are reviewed. The application of exergy analysis to the design of energy conversion devices, like solar thermal collectors, for the required heat of formation in a downdraft waste food bio-digester, is discussed. Thermal management in t...

  1. Analysis of atmospheric flow over a surface protrusion using the turbulence kinetic energy equation with reference to aeronautical operating systems

    Science.gov (United States)

    Frost, W.; Harper, W. L.

    1975-01-01

    Flow over surface obstructions can produce significantly large wind shears such that adverse flying conditions can occur for aeronautical systems (helicopters, STOL vehicles, etc.). Atmospheric flow fields resulting from a semi-elliptical surface obstruction in an otherwise horizontally homogeneous statistically stationary flow are modelled with the boundary-layer/Boussinesq-approximation of the governing equation of fluid mechanics. The turbulence kinetic energy equation is used to determine the dissipative effects of turbulent shear on the mean flow. Iso-lines of turbulence kinetic energy and turbulence intensity are plotted in the plane of the flow and highlight regions of high turbulence intensity in the stagnation zone and sharp gradients in intensity along the transition from adverse to favourable pressure gradient. Discussion of the effects of the disturbed wind field in CTOL and STOL aircraft flight path and obstruction clearance standards is given. The results indicate that closer inspection of these presently recommended standards as influenced by wind over irregular terrains is required.

  2. Moist Orographic Convection: Physical Mechanisms and Links to Surface-Exchange Processes

    Directory of Open Access Journals (Sweden)

    Daniel J. Kirshbaum

    2018-02-01

    Full Text Available This paper reviews the current understanding of moist orographic convection and its regulation by surface-exchange processes. Such convection tends to develop when and where moist instability coincides with sufficient terrain-induced ascent to locally overcome convective inhibition. The terrain-induced ascent can be owing to mechanical (airflow over or around an obstacle and/or thermal (differential heating over sloping terrain forcing. For the former, the location of convective initiation depends on the dynamical flow regime. In “unblocked” flows that ascend the barrier, the convection tends to initiate over the windward slopes, while in “blocked” flows that detour around the barrier, the convection tends to initiate upstream and/or downstream of the high terrain where impinging flows split and rejoin, respectively. Processes that destabilize the upstream flow for mechanically forced moist convection include large-scale moistening and ascent, positive surface sensible and latent heat fluxes, and differential advection in baroclinic zones. For thermally forced flows, convective initiation is driven by thermally direct circulations with sharp updrafts over or downwind of the mountain crest (daytime or foot (nighttime. Along with the larger-scale background flow, local evapotranspiration and transport of moisture, as well as thermodynamic heterogeneities over the complex terrain, regulate moist instability in such events. Longstanding limitations in the quantitative understanding of related processes, including both convective preconditioning and initiation, must be overcome to improve the prediction of this convection, and its collective effects, in weather and climate models.

  3. Coupling of kinetic Monte Carlo simulations of surface reactions to transport in a fluid for heterogeneous catalytic reactor modeling

    International Nuclear Information System (INIS)

    Schaefer, C.; Jansen, A. P. J.

    2013-01-01

    We have developed a method to couple kinetic Monte Carlo simulations of surface reactions at a molecular scale to transport equations at a macroscopic scale. This method is applicable to steady state reactors. We use a finite difference upwinding scheme and a gap-tooth scheme to efficiently use a limited amount of kinetic Monte Carlo simulations. In general the stochastic kinetic Monte Carlo results do not obey mass conservation so that unphysical accumulation of mass could occur in the reactor. We have developed a method to perform mass balance corrections that is based on a stoichiometry matrix and a least-squares problem that is reduced to a non-singular set of linear equations that is applicable to any surface catalyzed reaction. The implementation of these methods is validated by comparing numerical results of a reactor simulation with a unimolecular reaction to an analytical solution. Furthermore, the method is applied to two reaction mechanisms. The first is the ZGB model for CO oxidation in which inevitable poisoning of the catalyst limits the performance of the reactor. The second is a model for the oxidation of NO on a Pt(111) surface, which becomes active due to lateral interaction at high coverages of oxygen. This reaction model is based on ab initio density functional theory calculations from literature.

  4. Palladium mixed-metal surface-modified AB5-type intermetallides enhance hydrogen sorption kinetics

    Directory of Open Access Journals (Sweden)

    Roman V. Denys

    2010-09-01

    Full Text Available Surface engineering approaches were adopted in the preparation of advanced hydrogen sorption materials, based on ‘low-temperature’, AB5-type intermetallides. The approaches investigated included micro-encapsulation with palladium and mixed-metal mantles using electroless plating. The influence of micro-encapsulation on the surface morphology and kinetics of hydrogen charging were investigated. It was found that palladium-nickel (Pd-Ni co-deposition by electroless plating significantly improved the kinetics of hydrogen charging of the AB5-type intermetallides at low hydrogen pressure and temperature, after long-term pre-exposure to air. The improvement in the kinetics of hydrogen charging was credited to a synergistic effect between the palladium and nickel atoms in the catalytic mantle and the formation of an ‘interfacial bridge’ for hydrogen diffusion by the nickel atoms in the deposited layer. The developed surface-modified materials may find application in highly selective hydrogen extraction, purification, and storage from impure hydrogen feeds.

  5. CONVECTIVE HEAT EXCHANGE ON THE LATERAL SURFACE OF A RELATIVELY LONG CYCLONE CHAMBER

    Directory of Open Access Journals (Sweden)

    E. N. Saburov

    2016-01-01

    Full Text Available The high-turbulent swirling flows of heat carrier that are created by a cyclone chamber are used in industry. They make it possible to intensify processes of heat and mass exchange. The results of an experimental study of convective heat transfer on the lateral surface of the active volume of a relatively long cyclone chamber considerably exceeding the length of the chambers that were used in previously performed studies are presented and analyzed in the article. Air supply in the swirler of the chamber was performed tangentially from diametrically opposite sides of the two input channels. The gas outlet was implemented from the opposite end. The heat transfer by convection to the swirling air flow was studied by the method of changing the state of aggregation of a heating agent – condensation of slightly superheated steam. Collecting condensate from the working section was made through a water seal for maintaining a constant pressure calorimeter. The amount of heat transferred during experiment was determined by weight of the collected condensate. The specific features of influence of geometrical characteristics of cyclone chamber on intensity of heat exchange are considered. In the experiments we varied the relative diameter of the outlet port of the chamber dвых and the relative area of the input channels fвх. Segmental construction of the chamber made it possible to move a calorimeter on its length. The local heat transfer coefficient was determined for various values of the dimensionless longitudinal coordinate z coinciding with the axis of the chamber, and counted from the back end of the swirler. The estimated equations of heat transfer obtained during the research are presented and recommended for use in practice of engineering. The considered problem is of an interest from the point of view of further research of aerodynamics and of convective heat transfer in a highly swirling flow cyclone devices, in order to improve the

  6. Chemical kinetics: on the heterogeneous catalysis processes leading to an exchange between two phases. Example: isotopic exchange reactions; Cinetique chimique: sur les processus de catalyse 'heterogene' conduisant a un echange entre deux phases. Exemple: reactions d'echange isotopique

    Energy Technology Data Exchange (ETDEWEB)

    Dirian, G; Grandcollot, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-01

    For an exchange reaction between a gaseous and a liquid phase proceeding by 'heterogeneous' catalysis in the liquid phase, diffusion in the liquid and the chemical reaction are two simultaneous and indivisible processes. We have nevertheless been able to establish criteria making it possible to distinguish between a really homogeneous kinetic process and a pseudo-homogeneous one. (author) [French] Pour une reaction d'echange entre une phase gazeuse et une phase liquide procedant par catalyse 'heterogene' en phase liquide, la diffusion dans le liquide et la reaction chimique sont deux etapes simultanees et indissociables. Nous avons pu neanmoins etablir des criteres permettant de distinguer entre une cinetique homogene vraie et une cinetique pseudo-homogene. (auteur)

  7. Kinetic analysis of the reactivity of aromatic amino acids in the T-for-H exchange reaction

    International Nuclear Information System (INIS)

    Yoshida, Akira; Imaizumi, Hiroshi; Sato, Takayuki; Kano, Naoki

    2009-01-01

    To quantitatively evaluate the influence of tritium ( 3 H or T) on ecosystem, the hydrogen isotope exchange reaction (T-for-H exchange reaction) between each aromatic amino acid (L-tyrosine, L-phenylalanine, or L-2-phenylglycine) and HTO vapor was observed at 50-70degC in the gas-solid system. Applying the A''-McKay plot method to data (obtained in the exchange reaction), the rate constants (k) of functional groups of each aromatic amino acid in this reaction was obtained. Comparing the rate constants, following six matters have been found in the T-for-H exchange reaction. (1) The reactivity of the functional groups in each amino acid increases with increasing temperature. (2) The reactivity of the functional groups of the amino acids (used) increases in the order of L-tyrosine, L-phenylalanine, and L-2-phenylglycine. (3) As to l-tyrosine, 1) the temperature dependence of each functional group increases in the order of COOH group, OH one, and NH 2 one, 2) the reactivity of OH group is 3.8 times greater than that of NH 2 one, and 3) the reactivity of COOH group is 2.0 times greater than NH 2 one. (4) As to the influence of the substituent, the reactivity of NH 2 group is larger than that of the COOH one. (5) Using the A''-McKay plot method, the reactivity of each functional group in an amino acid can be nondestructively and simultaneously clarified without using masking reagent. (6) The results obtained in this work is useful for preventing T contamination and for evaluating the influence of T on environment. (author)

  8. Quantifying Hyporheic Exchanges in a Large Scale River Reach Using Coupled 3-D Surface and Subsurface Computational Fluid Dynamics Simulations.

    Energy Technology Data Exchange (ETDEWEB)

    Hammond, Glenn Edward; Bao, J; Huang, M; Hou, Z; Perkins, W; Harding, S; Titzler, S; Ren, H; Thorne, P; Suffield, S; Murray, C; Zachara, J

    2017-03-01

    Hyporheic exchange is a critical mechanism shaping hydrological and biogeochemical processes along a river corridor. Recent studies on quantifying the hyporheic exchange were mostly limited to local scales due to field inaccessibility, computational demand, and complexity of geomorphology and subsurface geology. Surface flow conditions and subsurface physical properties are well known factors on modulating the hyporheic exchange, but quantitative understanding of their impacts on the strength and direction of hyporheic exchanges at reach scales is absent. In this study, a high resolution computational fluid dynamics (CFD) model that couples surface and subsurface flow and transport is employed to simulate hyporheic exchanges in a 7-km long reach along the main-stem of the Columbia River. Assuming that the hyporheic exchange does not affect surface water flow conditions due to its negligible magnitude compared to the volume and velocity of river water, we developed a one-way coupled surface and subsurface water flow model using the commercial CFD software STAR-CCM+. The model integrates the Reynolds-averaged Navier-Stokes (RANS) equation solver with a realizable κ-ε two-layer turbulence model, a two-layer all y+ wall treatment, and the volume of fluid (VOF) method, and is used to simulate hyporheic exchanges by tracking the free water-air interface as well as flow in the river and the subsurface porous media. The model is validated against measurements from acoustic Doppler current profiler (ADCP) in the stream water and hyporheic fluxes derived from a set of temperature profilers installed across the riverbed. The validated model is then employed to systematically investigate how hyporheic exchanges are influenced by surface water fluid dynamics strongly regulated by upstream dam operations, as well as subsurface structures (e.g. thickness of riverbed and subsurface formation layers) and hydrogeological properties (e.g. permeability). The results

  9. Surface energy exchanges along a tundra-forest transition and feedbacks to climate

    Science.gov (United States)

    Beringer, J.; Chapin, F. S.; Thompson, Catharine Copass; McGuire, A.D.

    2005-01-01

    Surface energy exchanges were measured in a sequence of five sites representing the major vegetation types in the transition from arctic tundra to forest. This is the major transition in vegetation structure in northern high latitudes. We examined the influence of vegetation structure on the rates of sensible heating and evapotranspiration to assess the potential feedbacks to climate if high-latitude warming were to change the distribution of these vegetation types. Measurements were made at Council on the Seward Peninsula, Alaska, at representative tundra, low shrub, tall shrub, woodland (treeline), and boreal forest sites. Structural differences across the transition from tundra to forest included an increase in the leaf area index (LAI) from 0.52 to 2.76, an increase in canopy height from 0.1 to 6.1 m, and a general increase in canopy complexity. These changes in vegetation structure resulted in a decrease in albedo from 0.19 to 0.10 as well as changes to the partitioning of energy at the surface. Bulk surface resistance to water vapor flux remained virtually constant across sites, apparently because the combined soil and moss evaporation decreased while transpiration increased along the transect from tundra to forest. In general, sites became relatively warmer and drier along the transect with the convective fluxes being increasingly dominated by sensible heating, as evident by an increasing Bowen ratio from 0.94 to 1.22. The difference in growing season average daily sensible heating between tundra and forest was 21 W m-2. Fluxes changed non-linearly along the transition, with both shrubs and trees substantially enhancing heat transfer to the atmosphere. These changes in vegetation structure that increase sensible heating could feed back to enhance warming at local to regional scales. The magnitude of these vegetation effects on potential high-latitude warming is two to three times greater than suggested by previous modeling studies. ?? 2005 Elsevier B.V. All

  10. How intensive agriculture affects surface-atmosphere exchange of nitrogen and carbon compounds over peatland

    Science.gov (United States)

    Bruemmer, C.; Richter, U.; Schrader, F.; Hurkuck, M.; Kutsch, W. L.

    2016-12-01

    Mid-latitude peatlands are often exposed to high atmospheric nitrogen deposition when located in close vicinity to agricultural land. As the impacts of altered deposition rates on nitrogen-limited ecosystems are poorly understood, we investigated the surface-atmosphere exchange of several nitrogen and carbon compounds using multiple high-resolution measurement techniques and modeling. Our study site was a protected semi-natural bog ecosystem. Local wind regime and land use in the adjacent area clearly regulated whether total reactive nitrogen (∑Nr) concentrations were ammonia (NH3) or NOx-dominated. Eddy-covariance measurements of NH3 and ∑Nr revealed concentration, temperature and surface wetness-dependent deposition rates. Intermittent periods of NH3 and ∑Nr emission likely attributed to surface water re-emission and soil efflux, respectively, were found, thereby indicating nitrogen oversaturation in this originally N-limited ecosystem. Annual dry plus wet deposition resulted in 20 to 25 kg N ha-1 depending on method and model used, which translated into a four- to fivefold exceedance of the ecosystem-specific critical load. As the bog site had likely been exposed to the observed atmospheric nitrogen burden over several decades, a shift in grass species' composition towards a higher number of nitrophilous plants was already visible. Three years of CO2 eddy flux measurements showed that the site was a small net sink in the range of 33 to 268 g CO2 m-2 yr-1. Methane emissions of 32 g CO2-eq were found to partly offset the sequestered carbon through CO2. Our study demonstrates the applicability of novel micrometeorological measurement techniques in biogeochemical sciences and stresses the importance of monitoring long-term changes in vulnerable ecosystems under anthropogenic pressure and climate change.

  11. Kinetic Rate Law Parameter Measurements on a Borosilicate Waste Glass: Effect of Temperature, pH, and Solution Composition on Alkali Ion Exchange

    International Nuclear Information System (INIS)

    Pierce, Eric M.; McGrail, B PETER.; Icenhower, J P.; Rodriguez, Elsa A.; Steele, Jackie L.; Baum, Steven R.

    2004-01-01

    The reaction kinetics of glass is controlled by matrix dissolution and ion exchange (IEX). Dissolution of an alkali-rich simulated borosilicate waste glass was investigated using single-pass flow-through (SPFT) experiments. Experiments were conducted as a function of temperature, pH, and solution composition by varying the SiO 2 (aq) activity in the influent solution. Results showed that under dilute conditions matrix dissolution increased with increasing pH and temperature, and decreased with increasing SiO 2 (aq) activity. IEX rates decreased with increasing pH and temperature, and increased with increasing SiO 2 (aq) activity. Over the solution composition range interrogated in this study the dominant dissolution mechanism changed from matrix dissolution to IEX. These results suggest that ''secondary'' reactions may become dominant under certain environmental conditions and emphasize the need to incorporate these reactions into dissolution rate models

  12. Electrical conductivity and oxygen exchange kinetics of La2NiO4+delta thin films grown by chemical vapor deposition

    DEFF Research Database (Denmark)

    Garcia, G.; Burriel, M.; Bonanos, Nikolaos

    2008-01-01

    Epitaxial c-axis oriented La2NiO4+delta films were deposited onto SrTiO3 and NdGaO3 substrates by the pulsed injection metal organic chemical vapor deposition technique. Experimental conditions were optimized in order to accurately control the composition, thickness, and texture of the layers. X......-ray diffraction was used to confirm the high crystalline quality of the obtained material. Electrical characterizations were performed on thin (50 nm) and thick (335 nm) layers. The total specific conductivity, which is predominantly electronic, was found to be larger for the thinner films measured (50 nm......), probably due to the effect of the strain present in the layers. Those thin films (50 nm) showed values even larger than those observed for single crystals and, to our knowledge, are the largest conductivity values reported to date for the La2NiO4+delta material. The oxygen exchange kinetics was studied...

  13. Quasiclassical trajectory study of the molecular beam kinetics of the deuterium atom--hydrogen halide exchange reactions

    International Nuclear Information System (INIS)

    Raff, L.M.; Suzukawa, H.H. Jr.; Thompson, D.L.

    1975-01-01

    Unadjusted quasiclassical trajectory computations have been carried out to simulate the molecular beam scattering of thermal D atom beams at 2800 degreeK crossed with beams of HCl and HI at 250 degreeK. Total reaction cross sections, energy partitioning distributions, and differential scattering cross sections have been computed for the exchange reactions D+HCl → DCl+H and D+HI → DI+H while total reaction cross sections are reported for the corresponding abstractions, i.e., D+HCl → HD+Cl and D+HI → HD+I. For the exchange reactions, the computed reaction cross sections are within the range estimated from the crossed beam experiments. The calculated average energy partitioned into relative translational motion of products is in near quantitative agreement with the beam results, and the predicted differential scattering cross sections appear to be in qualitative accord with the beam experiments. The over-all agreement between theory and experiment indicates that previously computed values for the thermal rate coefficients for the exchange reactions are of the right order and that a systematic error exists in the interpretation of photolysis data in the hydrogen--hydrogen halide systems

  14. Kinetic parameters, collision rates, energy exchanges and transport coefficients of non-thermal electrons in premixed flames at sub-breakdown electric field strengths

    KAUST Repository

    Bisetti, Fabrizio

    2014-01-02

    The effects of an electric field on the collision rates, energy exchanges and transport properties of electrons in premixed flames are investigated via solutions to the Boltzmann kinetic equation. The case of high electric field strength, which results in high-energy, non-thermal electrons, is analysed in detail at sub-breakdown conditions. The rates of inelastic collisions and the energy exchange between electrons and neutrals in the reaction zone of the flame are characterised quantitatively. The analysis includes attachment, ionisation, impact dissociation, and vibrational and electronic excitation processes. Our results suggest that Townsend breakdown occurs for E/N = 140 Td. Vibrational excitation is the dominant process up to breakdown, despite important rates of electronic excitation of CO, CO2 and N2 as well as impact dissociation of O2 being apparent from 50 Td onwards. Ohmic heating in the reaction zone is found to be negligible (less than 2% of peak heat release rate) up to breakdown field strengths for realistic electron densities equal to 1010 cm-3. The observed trends are largely independent of equivalence ratio. In the non-thermal regime, electron transport coefficients are insensitive to mixture composition and approximately constant across the flame, but are highly dependent on the electric field strength. In the thermal limit, kinetic parameters and transport coefficients vary substantially across the flame due to the spatially inhomogeneous concentration of water vapour. A practical approach for identifying the plasma regime (thermal versus non-thermal) in studies of electric field effects on flames is proposed. © 2014 Taylor & Francis.

  15. Correlation and prediction of ion exchange equilibria on weak-acid resins by means of the surface complex formation model

    International Nuclear Information System (INIS)

    Horst, J.

    1988-11-01

    The present work summarizes investigations of the equilibrium of the exchange of protons, copper, zinc, calcium, magnesium and sodium ions on two weak-acid exchange resins in hydrochloric and carbonic acid bearing solutions at 25 0 C. The description of the state of equilibrium between resin and solution is based on the individual chemical equilibria which have to be adjusted simultaneously. The equilibrium in the liquid phase is described by the mass action law and the condition of electroneutrality using activity coefficients calculated according to the theory of Debye and Hueckel. The exchange equilibria are described by means of a surface complex formation model, which was developed by Davis, James and Leckie for activated aluminia and which has been applied to weak-acid resins. The model concept assumes the resin as a plane surface in which the functional groups are distributed uniformly. (orig./RB) [de

  16. Full-dimensional analytical potential energy surface describing the gas-phase Cl + C2H6 reaction and kinetics study of rate constants and kinetic isotope effects.

    Science.gov (United States)

    Rangel, Cipriano; Espinosa-Garcia, Joaquin

    2018-02-07

    Within the Born-Oppenheimer approximation a full-dimensional analytical potential energy surface, PES-2017, was developed for the gas-phase hydrogen abstraction reaction between the chlorine atom and ethane, which is a nine body system. This surface presents a valence-bond/molecular mechanics functional form dependent on 60 parameters and is fitted to high-level ab initio calculations. This reaction presents little exothermicity, -2.30 kcal mol -1 , with a low height barrier, 2.44 kcal mol -1 , and intermediate complexes in the entrance and exit channels. We found that the energetic description was strongly dependent on the ab initio level used and it presented a very flat topology in the entrance channel, which represents a theoretical challenge in the fitting process. In general, PES-2017 reproduces the ab initio information used as input, which is merely a test of self-consistency. As a first test of the quality of the PES-2017, a theoretical kinetics study was performed in the temperature range 200-1400 K using two approaches, i.e. the variational transition-state theory and quasi-classical trajectory calculations, with spin-orbit effects. The rate constants show reasonable agreement with experiments in the whole temperature range, with the largest differences at the lowest temperatures, and this behaviour agrees with previous theoretical studies, thus indicating the inherent difficulties in the theoretical simulation of the kinetics of the title reaction. Different sources of error were analysed, such as the limitations of the PES and theoretical methods, recrossing effects, and the tunnelling effect, which is negligible in this reaction, and the manner in which the spin-orbit effects were included in this non-relativistic study. We found that the variation of spin-orbit coupling along the reaction path, and the influence of the reactivity of the excited Cl( 2 P 1/2 ) state, have relative importance, but do not explain the whole discrepancy. Finally, the

  17. Observations of surface momentum exchange over the marginal ice zone and recommendations for its parametrisation

    Directory of Open Access Journals (Sweden)

    A. D. Elvidge

    2016-02-01

    Full Text Available Comprehensive aircraft observations are used to characterise surface roughness over the Arctic marginal ice zone (MIZ and consequently make recommendations for the parametrisation of surface momentum exchange in the MIZ. These observations were gathered in the Barents Sea and Fram Strait from two aircraft as part of the Aerosol–Cloud Coupling And Climate Interactions in the Arctic (ACCACIA project. They represent a doubling of the total number of such aircraft observations currently available over the Arctic MIZ. The eddy covariance method is used to derive estimates of the 10 m neutral drag coefficient (CDN10 from turbulent wind velocity measurements, and a novel method using albedo and surface temperature is employed to derive ice fraction. Peak surface roughness is found at ice fractions in the range 0.6 to 0.8 (with a mean interquartile range in CDN10 of 1.25 to 2.85  ×  10−3. CDN10 as a function of ice fraction is found to be well approximated by the negatively skewed distribution provided by a leading parametrisation scheme (Lüpkes et al., 2012 tailored for sea-ice drag over the MIZ in which the two constituent components of drag – skin and form drag – are separately quantified. Current parametrisation schemes used in the weather and climate models are compared with our results and the majority are found to be physically unjustified and unrepresentative. The Lüpkes et al. (2012 scheme is recommended in a computationally simple form, with adjusted parameter settings. A good agreement holds for subsets of the data from different locations, despite differences in sea-ice conditions. Ice conditions in the Barents Sea, characterised by small, unconsolidated ice floes, are found to be associated with higher CDN10 values – especially at the higher ice fractions – than those of Fram Strait, where typically larger, smoother floes are observed. Consequently, the important influence of sea-ice morphology and floe size on

  18. Observations of surface momentum exchange over the marginal ice zone and recommendations for its parametrisation

    Science.gov (United States)

    Elvidge, A. D.; Renfrew, I. A.; Weiss, A. I.; Brooks, I. M.; Lachlan-Cope, T. A.; King, J. C.

    2016-02-01

    Comprehensive aircraft observations are used to characterise surface roughness over the Arctic marginal ice zone (MIZ) and consequently make recommendations for the parametrisation of surface momentum exchange in the MIZ. These observations were gathered in the Barents Sea and Fram Strait from two aircraft as part of the Aerosol-Cloud Coupling And Climate Interactions in the Arctic (ACCACIA) project. They represent a doubling of the total number of such aircraft observations currently available over the Arctic MIZ. The eddy covariance method is used to derive estimates of the 10 m neutral drag coefficient (CDN10) from turbulent wind velocity measurements, and a novel method using albedo and surface temperature is employed to derive ice fraction. Peak surface roughness is found at ice fractions in the range 0.6 to 0.8 (with a mean interquartile range in CDN10 of 1.25 to 2.85 × 10-3). CDN10 as a function of ice fraction is found to be well approximated by the negatively skewed distribution provided by a leading parametrisation scheme (Lüpkes et al., 2012) tailored for sea-ice drag over the MIZ in which the two constituent components of drag - skin and form drag - are separately quantified. Current parametrisation schemes used in the weather and climate models are compared with our results and the majority are found to be physically unjustified and unrepresentative. The Lüpkes et al. (2012) scheme is recommended in a computationally simple form, with adjusted parameter settings. A good agreement holds for subsets of the data from different locations, despite differences in sea-ice conditions. Ice conditions in the Barents Sea, characterised by small, unconsolidated ice floes, are found to be associated with higher CDN10 values - especially at the higher ice fractions - than those of Fram Strait, where typically larger, smoother floes are observed. Consequently, the important influence of sea-ice morphology and floe size on surface roughness is recognised, and

  19. Observations of surface momentum exchange over the marginal-ice-zone and recommendations for its parameterization

    Science.gov (United States)

    Elvidge, A. D.; Renfrew, I. A.; Weiss, A. I.; Brooks, I. M.; Lachlan-Cope, T. A.; King, J. C.

    2015-10-01

    Comprehensive aircraft observations are used to characterise surface roughness over the Arctic marginal ice zone (MIZ) and consequently make recommendations for the parameterization of surface momentum exchange in the MIZ. These observations were gathered in the Barents Sea and Fram Strait from two aircraft as part of the Aerosol-Cloud Coupling And Climate Interactions in the Arctic (ACCACIA) project. They represent a doubling of the total number of such aircraft observations currently available over the Arctic MIZ. The eddy covariance method is used to derive estimates of the 10 m neutral drag coefficient (CDN10) from turbulent wind velocity measurements, and a novel method using albedo and surface temperature is employed to derive ice fraction. Peak surface roughness is found at ice fractions in the range 0.6 to 0.8 (with a mean interquartile range in CDN10 of 1.25 to 2.85 × 10-3). CDN10 as a function of ice fraction is found to be well approximated by the negatively skewed distribution provided by a leading parameterization scheme (Lüpkes et al., 2012) tailored for sea ice drag over the MIZ in which the two constituent components of drag - skin and form drag - are separately quantified. Current parameterization schemes used in the weather and climate models are compared with our results and the majority are found to be physically unjustified and unrepresentative. The Lüpkes et al. (2012) scheme is recommended in a computationally simple form, with adjusted parameter settings. A good agreement is found to hold for subsets of the data from different locations despite differences in sea ice conditions. Ice conditions in the Barents Sea, characterised by small, unconsolidated ice floes, are found to be associated with higher CDN10 values - especially at the higher ice fractions - than those of Fram Strait, where typically larger, smoother floes are observed. Consequently, the important influence of sea ice morphology and floe size on surface roughness is

  20. The Effect of Landing Surface on the Plantar Kinetics of Chinese Paratroopers Using Half-Squat Landing

    Science.gov (United States)

    Li, Yi; Wu, Ji; Zheng, Chao; Huang, Rong Rong; Na, Yuhong; Yang, Fan; Wang, Zengshun; Wu, Di

    2013-01-01

    The objective of the study was to determine the effect of landing surface on plantar kinetics during a half-squat landing. Twenty male elite paratroopers with formal parachute landing training and over 2 years of parachute jumping experience were recruited. The subjects wore parachuting boots in which pressure sensing insoles were placed. Each subject was instructed to jump off a platform with a height of 60 cm, and land on either a hard or soft surface in a half-squat posture. Outcome measures were maximal plantar pressure, time to maximal plantar pressure (T-MPP), and pressure-time integral (PTI) upon landing on 10 plantar regions. Compared to a soft surface, hard surface produced higher maximal plantar pressure in the 1st to 4th metatarsal and mid-foot regions, but lower maximal plantar pressure in the 5th metatarsal region. Shorter T- MPP was found during hard surface landing in the 1st and 2nd metatarsal and medial rear foot. Landing on a hard surface landing resulted in a lower PTI than a soft surface in the 1stphalangeal region. For Chinese paratroopers, specific foot prosthesis should be designed to protect the1st to 4thmetatarsal region for hard surface landing, and the 1stphalangeal and 5thmetatarsal region for soft surface landing. Key Points Understanding plantar kinetics during the half-squat landing used by Chinese paratroopers can assist in the design of protective footwear. Compared to landing on a soft surface, a hard surface produced higher maximal plantar pressure in the 1st to 4th metatarsal and mid-foot regions, but lower maximal plantar pressure in the 5th metatarsal region. A shorter time to maximal plantar pressure was found during a hard surface landing in the 1st and 2nd metatarsals and medial rear foot. Landing on a hard surface resulted in a lower pressure-time integral than landing on a soft surface in the 1st phalangeal region. For Chinese paratroopers, specific foot prosthesis should be designed to protect the 1st to 4th metatarsal

  1. Kinetic analysis of a monoclonal therapeutic antibody and its single-chain homolog by surface plasmon resonance.

    Science.gov (United States)

    Patel, Rekha; Andrien, Bruce A

    2010-01-01

    Monoclonal antibodies (mAbs) and antibody fragments have become an emerging class of therapeutics since 1986. Their versatility enables them to be engineered for optimal efficiency and decreased immunogenicity, and the path to market has been set by recent regulatory approvals. One of the initial criteria for success of any protein or antibody therapeutic is to understand its binding characteristics to the target antigen. Surface plasmon resonance (SPR) has been widely used and is an important tool for ligand-antigen binding characterization. In this work, the binding kinetics of a recombinant mAb and its single-chain antibody homolog, single-chain variable fragment (scFv), was analyzed by SPR. These two proteins target the same antigen. The binding kinetics of the mAb (bivalent antibody) and scFv (monovalent scFv) for this antigen was analyzed along with an assessment of the thermodynamics of the binding interactions. Alternative binding configurations were investigated to evaluate potential experimental bias because theoretically experimental binding configuration should have no impact on binding kinetics. Self-association binding kinetics in the proteins' respective formulation solutions and antigen epitope mapping were also evaluated. Functional characterization of monoclonal and single-chain antibodies has become just as important as structural characterization in the biotechnology field.

  2. Processes of ammonia air–surface exchange in a fertilized Zea mays canopy

    Directory of Open Access Journals (Sweden)

    E. Nemitz

    2013-02-01

    Full Text Available Recent incorporation of coupled soil biogeochemical and bi-directional NH3 air–surface exchange algorithms into regional air quality models holds promise for further reducing uncertainty in estimates of NH3 emissions from fertilized soils. While this represents a significant advancement over previous approaches, the evaluation and improvement of such modeling systems for fertilized crops requires process-level field measurements over extended periods of time that capture the range of soil, vegetation, and atmospheric conditions that drive short-term (i.e., post-fertilization and total growing season NH3 fluxes. This study examines the processes of NH3 air–surface exchange in a fertilized corn (Zea mays canopy over the majority of a growing season to characterize soil emissions after fertilization and investigate soil–canopy interactions. Micrometeorological flux measurements above the canopy, measurements of soil, leaf apoplast and dew/guttation chemistry, and a combination of in-canopy measurements, inverse source/sink, and resistance modeling were employed. Over a period of approximately 10 weeks following fertilization, daily mean and median net canopy-scale fluxes yielded cumulative total N losses of 8.4% and 6.1%, respectively, of the 134 kg N ha−1 surface applied to the soil as urea ammonium nitrate (UAN. During the first month after fertilization, daily mean emission fluxes were positively correlated with soil temperature and soil volumetric water. Diurnally, maximum hourly average fluxes of ≈ 700 ng N m−2 s−1 occurred near mid-day, coincident with the daily maximum in friction velocity. Net emission was still observed 5 to 10 weeks after fertilization, although mid-day peak fluxes had declined to ≈ 125 ng N m−2 s−1. A key finding of the surface chemistry measurements was the observation of high pH (7.0–8.5 in leaf dew/guttation, which reduced the ability of the canopy to recapture soil emissions during wet periods

  3. Isotopically exchangeable phosphorus

    International Nuclear Information System (INIS)

    Barbaro, N.O.

    1984-01-01

    A critique revision of isotope dilution is presented. The concepts and use of exchangeable phosphorus, the phosphate adsorption, the kinetics of isotopic exchange and the equilibrium time in soils are discussed. (M.A.C.) [pt

  4. Research on Land Surface Thermal-Hydrologic Exchange in Southern China under Future Climate and Land Cover Scenarios

    Directory of Open Access Journals (Sweden)

    Jianwu Yan

    2013-01-01

    Full Text Available Climate change inevitably leads to changes in hydrothermal circulation. However, thermal-hydrologic exchanging caused by land cover change has also undergone ineligible changes. Therefore, studying the comprehensive effects of climate and land cover changes on land surface water and heat exchanges enables us to well understand the formation mechanism of regional climate and predict climate change with fewer uncertainties. This study investigated the land surface thermal-hydrologic exchange across southern China for the next 40 years using a land surface model (ecosystem-atmosphere simulation scheme (EASS. Our findings are summarized as follows. (i Spatiotemporal variation patterns of sensible heat flux (H and evapotranspiration (ET under the land cover scenarios (A2a or B2a and climate change scenario (A1B are unanimous. (ii Both H and ET take on a single peak pattern, and the peak occurs in June or July. (iii Based on the regional interannual variability analysis, H displays a downward trend (10% and ET presents an increasing trend (15%. (iv The annual average H and ET would, respectively, increase and decrease by about 10% when woodland converts to the cultivated land. Through this study, we recognize that land surface water and heat exchanges are affected greatly by the future climate change as well as land cover change.

  5. The importance of kinetics and redox in the biogeochemical cycling of iron in the surface ocean.

    Directory of Open Access Journals (Sweden)

    Peter L. Croot

    2012-06-01

    Full Text Available It is now well established that Iron (Fe is a limiting element in many regions of the open ocean. Our current understanding of the key processes which control iron distribution in the open ocean have been largely based on thermodynamic measurements performed under the assumption of equilibrium conditions. Using this equilibrium approach, researchers have been able to detect and quantify organic complexing ligands in seawater and examine their role in increasing the overall solubility of iron. Our current knowledge about iron bioavailability to phytoplankton and bacteria is also based heavily on carefully controlled laboratory studies where it is assumed the chemical species are in equilibrium in line with the free ion association model (FIAM and/or its successor the biotic ligand model (BLM. Similarly most field work on Fe biogeochemistry generally consists of a single profile which is in essence a ‘snap-shot’ in time of the system under investigation. However it is well known that the surface ocean is an extremely dynamic environment and it is unlikely if thermodynamic equilibrium between all the iron species present is ever truly achieved. In sunlit waters this is mostly due to the daily passage of the sun across the sky leading to photoredox processes which alter Fe speciation by cycling between redox states and between inorganic and organic species. Episodic deposition events, are also important perturbations to iron cycling as they bring new iron to the system altering the equilibrium between species and phases. Over the last 20 years the mesoscale iron enrichment experiments (e.g. IronEx I /II, SOIREE, EisenEx, SOFeX, EIFeX, SAGE, SEEDS and SERIES I /II and the FeCycle (I/II experiments have provided the first insights into processes altering iron speciation and distribution which occur over temporal scales of days to weeks. Here we utilize new field data collected in the open ocean on the redox and complexation kinetics of iron in the

  6. Kinetics and thermodynamics studies on the BMP-2 adsorption onto hydroxyapatite surface with different multi-morphological features.

    Science.gov (United States)

    Lu, Zhiwei; Huangfu, Changxin; Wang, Yanying; Ge, Hongwei; Yao, Yao; Zou, Ping; Wang, Guangtu; He, Hua; Rao, Hanbing

    2015-01-01

    The effect of the surface topography on protein adsorption process is of great significance for designing hydroxyapatite (HA) ceramic material surfaces. In this work, three different topographies of HA materials HA-sheet, HA-rod, and HA-whisker were synthesized and testified by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Brunauer-Emmett-Teller (BET) and a field emission scanning electron microscopy (FE-SEM). We have systematically investigated the adsorption kinetics and thermodynamics of bone morphogenetic proteins (BMP-2) on the three different topography surfaces of HA, respectively. The results showed that the maximum adsorption capacities of HA-sheet, HA-rod and HA-whisker were (219.96 ± 10.18), (247.13 ± 12.35), and (354.67 ± 17.73) μg · g(-1), respectively. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated as well as discussed. It demonstrated that the adsorption of BMP-2 onto HA could be described by the pseudo second-order equation. Adsorption of BMP-2 onto HA followed the Langmuir isotherm. It confirmed that compared with other samples HA-whisker had more adsorption sites for its high specific surface area which could provide more opportunities for protein molecules. The adsorption processes were endothermic (ΔH > 0), spontaneous (ΔG 0). A possible adsorption mechanism has been proposed. In addition, the BMP-2 could be adsorbed to the surface which existed slight conformational changes by FT-IR. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Development of a novel once-through flow visualization technique for kinetic study of bulk and surface scaling

    Science.gov (United States)

    Sanni, O.; Bukuaghangin, O.; Huggan, M.; Kapur, N.; Charpentier, T.; Neville, A.

    2017-10-01

    There is a considerable interest to investigate surface crystallization in order to have a full mechanistic understanding of how layers of sparingly soluble salts (scale) build on component surfaces. Despite much recent attention, a suitable methodology to improve on the understanding of the precipitation/deposition systems to enable the construction of an accurate surface deposition kinetic model is still needed. In this work, an experimental flow rig and associated methodology to study mineral scale deposition is developed. The once-through flow rig allows us to follow mineral scale precipitation and surface deposition in situ and in real time. The rig enables us to assess the effects of various parameters such as brine chemistry and scaling indices, temperature, flow rates, and scale inhibitor concentrations on scaling kinetics. Calcium carbonate (CaCO3) scaling at different values of the saturation ratio (SR) is evaluated using image analysis procedures that enable the assessment of surface coverage, nucleation, and growth of the particles with time. The result for turbidity values measured in the flow cell is zero for all the SR considered. The residence time from the mixing point to the sample is shorter than the induction time for bulk precipitation; therefore, there are no crystals in the bulk solution as the flow passes through the sample. The study shows that surface scaling is not always a result of pre-precipitated crystals in the bulk solution. The technique enables both precipitation and surface deposition of scale to be decoupled and for the surface deposition process to be studied in real time and assessed under constant condition.

  8. Using diurnal temperature signals to infer vertical groundwater-surface water exchange

    Science.gov (United States)

    Irvine, Dylan J.; Briggs, Martin A.; Lautz, Laura K.; Gordon, Ryan P.; McKenzie, Jeffrey M.; Cartwright, Ian

    2017-01-01

    Heat is a powerful tracer to quantify fluid exchange between surface water and groundwater. Temperature time series can be used to estimate pore water fluid flux, and techniques can be employed to extend these estimates to produce detailed plan-view flux maps. Key advantages of heat tracing include cost-effective sensors and ease of data collection and interpretation, without the need for expensive and time-consuming laboratory analyses or induced tracers. While the collection of temperature data in saturated sediments is relatively straightforward, several factors influence the reliability of flux estimates that are based on time series analysis (diurnal signals) of recorded temperatures. Sensor resolution and deployment are particularly important in obtaining robust flux estimates in upwelling conditions. Also, processing temperature time series data involves a sequence of complex steps, including filtering temperature signals, selection of appropriate thermal parameters, and selection of the optimal analytical solution for modeling. This review provides a synthesis of heat tracing using diurnal temperature oscillations, including details on optimal sensor selection and deployment, data processing, model parameterization, and an overview of computing tools available. Recent advances in diurnal temperature methods also provide the opportunity to determine local saturated thermal diffusivity, which can improve the accuracy of fluid flux modeling and sensor spacing, which is related to streambed scour and deposition. These parameters can also be used to determine the reliability of flux estimates from the use of heat as a tracer.

  9. Ray effects in the discrete-ordinate solution for surface radiation exchange

    Energy Technology Data Exchange (ETDEWEB)

    Liou, B T [Dept. of Mechanical Engineering, National Cheng Kung Univ., Tainan (Taiwan, Province of China); Wu, C Y [Dept. of Mechanical Engineering, National Cheng Kung Univ., Tainan (Taiwan, Province of China)

    1997-04-01

    A study of the application of the discrete-ordinate method (DOM) with remedy for the ray effects to the solution of surface radiation exchange is presented in this paper. The remedy for the ray effects is achieved by dividing the radiative intensity into the attenuated incident and the medium emitting components. To demonstrate the application of the technique, this work considers radiative heat transfer in a two-dimensional cylindrical enclosure filled with a nearly transparent medium. The results obtained by the present DOM are in excellent agreement with those by the radiosity/irradiation method. (orig.). With 4 figs., 3 tabs. [Deutsch] In der Arbeit wird ein Weg aufgezeigt, wie die Stoerstrahlungseffekte bei Anwendung der Methode der diskreten Ordinaten auf die Berechnung des Energietausches zwischen Oberflaechenstrahlern vermieden werden koennen. Dies laesst sich durch Aufspaltung der Strahlungsintensitaet in die abgeschwaechte einfallende und die vom Medium emittierte Komponente erreichen. Als Beispiel fuer die Anwendung dieses Verfahrens dient der Waermeaustausch durch Strahlung in einem zweidimensionalen zylindrischen Behaeltnis, das mit einem nahezu transparenten Medium befuellt ist. Die mit der modifizierten Methode erhaltenen Ergebnisse stimmen ausgezeichnet mit jenen nach dem klassischen Brutto-Verfahren ueberein. (orig.)

  10. Exercise on-transition uncoupling of ventilatory, gas exchange and cardiac hemodynamic kinetics accompany pulmonary oxygen stores depletion to impact exercise intolerance in human heart failure.

    Science.gov (United States)

    Van Iterson, E H; Smith, J R; Olson, T P

    2018-03-25

    In contrast to knowledge that heart failure (HF) patients demonstrate peak exercise uncoupling across ventilation, gas exchange and cardiac haemodynamics, whether this dyssynchrony follows that at the exercise on-transition is unclear. This study tested whether exercise on-transition temporal lag for ventilation relative to gas exchange and oxygen pulse (O 2 pulse) couples with effects from abnormal pulmonary gaseous oxygen store (O 2store ) contributions to V˙O 2 to interdependently precipitate persistently elevated ventilatory demand and low oxidative metabolic capacity in HF. Beat-to-beat HR and breath-to-breath ventilation and gas exchange were continuously acquired in HF (N = 9, ejection fraction = 30 ± 9%) and matched controls (N = 10) during square-wave ergometry at 60% V˙O 2peak (46 ± 14 vs 125 ± 54-W, P < .001). Temporal responses across V˙ E , V˙O 2 and O 2 pulse were assessed for the exercise on-transition using single exponential model Phase II on-kinetic time constants (τ = time to reach 63% steady-state rise). Breath-to-breath gas fractions and respiratory flows were used to determine O 2stores . HF vs controls: τ for V˙ E (137 ± 93 vs 74 ± 40-seconds, P = .03), V˙O 2 (60 ± 40 vs 23 ± 5-seconds, P = .03) and O 2 pulse (28 ± 18 vs 23 ± 15-seconds, P = .59). Within HF, τ for V˙ E differed from O 2 pulse (P < .02), but not V˙O 2 . Exercise V˙ E rise (workload indexed) differed in HF vs controls (545 ± 139 vs 309 ± 88-mL min -1 W -1 , P < .001). Exercise on-transition O 2store depletion in HF exceeded controls, generally persisting to end-exercise. These data suggest HF demonstrated exercise on-transition O 2store depletion (high O 2store contribution to V˙O 2 ) coupled with dyssynchronous V˙ E , V˙O 2 and O 2 pulse kinetics-not attributable to prolonged cardiac haemodynamics. Persistent high ventilatory demand and low oxidative metabolic capacity in HF may be precipitated by physiological uncoupling occurring within the exercise

  11. Electro-Kinetic Pumping with Slip Irreversibility in Heat Exchange of CSP-Powered Bio-Digester Assemblies

    Directory of Open Access Journals (Sweden)

    Emmanuel O.B. Ogedengbe

    2012-12-01

    Full Text Available Parametric studies of the effects of slip irreversibility in concentrating solar power (CSP-powered bio-digester assemblies are investigated. Complexities regarding the identification of the appropriate electro-kinetic phenomena for certain electrolyte phases are reviewed. The application of exergy analysis to the design of energy conversion devices, like solar thermal collectors, for the required heat of formation in a downdraft waste food bio-digester, is discussed. Thermal management in the silicon-based substrate of the energy system is analyzed. The rectangular-shaped micro-channels are simulated with a finite-volume, staggered coupling of the pressure-velocity fields. Entropy generation transport within the energy system is determined and coupled with the solution procedure. Consequently, the effects of channel size perturbation, Reynolds number, and pressure ratios on the thermal performance and exergy destruction are presented. A comparative analysis of the axial heat conduction for thermal management in energy conversion devices is proposed.

  12. Kinetics and thermodynamics studies on the BMP-2 adsorption onto hydroxyapatite surface with different multi-morphological features

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Zhiwei; Huangfu, Changxin; Wang, Yanying; Ge, Hongwei; Yao, Yao; Zou, Ping; Wang, Guangtu [College of Science, Sichuan Agricultural University, Ya' an 625014 (China); He, Hua [Institute of Animal Genetics and Breeding, Sichuan Agricultural University, Wenjiang, Sichuan 611130 (China); Rao, Hanbing, E-mail: rhbscu@gmail.com [College of Science, Sichuan Agricultural University, Ya' an 625014 (China)

    2015-07-01

    The effect of the surface topography on protein adsorption process is of great significance for designing hydroxyapatite (HA) ceramic material surfaces. In this work, three different topographies of HA materials HA-sheet, HA-rod, and HA-whisker were synthesized and testified by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Brunauer–Emmett–Teller (BET) and a field emission scanning electron microscopy (FE-SEM). We have systematically investigated the adsorption kinetics and thermodynamics of bone morphogenetic proteins (BMP-2) on the three different topography surfaces of HA, respectively. The results showed that the maximum adsorption capacities of HA-sheet, HA-rod and HA-whisker were (219.96 ± 10.18), (247.13 ± 12.35), and (354.67 ± 17.73) μg · g{sup −1}, respectively. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated as well as discussed. It demonstrated that the adsorption of BMP-2 onto HA could be described by the pseudo second-order equation. Adsorption of BMP-2 onto HA followed the Langmuir isotherm. It confirmed that compared with other samples HA-whisker had more adsorption sites for its high specific surface area which could provide more opportunities for protein molecules. The adsorption processes were endothermic (ΔH > 0), spontaneous (ΔG < 0) and entropy increasing (ΔS > 0). A possible adsorption mechanism has been proposed. In addition, the BMP-2 could be adsorbed to the surface which existed slight conformational changes by FT-IR. - Highlights: • A novel protein adsorption studies based on sheet, rod and whisker of HA were designed. • Kinetic and thermodynamics parameters of BMP-2 and HA bonded materials were evaluated. • Surface topographies of the HA effect BMP-2 adsorption • The HA-whisker material had excellent adsorption performance for protein enrichment. • The electrostatic interaction is responsible for the

  13. Kinetics and thermodynamics studies on the BMP-2 adsorption onto hydroxyapatite surface with different multi-morphological features

    International Nuclear Information System (INIS)

    Lu, Zhiwei; Huangfu, Changxin; Wang, Yanying; Ge, Hongwei; Yao, Yao; Zou, Ping; Wang, Guangtu; He, Hua; Rao, Hanbing

    2015-01-01

    The effect of the surface topography on protein adsorption process is of great significance for designing hydroxyapatite (HA) ceramic material surfaces. In this work, three different topographies of HA materials HA-sheet, HA-rod, and HA-whisker were synthesized and testified by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Brunauer–Emmett–Teller (BET) and a field emission scanning electron microscopy (FE-SEM). We have systematically investigated the adsorption kinetics and thermodynamics of bone morphogenetic proteins (BMP-2) on the three different topography surfaces of HA, respectively. The results showed that the maximum adsorption capacities of HA-sheet, HA-rod and HA-whisker were (219.96 ± 10.18), (247.13 ± 12.35), and (354.67 ± 17.73) μg · g −1 , respectively. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated as well as discussed. It demonstrated that the adsorption of BMP-2 onto HA could be described by the pseudo second-order equation. Adsorption of BMP-2 onto HA followed the Langmuir isotherm. It confirmed that compared with other samples HA-whisker had more adsorption sites for its high specific surface area which could provide more opportunities for protein molecules. The adsorption processes were endothermic (ΔH > 0), spontaneous (ΔG < 0) and entropy increasing (ΔS > 0). A possible adsorption mechanism has been proposed. In addition, the BMP-2 could be adsorbed to the surface which existed slight conformational changes by FT-IR. - Highlights: • A novel protein adsorption studies based on sheet, rod and whisker of HA were designed. • Kinetic and thermodynamics parameters of BMP-2 and HA bonded materials were evaluated. • Surface topographies of the HA effect BMP-2 adsorption • The HA-whisker material had excellent adsorption performance for protein enrichment. • The electrostatic interaction is responsible for the BMP-2

  14. Kinetic electron emission from metal surfaces induced by impact of slow ions

    Czech Academy of Sciences Publication Activity Database

    Šroubek, Zdeněk; Lorinčík, Jan

    -, č. 625 (2014), s. 7-9 ISSN 0039-6028 R&D Projects: GA MŠk(CZ) ME10086 Institutional support: RVO:67985882 Keywords : Ion induced kinetic electron emission * Electronic excitation Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 1.925, year: 2014

  15. Kinetic analysis of the reactivity of aliphatic cyclic alcohols and carboxylic acids in the T-for-H exchange reaction

    International Nuclear Information System (INIS)

    Tamura, Kiyoshi; Imaizumi, Hiroshi; Kano, Naoki

    2007-01-01

    In order to quantitatively evaluate the influence of tritium ( 3 He or T) on various functional groups in environment, the hydrogen isotope exchange reaction (T-for-H exchange reaction) between tritium-labeled poly-(vinyl alcohol) and each aliphatic cyclic alcohol (or carboxylic acid) has been dynamically observed in the range of 50 to 90degC. Consequently, the activities of the aliphatic cyclic alcohol and carboxylic acid increased with increasing reaction time. Applying in A''-McKay plot method to the observed data, the rate constants (k) for these materials were obtained. Using the k, the relation between the number of carbon atoms in the ring in each alcohol and the reactivity of the alcohol was quantitatively compared. Then, to clarify the effect of relative atomic charge of O atom (connected with the H atom in the hydroxy (or carboxy) group in the material) on the reactivity of the material, the MOPAC method was used. From both the above-mentioned and the obtained previously, the following nine items were found as to aliphatic cyclic alcohols (and carboxylic acids) in the T-for-H exchange reaction. (1) The reactivity of aliphatic cyclic alcohols (and carboxylic acids) depends on the temperature. (2) The reactivity of the cyclic materials decreases with increasing number of carbon atoms in the ring. (3) The reactivity of the aliphatic cyclic carboxylic acid seems to be smaller than that of aliphatic cyclic alcohol, and be larger than that of aliphatic cyclic amine. (4) For aliphatic cyclic alcohols, correlation exists between k and relative atomic charges of O atom obtained by the MOPAC method, but the tendency for aliphatic cyclic carboxylic acid is not clear. (5) As to having the same number of carbon atoms in each ring, the reactivity of the aliphatic cyclic carboxylic acid including the side chain is smaller than of the aliphatic cyclic carboxylic acid including no side chain. (6) The reactivity of aliphatic cyclic carboxylic acid is larger than that of

  16. Formation of ZnSe/Bi2Se3 QDs by surface cation exchange and high photothermal conversion

    Directory of Open Access Journals (Sweden)

    Guozhi Jia

    2015-08-01

    Full Text Available Water-dispersed core/shell structure ZnSe/Bi2Se3 quantum dots were synthesized by ultrasonicwave-assisted cation exchange reaction. Only surface Zn ion can be replaced by Bi ion in ZnSe quantum dots, which lead to the ultrathin Bi2Se3 shell layer formed. It is significance to find to change the crystal of QDs due to the acting of ultrasonicwave. Cation exchange mechanism and excellent photothermal conversion properties are discussed in detail.

  17. The effect of carbonic anhydrase on the kinetics and equilibrium of the oxygen isotope exchange in the CO2-H2O system: Implications for δ18O vital effects in biogenic carbonates

    Science.gov (United States)

    Uchikawa, Joji; Zeebe, Richard E.

    2012-10-01

    Interpretations of the primary paleoceanographic information recorded in stable oxygen isotope values (δ18O) of biogenic CaCO3 can be obscured by disequilibrium effects. CaCO3 is often depleted in 18O relative to the δ18O values expected for precipitation in thermodynamic equilibrium with ambient seawater as a result of vital effects. Vital effects in δ18O have been explained in terms of the influence of fluid pH on the overall δ18O of the sum of dissolved inorganic carbon (DIC) species (often referred to as "pH model") and in terms of 18O depletion as a result of the kinetic effects associated with CO2 hydration (CO2 + H2O ↔ H2CO3 ↔ HCO3- + H+) and CO2 hydroxylation (CO2 + OH- ↔ HCO3-) in the calcification sites (so-called "kinetic model"). This study addresses the potential role of an enzyme, carbonic anhydrase (CA), that catalyzes inter-conversion of CO2 and HCO3- in relation to the underlying mechanism of vital effects. We performed quantitative inorganic carbonate precipitation experiments in order to examine the changes in 18O equilibration rate as a function of CA concentration. Experiments were performed at pH 8.3 and 8.9. These pH values are comparable to the average surface ocean pH and elevated pH levels observed in the calcification sites of some coral and foraminiferal species, respectively. The rate of uncatalyzed 18O exchange in the CO2-H2O system is governed by the pH-dependent DIC speciation and the kinetic rate constant for CO2 hydration and hydroxylation, which can be summarized by a simple mathematical expression. The results from control experiments (no CA addition) are in agreement with this expression. The results from control experiments also suggest that the most recently published kinetic rate constant for CO2 hydroxylation has been overestimated. When CA is present, the 18O equilibration process is greatly enhanced at both pH levels due to the catalysis of CO2 hydration by the enzyme. For example, the time required for 18O

  18. Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO{sub 2} surface: The case of terminal oxygen atom exchange

    Energy Technology Data Exchange (ETDEWEB)

    Kevorkyants, Ruslan, E-mail: ruslan.kevorkyants@gmail.com; Sboev, Mikhail N.; Chizhov, Yuri V.

    2017-05-01

    Highlights: • DFT R1 mechanism of photostimulated oxygen isotope exchange between {sup 16}O{sup 18}O and terminal oxygen atom of a defect surface of nanocrystalline TiO{sub 2} is proposed. • The mechanism involves four adsorption intermediates and five transition states. • Activation energy of the reaction is 0.24 eV. • G-tensors of O{sub 3}{sup −} intermediates match EPR data on O{sub 2} adsorbed on UV-irradiated TiO{sub 2} surface. - Abstract: Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between {sup 16}O{sup 18}O and terminal oxygen atom of a defect TiO{sub 2} surface, which is modeled by amorphous Ti{sub 8}O{sub 16} nanocluster in excited S{sup 1} electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24 eV. The computed g-tensors of the predicted ozonide O{sub 3}{sup −} chemisorption species match well EPR data on O{sub 2} adsorption on UV-irradiated nanocrystalline TiO{sub 2}. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction’s mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VO{sub x}/TiO{sub 2} reported earlier.

  19. Mechanistic investigations of the hydrolysis of amides, oxoesters and thioesters via kinetic isotope effects and positional isotope exchange.

    Science.gov (United States)

    Robins, Lori I; Fogle, Emily J; Marlier, John F

    2015-11-01

    The hydrolysis of amides, oxoesters and thioesters is an important reaction in both organic chemistry and biochemistry. Kinetic isotope effects (KIEs) are one of the most important physical organic methods for determining the most likely transition state structure and rate-determining step of these reaction mechanisms. This method induces a very small change in reaction rates, which, in turn, results in a minimum disturbance of the natural mechanism. KIE studies were carried out on both the non-enzymatic and the enzyme-catalyzed reactions in an effort to compare both types of mechanisms. In these studies the amides and esters of formic acid were chosen because this molecular structure allowed development of methodology to determine heavy-atom solvent (nucleophile) KIEs. This type of isotope effect is difficult to measure, but is rich in mechanistic information. Results of these investigations point to transition states with varying degrees of tetrahedral character that fit a classical stepwise mechanism. This article is part of a special issue entitled: Enzyme Transition States from Theory and Experiment. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Combining Microbial Enzyme Kinetics Models with Light Use Efficiency Models to Predict CO2 and CH4 Ecosystem Exchange from Flooded and Drained Peatland Systems

    Science.gov (United States)

    Oikawa, P. Y.; Jenerette, D.; Knox, S. H.; Sturtevant, C. S.; Verfaillie, J. G.; Baldocchi, D. D.

    2014-12-01

    Under California's Cap-and-Trade program, companies are looking to invest in land-use practices that will reduce greenhouse gas (GHG) emissions. The Sacramento-San Joaquin River Delta is a drained cultivated peatland system and a large source of CO2. To slow soil subsidence and reduce CO2 emissions, there is growing interest in converting drained peatlands to wetlands. However, wetlands are large sources of CH4 that could offset CO2-based GHG reductions. The goal of our research is to provide accurate measurements and model predictions of the changes in GHG budgets that occur when drained peatlands are restored to wetland conditions. We have installed a network of eddy covariance towers across multiple land use types in the Delta and have been measuring CO2 and CH4 ecosystem exchange for multiple years. In order to upscale these measurements through space and time we are using these data to parameterize and validate a process-based biogeochemical model. To predict gross primary productivity (GPP), we are using a simple light use efficiency (LUE) model which requires estimates of light, leaf area index and air temperature and can explain 90% of the observed variation in GPP in a mature wetland. To predict ecosystem respiration we have adapted the Dual Arrhenius Michaelis-Menten (DAMM) model. The LUE-DAMM model allows accurate simulation of half-hourly net ecosystem exchange (NEE) in a mature wetland (r2=0.85). We are working to expand the model to pasture, rice and alfalfa systems in the Delta. To predict methanogenesis, we again apply a modified DAMM model, using simple enzyme kinetics. However CH4 exchange is complex and we have thus expanded the model to predict not only microbial CH4 production, but also CH4 oxidation, CH4 storage and the physical processes regulating the release of CH4 to the atmosphere. The CH4-DAMM model allows accurate simulation of daily CH4 ecosystem exchange in a mature wetland (r2=0.55) and robust estimates of annual CH4 budgets. The LUE

  1. Diffusion of small Cu islands on the Ni(111) surface: A self-learning kinetic Monte Carlo study

    Science.gov (United States)

    Acharya, Shree Ram; Shah, Syed Islamuddin; Rahman, Talat S.

    2017-08-01

    We elucidate the diffusion kinetics of a heteroepitaxial system consisting of two-dimensional small (1-8 atoms) Cu islands on the Ni(111) surface at (100-600) K using the Self-Learning Kinetic Monte Carlo (SLKMC-II) method. Study of the statics of the system shows that compact CuN (3≤N≤8) clusters made up of triangular units on fcc occupancy sites are the energetically most stable structures of those clusters. Interestingly, we find a correlation between the height of the activation energy barrier (Ea) and the location of the transition state (TS). The Ea of processes for Cu islands on the Ni(111) surface are in general smaller than those of their counterpart Ni islands on the same surface. We find this difference to correlate with the relative strength of the lateral interaction of the island atoms in the two systems. While our database consists of hundreds of possible processes, we identify and discuss the energetics of those that are the most dominant, or are rate-limiting, or most contributory to the diffusion of the islands. Since the Ea of single- and multi-atom processes that convert compact island shapes into non-compact ones are larger (with a significantly smaller Ea for their reverse processes) than that for the collective (concerted) motion of the island, the later dominate in the system kinetics - except for the cases of the dimer, pentamer and octamer. Short-jump involving one atom, long jump dimer-shearing, and long-jump corner shearing (via a single-atom) are, respectively, the dominating processes in the diffusion of the dimer, pentamer and octamer. Furthermore single-atom corner-rounding are the rate-limiting processes for the pentamer and octamer islands. Comparison of the energetics of selected processes and lateral interactions obtained from semi-empirical interatomic potentials with those from density functional theory show minor quantitative differences and overall qualitative agreement.

  2. Controlling drug delivery kinetics from mesoporous titania thin films by pore size and surface energy

    Directory of Open Access Journals (Sweden)

    Karlsson J

    2015-07-01

    Full Text Available Johan Karlsson, Saba Atefyekta, Martin Andersson Department of Chemical and Biological Engineering, Chalmers University of Technology, Gothenburg, Sweden Abstract: The osseointegration capacity of bone-anchoring implants can be improved by the use of drugs that are administrated by an inbuilt drug delivery system. However, to attain superior control of drug delivery and to have the ability to administer drugs of varying size, including proteins, further material development of drug carriers is needed. Mesoporous materials have shown great potential in drug delivery applications to provide and maintain a drug concentration within the therapeutic window for the desired period of time. Moreover, drug delivery from coatings consisting of mesoporous titania has shown to be promising to improve healing of bone-anchoring implants. Here we report on how the delivery of an osteoporosis drug, alendronate, can be controlled by altering pore size and surface energy of mesoporous titania thin films. The pore size was varied from 3.4 nm to 7.2 nm by the use of different structure-directing templates and addition of a swelling agent. The surface energy was also altered by grafting dimethylsilane to the pore walls. The drug uptake and release profiles were monitored in situ using quartz crystal microbalance with dissipation (QCM-D and it was shown that both pore size and surface energy had a profound effect on both the adsorption and release kinetics of alendronate. The QCM-D data provided evidence that the drug delivery from mesoporous titania films is controlled by a binding–diffusion mechanism. The yielded knowledge of release kinetics is crucial in order to improve the in vivo tissue response associated to therapeutic treatments. Keywords: mesoporous titania, controlled drug delivery, release kinetics, alendronate, QCM-D

  3. Optimization of acidified oil esterification catalyzed by sulfonated cation exchange resin using response surface methodology

    International Nuclear Information System (INIS)

    Ma, Lingling; Han, Ying; Sun, Kaian; Lu, Jie; Ding, Jincheng

    2015-01-01

    Highlights: • As lipid source, acidified oil are from industrial wastes for renewable energy. • The predicted conversion rate of FFAs was 75.24% under the RSM optimized conditions. • The adsorption system was employed to remove the water produced to shift the equilibrium toward ethyl ester production. • Maximum conversion rate of 98.32% was obtained using adsorption system at optimum process parameters. • Compared with tradition methods, molecular sieve dehydration method improved the conversion rate by 23.08%. - Abstract: The esterification of acidified oil with ethanol catalyzed by sulfonated cation exchange resins (SCER) was optimized using the response surface methodology (RSM). The effects of the molar ratio of ethanol to acidified oil, reaction time and catalyst loading on the conversion rate of free fatty acids (FFAs) were investigated at the temperature of the boiling point of ethanol. Results showed that the highest conversion rate of 75.24% was obtained at the molar ratio of ethanol to acidified oil of 23.2, reaction time of 8.0 h and catalyst loading of 35.0 wt.%. Moreover, the conversion rate of FFAs was increased to 98.32% by using a water adsorption apparatus under the RSM optimized conditions. Scanning electronic microscopic–energy dispersive spectrometric (SEM–EDS), X-ray diffractometric (XRD) and thermogravimetric–derivative thermogravimetric (TG–DTG) analyses confirmed that the morphology of catalysts did not change much and the mechanical and thermal stabilities were still good after the reaction. Furthermore, SCER exhibited a high catalytic activity and stability after being reused for five successive times. The fuel properties of the biodiesel were comparable to that of ASTM, EN and GB biodiesel standard

  4. Solid oxide fuel cell cathode infiltrate particle size control and oxygen surface exchange resistance determination

    Science.gov (United States)

    Burye, Theodore E.

    Over the past decade, nano-sized Mixed Ionic Electronic Conducting (MIEC) -- micro-sized Ionic Conducting (IC) composite cathodes produced by the infiltration method have received much attention in the literature due to their low polarization resistance (RP) at intermediate (500-700°C) operating temperatures. Small infiltrated MIEC oxide nano-particle size and low intrinsic MIEC oxygen surface exchange resistance (Rs) have been two critical factors allowing these Nano-Micro-Composite Cathodes (NMCCs) to achieve high performance and/or low temperature operation. Unfortunately, previous studies have not found a reliable method to control or reduce infiltrated nano-particle size. In addition, controversy exists on the best MIEC infiltrate composition because: 1) Rs measurements on infiltrated MIEC particles are presently unavailable in the literature, and 2) bulk and thin film Rs measurements on nominally identical MIEC compositions often vary by up to 3 orders of magnitude. Here, two processing techniques, precursor nitrate solution desiccation and ceria oxide pre-infiltration, were developed to systematically produce a reduction in the average La0.6Sr0.4Co0.8Fe 0.2O3-delta (LSCF) infiltrated nano-particle size from 50 nm to 22 nm. This particle size reduction reduced the SOFC operating temperature, (defined as the temperature where RP=0.1 Ocm 2) from 650°C to 540°C. In addition, Rs values for infiltrated MIEC particles were determined for the first time through finite element modeling calculations on 3D Focused Ion Beam-Scanning Electron Microscope (FIB-SEM) reconstructions of electrochemically characterized infiltrated electrodes.

  5. A consistent hierarchy of generalized kinetic equation approximations to the master equation applied to surface catalysis.

    Science.gov (United States)

    Herschlag, Gregory J; Mitran, Sorin; Lin, Guang

    2015-06-21

    We develop a hierarchy of approximations to the master equation for systems that exhibit translational invariance and finite-range spatial correlation. Each approximation within the hierarchy is a set of ordinary differential equations that considers spatial correlations of varying lattice distance; the assumption is that the full system will have finite spatial correlations and thus the behavior of the models within the hierarchy will approach that of the full system. We provide evidence of this convergence in the context of one- and two-dimensional numerical examples. Lower levels within the hierarchy that consider shorter spatial correlations are shown to be up to three orders of magnitude faster than traditional kinetic Monte Carlo methods (KMC) for one-dimensional systems, while predicting similar system dynamics and steady states as KMC methods. We then test the hierarchy on a two-dimensional model for the oxidation of CO on RuO2(110), showing that low-order truncations of the hierarchy efficiently capture the essential system dynamics. By considering sequences of models in the hierarchy that account for longer spatial correlations, successive model predictions may be used to establish empirical approximation of error estimates. The hierarchy may be thought of as a class of generalized phenomenological kinetic models since each element of the hierarchy approximates the master equation and the lowest level in the hierarchy is identical to a simple existing phenomenological kinetic models.

  6. Kinetics of boride layers formed on the surface of AISI 4140 steel

    International Nuclear Information System (INIS)

    Sen, S.; Sen, U.; Bindal, C.

    2004-01-01

    The present study reports on boride layer growth kinetics of borided AISI 4140 steel. Steels were boronized in molten borax, boric acid and ferro-silicon bath at 1123 K 1173 K and 1223 K for 2, 4, 6 and 8 hours. Boride layer thickness ranged from 38.4 to 225 μm. Layer growth kinetics were analysed by measuring the extent of penetration of FeB and Fe 2 B sublayers as a function of boronizing time and temperature in the range of 1123-1223 K. The depth of the tips of the most deeply penetrated FeB and Fe 2 B needles are taken as measures for diffusion in the fast directions. The kinetics of the reaction, K=K 0 exp(-Q/RT) have also been determined by varying the boriding temperature and time. The results showed that K increase with boronizing temperature. Activation energy (Q) for present study was determined as 215 kj.mol -1 . The diffusion coefficient (K) ranged from 3 x 10 -9 cm 2 s -1 to 2 x 10 -8 cm 2 s -1 . Also temperature-dependent constant (K 0 ) at temperatures 1123 K, 1173 K and 1223 K was 179.4 cm 2 s -1 . (orig.)

  7. Kinetics of boride layers formed on the surface of AISI 4140 steel

    Energy Technology Data Exchange (ETDEWEB)

    Sen, S.; Sen, U. [Sakarya Univ., Dept. of Metal Education, Sakarya (Turkey); Bindal, C. [Sakarya Univ., Dept. of Materials and Metallurgy, Sakarya (Turkey)

    2004-07-01

    The present study reports on boride layer growth kinetics of borided AISI 4140 steel. Steels were boronized in molten borax, boric acid and ferro-silicon bath at 1123 K 1173 K and 1223 K for 2, 4, 6 and 8 hours. Boride layer thickness ranged from 38.4 to 225 {mu}m. Layer growth kinetics were analysed by measuring the extent of penetration of FeB and Fe{sub 2}B sublayers as a function of boronizing time and temperature in the range of 1123-1223 K. The depth of the tips of the most deeply penetrated FeB and Fe{sub 2}B needles are taken as measures for diffusion in the fast directions. The kinetics of the reaction, K=K{sub 0} exp(-Q/RT) have also been determined by varying the boriding temperature and time. The results showed that K increase with boronizing temperature. Activation energy (Q) for present study was determined as 215 kj.mol{sup -1}. The diffusion coefficient (K) ranged from 3 x 10{sup -9} cm{sup 2}s{sup -1} to 2 x 10{sup -8} cm{sup 2}s{sup -1}. Also temperature-dependent constant (K{sub 0}) at temperatures 1123 K, 1173 K and 1223 K was 179.4 cm{sup 2}s{sup -1}. (orig.)

  8. Study on fermentation conditions of palm juice vinegar by response surface methodology and development of a kinetic model

    Directory of Open Access Journals (Sweden)

    S. Ghosh

    2012-09-01

    Full Text Available Natural vinegar is one of the fermented products which has some potentiality with respect to a nutraceutical standpoint. The present study is an optimization of the fermentation conditions for palm juice vinegar production from palm juice (Borassus flabellifer wine, this biochemical process being aided by Acetobacter aceti (NCIM 2251. The physical parameters of the fermentation conditions such as temperature, pH, and time were investigated by Response Surface Methodology (RSM with 2³ factorial central composite designs (CCD. The optimum pH, temperature and time were 5.5, 30 °C and 72 hrs for the highest yield of acetic acid (68.12 g / L. The quadratic model equation had a R² value of 0.992. RSM played an important role in elucidating the basic mechanisms in a complex situation, thus providing better process control by maximizing acetic acid production with the respective physical parameters. At the optimized conditions of temperature, pH and time and with the help of mathematical kinetic equations, the Monod specific growth rate ( µ max= 0.021 h-1, maximum Logistic specific growth rate ( µ 'max = 0.027 h-1 and various other kinetic parameters were calculated, which helped in validation of the experimental data. Therefore, the established kinetic models may be applied for the production of natural vinegar by fermentation of low cost palm juice.

  9. Evaluation of Degradation Kinetic of Tomato Paste Color in Heat Processing and Modeling of These Changes by Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    M. Ganjeh

    2015-12-01

    Full Text Available Color is an important qualitative factor in tomato products such as tomato paste which is affected by heat processing. The main goal of this study was to evaluate the degradation kinetics of tomato paste color during heat processing by Arrhenius equation and modeling of these changes by response surface methodology (RSM. Considering this purpose, tomato paste was processed at three temperatures of 60, 70 and 80 °C for 25-100 minutes and by three main color indices including L, a and b, a/b ratio, total color difference (TCD, Saturation index (SI and hue angle (HU was analyzed. Degradation kinetics of these parameters was evaluated by Arrhenius equation and their changing trends were modeled by RSM. All parameters except TCA (zero order followed a first order reaction. The b index by highest and TCA and a/b by least activation energies had the maximum and minimum sensitivity to the temperature changes, respectively. Also, TCD and b had the maximum and minimum changing rates, respectively. All responses were influenced by independent parameters (the influence of temperature was more than time and RSM was capable of modeling and predicting these responses. In general, Arrhenius equation was appropriate to evaluate degradation kinetics of tomato paste color changes and RSM was able to estimate independent and interaction effects of time and temperature so that quadratic models were capable to predict these changes by a high accuracy (R2 > 0.95.

  10. Changes in surface electromyography signals and kinetics associated with progression of fatigue at two speeds during wheelchair propulsion.

    Science.gov (United States)

    Qi, Liping; Wakeling, James; Grange, Simon; Ferguson-Pell, Martin

    2012-01-01

    The purpose of this study was to determine whether muscle balance is influenced by fatigue in a recordable way, toward creating novel defensive activity strategies for manual wheelchair users (MWUs). Wheelchair propulsion to a point of mild fatigue, level 15 on the Rating of Perceived Exertion scale, was investigated at two different speeds. Surface electromyographic (EMG) activity of 7 muscles was recorded on 14 nondisabled participants. Kinetic variables were measured using a SmartWheel. No significant effect was found of percentage endurance time on kinetic variables for the two propulsion speeds. Fatigue-related changes in the EMG spectra were identified as an increase of EMG intensity and a decrease of mean power frequency as a function of percent endurance time for the tested muscles under both fast and slow speed conditions. The greater increases in activity for propulsive muscles compared with recovery muscles during fast speed wheelchair propulsion indicated muscle imbalance associated with fatiguing wheelchair propulsion. This study shows how kinetic and EMG information might be used as feedback to MWUs to ensure that they conduct activity in ways that do not precipitate injury.

  11. Analysis of the ways to decrease residual stresses on heat exchanging tubes and steam generator collector surfaces for reducing the material corrosion damage

    International Nuclear Information System (INIS)

    Stepanov, G.V.; Kharchenko, V.V.; Shatco, A.A.; Dranchenko, V.V.; Titov, V.F.

    1994-01-01

    Computer simulations have been carried out to analyze the effect of heat exchanger tube pressing forming process into a steam generator collector, on its residual stresses and strains. The program takes into consideration kinetic process peculiarities, material non-linear rheological properties, separate deformation of tubes and collectors in the presence of a clearance and their contact interaction, damage and crack appearance. 4 figs

  12. Iron oxidation kinetics and phosphorus immobilization at the groundwater-surface water interface

    NARCIS (Netherlands)

    van der Grift, Bas; Rozemeijer, Joachim; Griffioen, Jasper; van der Velde, Ype

    2014-01-01

    Eutrophication of freshwater environments following diffuse nutrient loads is a widely recognized water quality problem in catchments. Fluxes of non-point P sources to surface waters originate from surface runoff and flow from soil water and groundwater into surface water. The availability of P in

  13. Surface kinetics for catalytic combustion of hydrogen-air mixtures on platinum at atmospheric pressure in stagnation flows

    Science.gov (United States)

    Ikeda, H.; Sato, J.; Williams, F. A.

    1995-03-01

    Experimental studies of the combustion of premixed hydrogen-air mixtures impinging on the surface of a heated platinum plate at normal atmospheric pressure were performed and employed to draw inferences concerning surface reaction mechanisms and rate parameters applicable under practical conditions of catalytic combustion. Plate and gas temperatures were measured by thermocouples, and concentration profiles of major stable species in the gas were measured by gas-chromatographic analyses of samples withdrawn by quartz probes. In addition, ignition and extinction phenomena were recorded and interpreted with the aid of a heat balance at the surface and a previous flow-field analysis of the stagnation-point boundary layer. From the experimental and theoretical results, conclusions were drawn concerning the surface chemical-kinetic mechanisms and values of the elementary rate parameters that are consistent with the observations. In particular, the activation energy for the surface oxidation step H + OH → H 2O is found to be appreciably less at these high surface coverages than in the low-coverage limit.

  14. A first principles kinetic Monte Carlo investigation of the adsorption and mobility of gadolinium on the (100) surface of tungsten

    International Nuclear Information System (INIS)

    Samin, Adib J.; Zhang, Jinsuo

    2017-01-01

    An accurate characterization of lanthanide adsorption and mobility on tungsten surfaces is important for pyroprocessing. In the present study, the adsorption and diffusion of gadolinium on the (100) surface of tungsten was investigated. It was found that the hollow sites were the most energetically favorable for the adsorption. It was further observed that a magnetic moment was induced following the adsorption of gadolinium on the tungsten surface and that the system with adsorbed hollow sites had the largest magnetization. A pathway for the surface diffusion of gadolinium was determined to occur by hopping between the nearest neighbor hollow sites via the bridge site and the activation energy for the hop was calculated to be 0.75 eV. The surface diffusion process was further assessed using two distinct kinetic Monte Carlo models; one that accounted for lateral adsorbate interactions up to the second nearest neighbor and one that did not account for such interatomic interactions in the adlayer. When the lateral interactions were included in the simulations, the diffusivity was observed to have a strong dependence on coverage (for the coverage values being studied). The effects of lateral interactions were further observed in a one-dimensional simulation of the diffusion equation where the asymmetry in the surface coverage profile upon its approach to a steady state distribution was clear in comparison with the simulations which did not account for those interactions.

  15. A first principles kinetic Monte Carlo investigation of the adsorption and mobility of gadolinium on the (100) surface of tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Samin, Adib J., E-mail: samin.2@osu.edu; Zhang, Jinsuo

    2017-05-15

    An accurate characterization of lanthanide adsorption and mobility on tungsten surfaces is important for pyroprocessing. In the present study, the adsorption and diffusion of gadolinium on the (100) surface of tungsten was investigated. It was found that the hollow sites were the most energetically favorable for the adsorption. It was further observed that a magnetic moment was induced following the adsorption of gadolinium on the tungsten surface and that the system with adsorbed hollow sites had the largest magnetization. A pathway for the surface diffusion of gadolinium was determined to occur by hopping between the nearest neighbor hollow sites via the bridge site and the activation energy for the hop was calculated to be 0.75 eV. The surface diffusion process was further assessed using two distinct kinetic Monte Carlo models; one that accounted for lateral adsorbate interactions up to the second nearest neighbor and one that did not account for such interatomic interactions in the adlayer. When the lateral interactions were included in the simulations, the diffusivity was observed to have a strong dependence on coverage (for the coverage values being studied). The effects of lateral interactions were further observed in a one-dimensional simulation of the diffusion equation where the asymmetry in the surface coverage profile upon its approach to a steady state distribution was clear in comparison with the simulations which did not account for those interactions.

  16. The impact of surface composition on Tafel kinetics leading to enhanced electrochemical insertion of hydrogen in palladium

    Science.gov (United States)

    Dmitriyeva, Olga; Hamm, Steven C.; Knies, David L.; Cantwell, Richard; McConnell, Matt

    2018-05-01

    Our previous work experimentally demonstrated the enhancement of electrochemical hydrogen insertion into palladium by modifying the chemical composition of the cathode surface with Pb, Pt and Bi, referred to as surface promoters. The experiment demonstrated that an optimal combination of the surface promoters led to an increase in hydrogen fugacity of more than three orders of magnitude, while maintaining the same current density. This manuscript discusses the application of Density Functional Theory (DFT) to elucidate the thermodynamics and kinetics of observed enhancement of electrochemical hydrogen insertion into palladium. We present theoretical simulations that: (1) establish the elevation of hydrogen's chemical potential on Pb and Bi surfaces to enhance hydrogen insertion, (2) confirm the increase of a Tafel activation barrier that results in a decrease of the reaction rate at the given hydrogen overpotential, and (3) explain why the surface promoter's coverage needs to be non-uniform, namely to allow hydrogen insertion into palladium bulk while simultaneously locking hydrogen below the surface (the corking effect). The discussed DFT-based method can be used for efficient scanning of different material configurations to design a highly effective hydrogen storage system.

  17. Development of a Thin Film Primary Surface Heat Exchanger for Advanced Power Cycles

    Energy Technology Data Exchange (ETDEWEB)

    Allison, Tim [Southwest Research Inst., San Antonio, TX (United States); Beck, Griffin [Southwest Research Inst., San Antonio, TX (United States); Bennett, Jeffrey [Southwest Research Inst., San Antonio, TX (United States); Hoopes, Kevin [Southwest Research Inst., San Antonio, TX (United States); Miller, Larry [Southwest Research Inst., San Antonio, TX (United States)

    2016-06-29

    This project objective is to develop a high-temperature design upgrade for an existing primary surface heat exchanger so that the redesigned hardware is capable of operation in CO2 at temperatures up to 1,510°F (821°C) and pressure differentials up to 130 psi (9 bar). The heat exchanger is proposed for use as a recuperator in an advanced low-pressure oxy-fuel Brayton cycle that is predicted to achieve over 50% thermodynamic efficiency, although the heat exchanger could also be used in other high-temperature, low-differential pressure cycles. This report describes the progress to date, which includes continuing work performed to select and test new candidate materials for the recuperator redesign, final mechanical and thermal performance analysis results of various redesign concepts, and the preliminary design of a test loop for the redesigned recuperator including a budgetary estimate for detailed test loop design, procurement, and test operation. A materials search was performed in order to investigate high-temperature properties of many candidate materials, including high-temperature strength and nickel content. These properties were used to rank the candidate materials, resulting in a reduced list of nine materials for corrosion testing. Multiple test rigs were considered and analyzed for short-term corrosion testing and Thermal Gravimetric Analysis (TGA) was selected as the most cost-effective option for evaluating corrosion resistance of the candidate materials. In addition, tantalum, niobium, and chromium coatings were identified as potential options for increased corrosion resistance. The test results show that many materials exhibit relatively low weight gain rates, and that niobium and tantalum coatings may improve corrosion resistance for many materials, while chromium coatings appear to oxidize and debond quickly. Metallurgical analysis of alloys was also performed, showing evidence of intergranular attack in 282 that may cause long

  18. Experimental study of heat transfer enhancement due to the surface vibrations in a flexible double pipe heat exchanger

    Science.gov (United States)

    Hosseinian, A.; Meghdadi Isfahani, A. H.

    2018-04-01

    In this study, the heat transfer enhancement due to the surface vibration for a double pipe heat exchanger, made of PVDF, is investigated. In order to create forced vibrations (3-9 m/s2, 100 Hz) on the outer surface of the heat exchanger electro-dynamic vibrators are used. Experiments were performed at inner Reynolds numbers ranging from 2533 to 9960. The effects of volume flow rate and temperature on heat transfer performance are evaluated. Results demonstrated that heat transfer coefficient increases by increasing vibration level and mass flow rate. The most increase in heat transfer coefficient is 97% which is obtained for the highest vibration level (9 m/s2) in the experiment range.

  19. Polyethylene imine/graphene oxide layer-by-layer surface functionalization for significantly improved limit of detection and binding kinetics of immunoassays on acrylate surfaces.

    Science.gov (United States)

    Miyazaki, Celina M; Mishra, Rohit; Kinahan, David J; Ferreira, Marystela; Ducrée, Jens

    2017-10-01

    Antibody immobilization on polymeric substrates is a key manufacturing step for microfluidic devices that implement sample-to-answer automation of immunoassays. In this work, a simple and versatile method to bio-functionalize poly(methylmethacrylate) (PMMA), a common material of such "Lab-on-a-Chip" systems, is proposed; using the Layer-by-Layer (LbL) technique, we assemble nanostructured thin films of poly(ethylene imine) (PEI) and graphene oxide (GO). The wettability of PMMA surfaces was significantly augmented by the surface treatment with (PEI/GO) 5 film, with an 81% reduction of the contact angle, while the surface roughness increased by 600%, thus clearly enhancing wettability and antibody binding capacity. When applied to enzyme-linked immunosorbent assays (ELISAs), the limit of detection of PMMA surface was notably improved from 340pgmL -1 on commercial grade polystyrene (PS) and 230pgmL -1 on plain PMMA surfaces to 130pgmL -1 on (PEI/GO) 5 treated PMMA. Furthermore, the accelerated antibody adsorption kinetics on the LbL films of GO allowed to substantially shorten incubation times, e.g. for anti-rat IgG adsorption from 2h down to 15min on conventional and treated surfaces, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Effect of structural modifications on the drying kinetics of foods: changes in volume, surface area and product shape

    Directory of Open Access Journals (Sweden)

    Antonio De Michelis

    2013-10-01

    Full Text Available Macro and micro-structural changes take place during food dehydration. Macro-structural changes encompass modifications in shape, area and volume. Studies of such changes are important because dehydration kinetics (essential for calculating industrial dryers may be highly influenced by changes in food shape and dimensions. The overall changes in volume, surface area (“shrinkage” and shape (Heywood factor, with provides a close description of food shape were determined experimentally, and the results were correlated with simple expressions. Hence, although dehydration kinetics can be modeled with simplified overall shrinkage expressions, the possibility of selecting a suitable geometry and predicting the characteristics dimensions will provide higher accuracy. An additional unresolved problem is the lack of a general model that predicts macro-structural changes for various foods and diverse geometries. In this work, based on experimental data of sweet and sour cherries, and rose hip fruits, a simplified general model to predict changes in volume and surface area are proposed. To estimate how the changes in characteristic dimensions affect the kinetic studies, experimental drying curves for the three fruits by means of a diffusional model considered the following variants for the characteristic dimensions: (i The radius of the fresh food, assumed constant; (ii The radius of the partially dehydrated product; (iii The radius predicted by the correlation for structural changes, especially volume, obtained in this work and generalized for the three fruits, and (iv to demonstrate the need to study the macro-structural changes for all dehydrated foods, also be present the case of a restructured food.

  1. A kinetic model for borosilicate glass dissolution based on the dissolution affinity of a surface alteration layer

    International Nuclear Information System (INIS)

    Bourcier, W.L.; Peiffer, D.W.; Knauss, K.G.; McKeegan, K.D.; Smith, D.K.

    1989-11-01

    A kinetic model for the dissolution of borosilicate glass is used to predict the dissolution rate of a nuclear waste glass. In the model, the glass dissolution rate is controlled by the rate of dissolution of an alkali-depleted amorphous surface (gel) layer. Our model predicts that all components concentrated in the surface layer, affect glass dissolution rates. The good agreement between predicted and observed elemental dissolution rates suggests that the dissolution rate of the gel layer limits the overall rate of glass dissolution. The model predicts that the long-term rate of glass dissolution will depend mainly on ion concentrations in solution, and therefore on the secondary phases which precipitate and control ion concentrations. 10 refs., 5 figs., 1 tab

  2. Effects of Iron-Oxide Nanoparticle Surface Chemistry on Uptake Kinetics and Cytotoxicity in CHO-K1 Cells

    Directory of Open Access Journals (Sweden)

    Camille C. Hanot

    2015-12-01

    Full Text Available Superparamagnetic iron-oxide nanoparticles (SPIONs show great promise for multiple applications in biomedicine. While a number of studies have examined their safety profile, the toxicity of these particles on reproductive organs remains uncertain. The goal of this study was to evaluate the cytotoxicity of starch-coated, aminated, and PEGylated SPIONs on a cell line derived from Chinese Hamster ovaries (CHO-K1 cells. We evaluated the effect of particle diameter (50 and 100 nm and polyethylene glycol (PEG chain length (2k, 5k and 20k Da on the cytotoxicity of SPIONs by investigating cell viability using the tetrazolium dye 3-(4,5-dimethylthiazol-2-yl-2,5-diphenyltetrazolium bromide (MTT and sulforhodamine B (SRB assays. The kinetics and extent of SPION uptake by CHO-K1 cells was also studied, as well as the resulting generation of intracellular reactive oxygen species (ROS. Cell toxicity profiles of SPIONs correlated strongly with their cellular uptake kinetics, which was strongly dependent on surface properties of the particles. PEGylation caused a decrease in both uptake and cytotoxicity compared to aminated SPIONs. Interestingly, 2k Da PEG-modifed SPIONs displayed the lowest cellular uptake and cytotoxicity among all studied particles. These results emphasize the importance of surface coatings when engineering nanoparticles for biomedical applications.

  3. Heat exchanger

    International Nuclear Information System (INIS)

    Dostatni, A.W.; Dostatni, Michel.

    1976-01-01

    In the main patent, a description was given of a heat exchanger with an exchange surface in preformed sheet metal designed for the high pressure and temperature service particularly encountered in nuclear pressurized water reactors and which is characterised by the fact that it is composed of at least one exchanger bundle sealed in a containment, the said bundle or bundles being composed of numerous juxtaposed individual compartments whose exchange faces are built of preformed sheet metal. The present addendun certificate concerns shapes of bundles and their positioning methods in the exchanger containment enabling its compactness to be increased [fr

  4. The Pathogenic A2V Mutant Exhibits Distinct Aggregation Kinetics, Metal Site Structure, and Metal Exchange of the Cu2+ -Aβ Complex

    DEFF Research Database (Denmark)

    Somavarapu, Arun Kumar; Shen, Fei; Teilum, Kaare

    2017-01-01

    2V. 1H NMR relaxation exhibits the same trend for the non-coordinating aromatic residues (A2T2V), and implies markedly faster inter-peptide Cu2+exchange for the A2V variant than for WT and A2T. We therefore hypothesize that component I of the Cu–Aβ complex is related to pathogenicity......A prominent current hypothesis is that impaired metal ion homeostasis may contribute to Alzheimer's disease (AD). We elucidate the interaction of Cu2+ with wild-type (WT) Aβ1–40 and the genetic variants A2T and A2V which display increasing pathogenicity as A2T2V. Cu2+ significantly extends...... the lag phase in aggregation kinetics, in particular for the pathogenic A2V variant. Additionally, a rapid, initial, low intensity ThT response is observed, possibly reflecting formation of Cu2+ induced amorphous aggregates, as supported by atomic force microscopy (AFM) and circular dichroism (CD...

  5. Kinetics of soybean oil epoxidation with peracetic acid formed in situ in the presence of an ion exchange resin: Pseudo-homogeneous model

    Directory of Open Access Journals (Sweden)

    Janković Milovan

    2017-01-01

    Full Text Available A kinetic model was proposed for the epoxidation of vegetable oils with peracetic acid formed in situ from acetic acid and hydrogen peroxide in the presence of an acidic ion exchange resin as a catalyst. The model is pseudo-homogeneous with respect to the catalyst. Besides the main reactions of peracetic acid and epoxy ring formation, the model takes into account the side reaction of epoxy ring opening with acetic acid. The partitioning of acetic acid and peracetic acid between the aqueous and organic phases and the change in the phases’ volumes during the process were considered. The temperature dependency of the apparent reaction rate coefficients is described by a reparameterized Arrhenius equation. The constants in the proposed model were estimated by fitting the experimental data obtained for the epoxidations of soybean oil conducted under defined reaction conditions. The highest epoxy yield of 87.73% was obtained at 338 K when the mole ratio of oil unsaturation:acetic acid:hydrogen peroxide was 1:0.5:1.35 and when the amount of the catalyst Amberlite IR-120H was 4.04 wt.% of oil. Compared to the other reported pseudo-homogeneous models, the model proposed in this study better correlates the change of double bond and epoxy group contents during the epoxidation process. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. III45022

  6. Hydrogen exchange kinetics in a membrane protein determined by 15N NMR spectroscopy: Use of the INEPT [insensitive nucleus enhancement by polarization transfer] experiment to follow individual amides in detergent-solubilized M13 coat protein

    International Nuclear Information System (INIS)

    Henry, G.D.; Sykes, B.D.

    1990-01-01

    The coat protein of the filamentous coliphage M13 is a 50-residue polypeptide which spans the inner membrane of the Escherichia coli host upon infection. Amide hydrogen exchange kinetics have been used to probe the structure and dynamics of M13 coat protein which has been solubilized in sodium dodecyl sulfate (SDS) micelles. In a previous 1 H nuclear magnetic resonance (NMR) study, multiple exponential analysis of the unresolved amide proton envelope revealed the existence of two slow kinetic sets containing a total of about 30 protons. The slower set (15-20 amides) originates from the hydrophobic membrane-spanning region and exchanges at least 10 5 -fold slower than the unstructured, non-H-bonded model polypeptide poly(DL-alanine). Herein the authors use 15 N NMR spectroscopy of biosynthetically labeled coat protein to follow individual, assigned, slowly exchanging amides in or near the hydrophobic segment. The INEPT (insensitive nucleus enhancement by polarization transfer) experiments can be used to transfer magnetization to the 15 N nucleus from a coupled proton; when 15 N-labeled protonated protein is dissolved in 2 H 2 O, the INEPT signal disappears with time as the amide protons are replaced by solvent deuterons. Amide hydrogen exchange is catalyzed by both H + and OH - ions. The time-dependent exchange-out experiment is suitable for slow exchange rates (k ex ). The INEPT experiment was also adapted to measure some of the more rapidly exchanging amides in the coat protein using either saturation transfer from water or exchange effects on the polarization transfer step itself. The results of all of these experiments are consistent with previous models of the coat protein in which a stable segment extends from the hydrophobic membrane-spanning region through to the C-terminus, whereas the N-terminal region is undergoing more extensive dynamic fluctuations

  7. Kinetic evaluation of propyne surface diffusivity on silica-alumina-supported chromium(VI) using positron annihilation surface detection

    International Nuclear Information System (INIS)

    Ferrieri, R.A.; Wolf, A.P.

    1984-01-01

    A study has been performed on the rate of the translational surface diffusivity of propyne on a silica-alumina-supported Cr(VI) catalyst. This rate was measured via nonchemical acetylene-propyne sorbate interactions coupled with positron annihilation surface detection (PASD). The surface displacement rate of [ 11 C]acetylene by propyne was measured in a transient experiment as a function of the adjacent Cr-site distance and correlated to propyne surface diffusivity, D/sub s/. Results indicated that D/sub s/ increased linearly when the adjacent site distance was decreased for catalysts loaded with between 0.08 and 0.8 wt % of chromium. However, D/sub s/ fell off drastically to nearly zero when greater Cr-site dispersion was achieved at support loadings below 0.08 wt % of chromium. Catalytic selectivity for p-xylene production was also measured as a function of D/sub s/ and was shown to have a strong dependence of its rate. 25 references, 4 figures

  8. Retardation of heat exchanger surfaces mineral fouling by water-based diethylenetriamine pentaacetate-treated CNT nanofluids

    International Nuclear Information System (INIS)

    Teng, K.H.; Amiri, Ahmad; Kazi, S.N.; Bakar, M.A.; Chew, B.T.; Al-Shamma’a, A.; Shaw, A.

    2017-01-01

    Highlights: • Decoration EDTA on MWCNT surface to retard the rate of fouling. • Preparation of DTPA-treated MWCNT/water nanofluid. • Evaluating the mitigation of DTPA-treated MWCNT-based water nanofluids. • Retarding of calcium carbonate crystals by MWCNT-DTPA additives. • The effect of additive on the rate of fouling. - Abstract: Mineral scale deposition on heat exchanging surfaces increases the thermal resistance and reduces the operating service life. The effect is usually intensified at higher temperatures due to the inverse temperature solubility characteristics of some minerals in the cooling water. Scale formation build up when dissolved salt crystallize from solution onto the heated surface, forming an adherent deposit. It is very important for heat transfer applications to cope with the fouling problems in industry. In this present study, a set of fouling experiments was conducted to evaluate the mitigation of calcium carbonate scaling by applying DTPA-treated MWCNT-based water nanofluids on heat exchanger surfaces. Investigation of additive DTPA-treated MWCNT-based water nanofluids (benign to the environment) on fouling rate of deposition was performed. 300 mg L −1 of artificially-hardened calcium carbonate solution was prepared as a fouling solution for deposit analysis. Assessment of the deposition of calcium carbonate on the heat exchanger surface with respect to the inhibition of crystal growth was conducted by Scanning Electron Microscope (SEM). The results showed that the formation of calcium carbonate crystals can be retarded significantly by adding MWCNT-DTPA additives as inhibition in the solution.

  9. Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path.

    Science.gov (United States)

    Opitz, Alexander K; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Jürgen

    2011-11-30

    The oxygen exchange kinetics of platinum on yttria-stabilized zirconia (YSZ) was investigated by means of geometrically well-defined Pt microelectrodes. By variation of electrode size and temperature it was possible to separate two temperature regimes with different geometry dependencies of the polarization resistance. At higher temperatures (550-700 °C) an elementary step located close to the three phase boundary (TPB) with an activation energy of ∼1.6 eV was identified as rate limiting. At lower temperatures (300-400 °C) the rate limiting elementary step is related to the electrode area and exhibited a very low activation energy in the order of 0.2 eV. From these observations two parallel pathways for electrochemical oxygen exchange are concluded.The nature of these two elementary steps is discussed in terms of equivalent circuits. Two combinations of parallel rate limiting reaction steps are found to explain the observed geometry dependencies: (i) Diffusion through an impurity phase at the TPB in parallel to diffusion of oxygen through platinum - most likely along Pt grain boundaries - as area-related process. (ii) Co-limitation of oxygen diffusion along the Pt|YSZ interface and charge transfer at the interface with a short decay length of the corresponding transmission line (as TPB-related process) in parallel to oxygen diffusion through platinum.

  10. In situ photoemission spectroscopy using synchrotron radiation for O2 translational kinetic energy induced oxidation processes of partially-oxidized Si(001) surfaces

    International Nuclear Information System (INIS)

    Teraoka, Yuden; Yoshigoe, Akitaka

    2001-01-01

    The influence of translational kinetic energy of incident O 2 molecules for the passive oxidation process of partially-oxidized Si(001) surfaces has been studied by photoemission spectroscopy. The translational kinetic energy of O 2 molecules was controlled up to 3 eV by a supersonic seed beam technique using a high temperature nozzle. Two translational kinetic energy thresholds (1.0 eV and 2.6 eV) were found out in accordance with the first-principles calculation for the oxidation of clean surfaces. Si-2p photoemission spectra measured in representative translational kinetic energies revealed that the translational kinetic energy dependent oxidation of dimers and the second layer (subsurface) backbonds were caused by the direct dissociative chemisorption of O 2 molecules. Moreover, the difference in chemical bonds for oxygen atoms was found out to be as low and high binding energy components in O-1s photoemission spectra. Especially, the low binding energy component increased with increasing the translational kinetic energy that indicates the translational kinetic energy induced oxidation in backbonds. (author)

  11. Effect of the competition of Cu(II) and Ni(II) on the kinetic and thermodynamic stabilities of Cr(III)-organic ligand complexes using competitive ligand exchange (EDTA).

    Science.gov (United States)

    Cunha, Graziele da Costa; Goveia, Danielle; Romão, Luciane Pimenta Cruz; de Oliveira, Luciana Camargo

    2015-05-01

    The effect of competition of Cu(II) and Ni(II) on the kinetic stability of Cr(III) complexed with natural organic matter (NOM) was characterized using EDTA exchange with single-stage tangential-flow ultrafiltration. For a water sample from Serra de Itabaiana, 3% of spiked Cr(III) was exchanged, while for a sample from the Itapanhaú River, 7, 10, 10, and 21% was exchanged in experiments using Cr(III) alone and in combination with Cu(II), Ni(II), or Cu(II) + Ni(II), respectively. Times required to reach exchange equilibrium with EDTA were less than 360 min. The influence of competition from Ni(II) and Cu(II) on the availability of complexed Cr(III) was low, demonstrating preference of the ligand sites for Cr(III). This was correlated with sample humification, as confirmed by EPR and (13)C NMR analyses. Exchange efficiency was in the order Cu > Ni > Cr, and the process could be readily described by first order kinetics, with average rate constants of 0.35-0.37 h(-1). Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. First-order exchange coefficient coupling for simulating surface water-groundwater interactions: Parameter sensitivity and consistency with a physics-based approach

    Science.gov (United States)

    Ebel, B.A.; Mirus, B.B.; Heppner, C.S.; VanderKwaak, J.E.; Loague, K.

    2009-01-01

    Distributed hydrologic models capable of simulating fully-coupled surface water and groundwater flow are increasingly used to examine problems in the hydrologic sciences. Several techniques are currently available to couple the surface and subsurface; the two most frequently employed approaches are first-order exchange coefficients (a.k.a., the surface conductance method) and enforced continuity of pressure and flux at the surface-subsurface boundary condition. The effort reported here examines the parameter sensitivity of simulated hydrologic response for the first-order exchange coefficients at a well-characterized field site using the fully coupled Integrated Hydrology Model (InHM). This investigation demonstrates that the first-order exchange coefficients can be selected such that the simulated hydrologic response is insensitive to the parameter choice, while simulation time is considerably reduced. Alternatively, the ability to choose a first-order exchange coefficient that intentionally decouples the surface and subsurface facilitates concept-development simulations to examine real-world situations where the surface-subsurface exchange is impaired. While the parameters comprising the first-order exchange coefficient cannot be directly estimated or measured, the insensitivity of the simulated flow system to these parameters (when chosen appropriately) combined with the ability to mimic actual physical processes suggests that the first-order exchange coefficient approach can be consistent with a physics-based framework. Copyright ?? 2009 John Wiley & Sons, Ltd.

  13. The efficiency of macroporous polystyrene ion-exchange resins in natural organic matter removal from surface water

    Directory of Open Access Journals (Sweden)

    Urbanowska Agnieszka

    2017-01-01

    Full Text Available Natural water sources used for water treatment contains various organic and inorganic compounds. Surface waters are commonly contaminated with natural organic matter (NOM. NOM removal from water is important e.g. due to lowering the risk of disinfection by-product formation during chlorination. Ion exchange with the use of synthetic ion-exchange resins is an alternative process to typical NOM removal approach (e.g. coagulation, adsorption or oxidation as most NOM compounds have anionic character. Moreover, neutral fraction could be removed from water due to its adsorption on resin surface. In this study, applicability of two macroporous, polystyrene ion exchange resins (BD400FD and A100 in NOM removal from water was assessed including comparison of treatment efficiency in various process set-ups and conditions. Moreover, resin regeneration effectivity was determined. Obtained results shown that examined resins could be applied in NOM removal and it should be noticed that column set-up yielded better results (contrary to batch set-up. Among the examined resins A100 one possessed better properties. It was determined that increase of solution pH resulted in a slight decrease in treatment efficiency while higher temperature improved it. It was also observed that regeneration efficiency was comparable in both tested methods but batch set-up required less reagents.

  14. Potential Impact of Rainfall on the Air-Surface Exchange of Total Gaseous Mercury from Two Common Urban Ground Surfaces

    Science.gov (United States)

    The impact of rainfall on total gaseous mercury (TGM) flux from pavement and street dirt surfaces was investigated in an effort to determine the influence of wet weather events on mercury transport in urban watersheds. Street dirt and pavement are common urban ground surfaces tha...

  15. Effects of fin pitch and array of the frost layer growth on extended surface of a heat exchanger

    International Nuclear Information System (INIS)

    Yang, Dong Keun; Lee, Kwan Soo

    2003-01-01

    This paper presents the effects of the fin array and pitch on the frost layer growth of a heat exchanger. The numerical results are compared with experimental data of a cold plate to validate the present model, and agree well with experimental data within a maximum error of 8%. The characteristics of the frost formation on staggered fin array are somewhat different from those of in-line array. For fin pitch below 10 mm, the frost layer growth of second fin in the staggered array is affected by that of first fin. The heat transfer of single fin deteriorate with decreasing fin pitch regardless of fin array, however, the thermal performance of a heat exchanger, considering increase of heat surface area, becomes better

  16. Kinetics and thermodynamics of interaction between sulfonamide antibiotics and humic acids: Surface plasmon resonance and isothermal titration microcalorimetry analysis

    International Nuclear Information System (INIS)

    Xu, Juan; Yu, Han-Qing; Sheng, Guo-Ping

    2016-01-01

    Highlights: • HA would significantly affect the migration and transformation of SMZ. • Kinetics and thermodynamics of HA–SMZ interactions were studied using SPR and ITC. • The interaction is enhanced by increasing ionic strength and decreasing temperature. • Hydrogen bond and electrostatic interaction play important roles in the process. - Abstract: The presence of sulfonamide antibiotics in the environments has been recognized as a crucial issue. Their migration and transformation in the environment is determined by natural organic matters that widely exist in natural water and soil. In this study, the kinetics and thermodynamics of interactions between humic acids (HA) and sulfamethazine (SMZ) were investigated by employing surface plasmon resonance (SPR) combined with isothermal titration microcalorimetry (ITC) technologies. Results show that SMZ could be effectively bound with HA. The binding strength could be enhanced by increasing ionic strength and decreasing temperature. High pH was not favorable for the interaction. Hydrogen bond and electrostatic interaction may play important roles in driving the binding process, with auxiliary contribution from hydrophobic interaction. The results implied that HA existed in the environment may have a significant influence on the migration and transformation of organic pollutants through the binding process.

  17. First experimental results on the kinetic processes in a surface-wave-sustained argon discharge at atmospheric pressure

    International Nuclear Information System (INIS)

    Calzada, M.D.; Gamero, A.; Sola, A.

    1995-01-01

    This communication presents an advance of the results of an experimental study of the kinetic processes in a surface-wave-sustained argon discharge at atmospheric pressure. We utilize the study developed by Fujimoto on the population and depopulation processes of the excited levels of atoms and ions. This theory has been applied by S. Daviaud and A. Hirabayashi to explain the kinetic processes in helium plasma at low pressure. Fujimoto has studied the ionization and recombination mechanisms of the plasma under various conditions and its relation to the population density distributions. This study establishes, for an hydrogenic ion with a core charge z, different zones in the atomic system (level map). Each zone is characterized by the dominant mechanisms of the population and depopulation of their excited levels, A level is characterized for the effective principal quantum number p, where p = z (E H /|E p |) 1/2 , E H is the hydrogen ionization energy and |E p | is the energy required to ionize the atom from the level considered. The population of each level p can be expressed in terms of the parameter b(p) defined as n(p)/n SB (p), n(p) and n SB (p) being the actual population and the Saha-Boltzmann equilibrium population of the level, respectively. Figure I shows the population and depopulation processes of a level p, which are both collisional and radiative that are characterized by their respective coefficients

  18. Kinetics and thermodynamics of interaction between sulfonamide antibiotics and humic acids: Surface plasmon resonance and isothermal titration microcalorimetry analysis

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Juan; Yu, Han-Qing; Sheng, Guo-Ping, E-mail: gpsheng@ustc.edu.cn

    2016-01-25

    Highlights: • HA would significantly affect the migration and transformation of SMZ. • Kinetics and thermodynamics of HA–SMZ interactions were studied using SPR and ITC. • The interaction is enhanced by increasing ionic strength and decreasing temperature. • Hydrogen bond and electrostatic interaction play important roles in the process. - Abstract: The presence of sulfonamide antibiotics in the environments has been recognized as a crucial issue. Their migration and transformation in the environment is determined by natural organic matters that widely exist in natural water and soil. In this study, the kinetics and thermodynamics of interactions between humic acids (HA) and sulfamethazine (SMZ) were investigated by employing surface plasmon resonance (SPR) combined with isothermal titration microcalorimetry (ITC) technologies. Results show that SMZ could be effectively bound with HA. The binding strength could be enhanced by increasing ionic strength and decreasing temperature. High pH was not favorable for the interaction. Hydrogen bond and electrostatic interaction may play important roles in driving the binding process, with auxiliary contribution from hydrophobic interaction. The results implied that HA existed in the environment may have a significant influence on the migration and transformation of organic pollutants through the binding process.

  19. Air–snow exchange of nitrate: a modelling approach to investigate physicochemical processes in surface snow at Dome C, Antarctica

    Directory of Open Access Journals (Sweden)

    J. Bock

    2016-10-01

    Full Text Available Snowpack is a multiphase (photochemical reactor that strongly influences the air composition in polar and snow-covered regions. Snowpack plays a special role in the nitrogen cycle, as it has been shown that nitrate undergoes numerous recycling stages (including photolysis in the snow before being permanently buried in the ice. However, the current understanding of these physicochemical processes remains very poor. Several modelling studies have attempted to reproduce (photochemical reactions inside snow grains, but these have relied on strong assumptions to characterise snow reactive properties, which are not well defined. Air–snow exchange processes such as adsorption, solid-state diffusion, or co-condensation also affect snow chemical composition. Here, we present a physically based model of these processes for nitrate. Using as input a 1-year-long time series of atmospheric nitrate concentration measured at Dome C, Antarctica, our model reproduces with good agreement the nitrate measurements in the surface snow. By investigating the relative importance of the main exchange processes, this study shows that, on the one hand, the combination of bulk diffusion and co-condensation allows a good reproduction of the measurements (correlation coefficient r = 0.95, with a correct amplitude and timing of summer peak concentration of nitrate in snow. During winter, nitrate concentration in surface snow is mainly driven by thermodynamic equilibrium, whilst the peak observed in summer is explained by the kinetic process of co-condensation. On the other hand, the adsorption of nitric acid on the surface of the snow grains, constrained by an already existing parameterisation for the isotherm, fails to fit the observed variations. During winter and spring, the modelled concentration of adsorbed nitrate is respectively 2.5 and 8.3-fold higher than the measured one. A strong diurnal variation driven by the temperature cycle and a peak occurring in early

  20. Bacterial biogeography influenced by shelf-basin exchange in the Arctic surface sediment at the Chukchi Borderland.

    Science.gov (United States)

    Han, Dukki; Nam, Seung-Il; Ha, Ho Kyung; Kim, Hyoungjun; Sadowsky, Michael J; Lee, Yoo Kyung; Hur, Hor-Gil

    2016-02-01

    It has been known that continental shelves around the Arctic Ocean play a major role in the ventilation of the deep basins as a consequence of shelf-basin exchange. In the present study, we found that bacterial assemblage of the surface sediment was different from that of seawater while seawater harboured local bacterial assemblages in response to the Arctic hydrography. This finding suggests that the Arctic seafloor sediments may have distinctive bacterial biogeography. Moreover, the distribution of bacterial assemblages and physicochemical properties in surface sediments changed gradually from the Arctic continental shelf to deep-sea basin. Based on the results, bacterial biogeography in the Arctic seafloor sediments may be influenced by winnowing and re-deposition of surface sediments through the sediment gravity flow. The present study offers a deeper understanding of shelf convection and its role for the construction of bacterial assemblages in the Arctic Ocean. © 2015 Society for Applied Microbiology and John Wiley & Sons Ltd.

  1. An experimental study of the surface chemistry and evaporation kinetics of liquid sodium

    International Nuclear Information System (INIS)

    Becker, C.H.

    1983-01-01

    The evaporation rate and internal energy distribution of Na 2 evaporating from clean liquid Na and liquid Na exposed separately to O 2 and benzene were investigated by laser spectroscopy. The evaporating Na 2 was always found to be in thermal equilibrium with the surface. Oxygen increased the evaporation rate while benzene diminished it. A 3 keV Ar + beam was used to examine the surface by monitoring secondary ion emission. Ion emission from clean and oxygen exposed Na was extremely low; only limits could be established. Ion emission from sodium exposed to benzene could be observed only at lowered temperatures. The secondary ion emission, as well as visual observations of Na( 2 P-> 2 S) emission, are found to correspond to the evaporation rate behavior indicating that the Na surface remains very metal rich even while reacting with impinging oxygen at high (10 monolayers/s) rates. (orig.)

  2. Modifications of the hydriding kinetics of a metallic surface, using ion implantation

    International Nuclear Information System (INIS)

    Crusset, D.

    1992-10-01

    Uranium reacts with hydrogen to form an hydride: this reaction leads to the total destruction of the material. To modify the reactivity of an uranium surface towards hydrogen, ion implantation was selected, among surface treatments techniques. Four elements (carbon, nitrogen, oxygen, sulfur) were implanted to different doses. The results show a modification of the hydriding mechanism and a significant increase in the reaction induction times, notably at high implantation doses. Several techniques (SIMS, X-rays phases analysis and residual stresses determination) were used to characterize the samples and understand the different mechanisms involved

  3. Thermodynamics, kinetics, and catalytic effect of dehydrogenation from MgH2 stepped surfaces and nanocluster: a DFT study

    Science.gov (United States)

    Reich, Jason; Wang, Linlin; Johnson, Duane

    2013-03-01

    We detail the results of a Density Functional Theory (DFT) based study of hydrogen desorption, including thermodynamics and kinetics with(out) catalytic dopants, on stepped (110) rutile and nanocluster MgH2. We investigate competing configurations (optimal surface and nanoparticle configurations) using simulated annealing with additional converged results at 0 K, necessary for finding the low-energy, doped MgH2 nanostructures. Thermodynamics of hydrogen desorption from unique dopant sites will be shown, as well as activation energies using the Nudged Elastic Band algorithm. To compare to experiment, both stepped structures and nanoclusters are required to understanding and predict the effects of ball milling. We demonstrate how these model systems relate to the intermediary sized structures typically seen in ball milling experiments.

  4. Self-learning kinetic Monte Carlo simulations of self-diffusion of small Ag islands on the Ag(111) surface

    International Nuclear Information System (INIS)

    Shah, Syed Islamuddin; Nandipati, Giridhar; Rahman, Talat S; Karim, Altaf

    2016-01-01

    We studied self-diffusion of small two-dimensional Ag islands, containing up to ten atoms, on the Ag(111) surface using self-learning kinetic Monte Carlo (SLKMC) simulations. Activation barriers are calculated using the semi-empirical embedded atom method (EAM) potential. We find that two- to seven-atom islands primarily diffuse via concerted translation processes with small contributions from multi-atom and single-atom processes, while eight- to ten-atom islands diffuse via single-atom processes, especially edge diffusion, corner rounding and kink detachment, along with a minimal contribution from concerted processes. For each island size, we give a detailed description of the important processes, and their activation barriers, responsible for its diffusion. (paper)

  5. Molecular projectile effects for kinetic electron emission from carbon- and metal-surfaces bombarded by slow hydrogen ions

    International Nuclear Information System (INIS)

    Cernusca, S.; Winter, H.P.; Aumayr, F.; Diez Muino, R.; Juaristi, J.I.

    2003-01-01

    Total yields for kinetic electron emission (KE) have been determined for impact of hydrogen monomer-, dimer- and trimer-ions (impact energy <10 keV) on atomically clean surfaces of carbon-fiber inforced graphite used as first-wall armour in magnetic fusion devices. The data are compared with KE yields for impact of same projectile ions on atomically clean highly oriented pyrolytic graphite and polycrystalline gold. We discuss KE yields for the different targets if bombarded by equally fast molecular and atomic ions in view to 'projectile molecular effects' (different yields per proton for equally fast atomic and molecular ions), which are expected from calculated electronic projectile energy losses in these target materials

  6. Molecular projectile effects for kinetic electron emission from carbon- and metal-surfaces bombarded by slow hydrogen ions

    CERN Document Server

    Cernusca, S; Aumayr, F; Diez-Muino, R; Juaristi, J I

    2003-01-01

    Total yields for kinetic electron emission (KE) have been determined for impact of hydrogen monomer-, dimer- and trimer-ions (impact energy <10 keV) on atomically clean surfaces of carbon-fiber inforced graphite used as first-wall armour in magnetic fusion devices. The data are compared with KE yields for impact of same projectile ions on atomically clean highly oriented pyrolytic graphite and polycrystalline gold. We discuss KE yields for the different targets if bombarded by equally fast molecular and atomic ions in view to 'projectile molecular effects' (different yields per proton for equally fast atomic and molecular ions), which are expected from calculated electronic projectile energy losses in these target materials.

  7. Self-consistent nonlocal feedback theory for electrocatalytic swimmers with heterogeneous surface chemical kinetics

    Science.gov (United States)

    Nourhani, Amir; Crespi, Vincent H.; Lammert, Paul E.

    2015-06-01

    We present a self-consistent nonlocal feedback theory for the phoretic propulsion mechanisms of electrocatalytic micromotors or nanomotors. These swimmers, such as bimetallic platinum and gold rods catalyzing decomposition of hydrogen peroxide in aqueous solution, have received considerable theoretical attention. In contrast, the heterogeneous electrochemical processes with nonlocal feedback that are the actual "engines" of such motors are relatively neglected. We present a flexible approach to these processes using bias potential as a control parameter field and a locally-open-circuit reference state, carried through in detail for a spherical motor. While the phenomenological flavor makes meaningful contact with experiment easier, required inputs can also conceivably come from, e.g., Frumkin-Butler-Volmer kinetics. Previously obtained results are recovered in the weak-heterogeneity limit and improved small-basis approximations tailored to structural heterogeneity are presented. Under the assumption of weak inhomogeneity, a scaling form is deduced for motor speed as a function of fuel concentration and swimmer size. We argue that this form should be robust and demonstrate a good fit to experimental data.

  8. Adsorption kinetics of WS2 quantum dots onto a polycrystalline gold surface.

    Science.gov (United States)

    Ozhukil Valappil, Manila; Roopesh, Mekkat; Alwarappan, Subbiah; Pillai, Vijayamohanan K

    2018-04-18

    In this work, we report the adsorption kinetics of electrochemically synthesized WS2 quantum dots (ca. 3 nm) onto a polycrystalline gold electrode. Langmuir adsorption isotherm approach was employed to explore the temperature and adsorbate concentration dependence of experimentally calculated equilibrium constant of adsorption (Keq) and free energy for adsorption (ΔGads). Subsequently, we extract other thermodynamic parameters such as adsorption rate constant (Kads), desorption rate constant (Kd), the enthalpy of adsorption (ΔHads) and the entropy of adsorption (ΔSads). Our findings indicate that ΔGads is temperature dependent and ca. -1.74 kcal mol-1, ΔHads = -10.697 kcal mol-1 and ΔSads = -30 cal/(mol.K). These investigations on the contribution of the enthalpic and entropic forces to the total free energy of this system underscore the role of entropic forces on the stability of the WS2 QDs monolayer and provide new thermodynamic insights into other TMDQDs monolayers as well.

  9. Equilibrium and kinetics of Sin Nombre hantavirus binding at DAF/CD55 functionalized bead surfaces.

    Science.gov (United States)

    Buranda, Tione; Swanson, Scarlett; Bondu, Virginie; Schaefer, Leah; Maclean, James; Mo, Zhenzhen; Wycoff, Keith; Belle, Archana; Hjelle, Brian

    2014-03-10

    Decay accelerating factor (DAF/CD55) is targeted by many pathogens for cell entry. It has been implicated as a co-receptor for hantaviruses. To examine the binding of hantaviruses to DAF, we describe the use of Protein G beads for binding human IgG Fc domain-functionalized DAF ((DAF)₂-Fc). When mixed with Protein G beads the resulting DAF beads can be used as a generalizable platform for measuring kinetic and equilibrium binding constants of DAF binding targets. The hantavirus interaction has high affinity (24-30 nM; k(on) ~ 10⁵ M⁻¹ s⁻¹, k(off) ~ 0.0045 s⁻¹). The bivalent (DAF)₂-Fc/SNV data agree with hantavirus binding to DAF expressed on Tanoue B cells (K(d) = 14.0 nM). Monovalent affinity interaction between SNV and recombinant DAF of 58.0 nM is determined from competition binding. This study serves a dual purpose of presenting a convenient and quantitative approach of measuring binding affinities between DAF and the many cognate viral and bacterial ligands and providing new data on the binding constant of DAF and Sin Nombre hantavirus. Knowledge of the equilibrium binding constant allows for the determination of the relative fractions of bound and free virus particles in cell entry assays. This is important for drug discovery assays for cell entry inhibitors.

  10. Mass and heat transfer between evaporation and condensation surfaces: Atomistic simulation and solution of Boltzmann kinetic equation.

    Science.gov (United States)

    Zhakhovsky, Vasily V; Kryukov, Alexei P; Levashov, Vladimir Yu; Shishkova, Irina N; Anisimov, Sergey I

    2018-04-16

    Boundary conditions required for numerical solution of the Boltzmann kinetic equation (BKE) for mass/heat transfer between evaporation and condensation surfaces are analyzed by comparison of BKE results with molecular dynamics (MD) simulations. Lennard-Jones potential with parameters corresponding to solid argon is used to simulate evaporation from the hot side, nonequilibrium vapor flow with a Knudsen number of about 0.02, and condensation on the cold side of the condensed phase. The equilibrium density of vapor obtained in MD simulation of phase coexistence is used in BKE calculations for consistency of BKE results with MD data. The collision cross-section is also adjusted to provide a thermal flux in vapor identical to that in MD. Our MD simulations of evaporation toward a nonreflective absorbing boundary show that the velocity distribution function (VDF) of evaporated atoms has the nearly semi-Maxwellian shape because the binding energy of atoms evaporated from the interphase layer between bulk phase and vapor is much smaller than the cohesive energy in the condensed phase. Indeed, the calculated temperature and density profiles within the interphase layer indicate that the averaged kinetic energy of atoms remains near-constant with decreasing density almost until the interphase edge. Using consistent BKE and MD methods, the profiles of gas density, mass velocity, and temperatures together with VDFs in a gap of many mean free paths between the evaporation and condensation surfaces are obtained and compared. We demonstrate that the best fit of BKE results with MD simulations can be achieved with the evaporation and condensation coefficients both close to unity.

  11. COMBINED THEORETICAL AND EXPERIMENTAL INVESTIGATION OF MECHANISMS AND KINETICS OF VAPOR-PHASE MERCURY UPTAKE BY CARBONACEOUS SURFACES; ANNUAL

    International Nuclear Information System (INIS)

    Radisav D. Vidic; Eric V. Borguet; Karl J. Johnson

    2000-01-01

    The overall goal of this research program is to gain fundamental understanding of the important chemistry and physics involved in mercury adsorption on carbonaceous surfaces. This knowledge will then be used to optimize adsorption processes and operating conditions to maximize the uptake of mercury within the required contact time. An additional long-term benefit of this research is the basic understanding of the Hg adsorption process, which may facilitate the design of new adsorbents for more efficient and cost-effective removal of Hg from a variety of effluent streams. Molecular modeling of the adsorption of Hg on carbonaceous surfaces will greatly increase the insight into the physics of the adsorption process and combined with in situ rate measurements of mercury adsorption and desorption (conventional and pulsed laser) on graphite using linear and nonlinear optical probes with real time optical resolution have the potential to provide fundamental insight into the process of mercury uptake by carbonaceous surfaces. Besides accurate assessment of key parameters influencing adsorption equilibrium, fundamental understanding of the kinetics of mercury adsorption, desorption, and diffusion will be developed in this study. These key physical and chemical processes postulated through molecular modeling efforts and verified by in situ measurements will be utilized to select (or develop) promising sorbents for mercury control, which will be tested under dynamic conditions using simulated flue gas

  12. Kinetic and Surface Study of Single-Walled Aluminosilicate Nanotubes and Their Precursors

    Directory of Open Access Journals (Sweden)

    Mauricio Molina

    2013-03-01

    Full Text Available The structural and surface changes undergone by the different precursors that are produced during the synthesis of imogolite are reported. The surface changes that occur during the synthesis of imogolite were determined by electrophoretic migration (EM measurements, which enabled the identification of the time at which the critical precursor of the nanoparticles was generated. A critical parameter for understanding the evolution of these precursors is the isoelectric point (IEP, of which variation revealed that the precursors modify the number of active ≡Al-OH and ≡Si-OH sites during the formation of imogolite. We also found that the IEP is displaced to a higher pH level as a consequence of the surface differentiation that occurs during the synthesis. At the same time, we established that the pH of the reaction (pHrx decreases with the evolution and condensation of the precursors during aging. Integration of all of the obtained results related to the structural and surface properties allows an overall understanding of the different processes that occur and the products that are formed during the synthesis of imogolite.

  13. Kinetic Electron Emission from Higly Oriented Pyrolytic Graphite Surfaces Induced by Singly Charged Ions

    Czech Academy of Sciences Publication Activity Database

    Cernusca, S.; Diem, A.; Winter, H. P.; Aumayr, F.; Lörinčík, Jan; Šroubek, Zdeněk

    2002-01-01

    Roč. 193, - (2002), s. 616-620 ISSN 0168-583X Institutional research plan: CEZ:AV0Z4040901 Keywords : clean metal-surface * slow * polycrystalline gold Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.158, year: 2002

  14. NOx Direct Decomposition: Potentially Enhanced Thermodynamics and Kinetics on Chemically Modified Ferroelectric Surfaces

    Science.gov (United States)

    Kakekhani, Arvin; Ismail-Beigi, Sohrab

    2014-03-01

    NOx are regulated pollutants produced during automotive combustion. As part of an effort to design catalysts for NOx decomposition that operate in oxygen rich environment and permit greater fuel efficiency, we study chemistry of NOx on (001) ferroelectric surfaces. Changing the polarization at such surfaces modifies electronic properties and leads to switchable surface chemistry. Using first principles theory, our previous work has shown that addition of catalytic RuO2 monolayer on ferroelectric PbTiO3 surface makes direct decomposition of NO thermodynamically favorable for one polarization. Furthermore, the usual problem of blockage of catalytic sites by strong oxygen binding is overcome by flipping polarization that helps desorb the oxygen. We describe a thermodynamic cycle for direct NO decomposition followed by desorption of N2 and O2. We provide energy barriers and transition states for key steps of the cycle as well as describing their dependence on polarization direction. We end by pointing out how a switchable order parameter of substrate,in this case ferroelectric polarization, allows us to break away from some standard compromises for catalyst design(e.g. the Sabatier principle). This enlarges the set of potentially catalytic metals. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

  15. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

    NARCIS (Netherlands)

    Van Der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; Van Der Velde, Y.

    2014-01-01

    The retention of phosphorus in surface waters through co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from

  16. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water.

    NARCIS (Netherlands)

    Grift, van der B.; Rozemeijer, J.C.; Griffioen, J.; Velde, van der Y.

    2014-01-01

    The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and 5 P immobilization along the flow-path

  17. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

    NARCIS (Netherlands)

    van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

    2014-01-01

    The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from

  18. Studying temporal and spatial variations of groundwater-surface water exchange flux for the Slootbeek (Belgium) using the LPML method

    Science.gov (United States)

    Anibas, Christian; Schneideweind, Uwe; Vandersteen, Gerd; Huysmans, Marijke; Batelaan, Okke

    2015-04-01

    Knowledge of groundwater-surface water interaction is important for the assessment of water resources and for the investigation of fate and transport of contaminants and nutrients. In streams and rivers exchange fluxes of water are sensitive to local and regional factors such as riverbed hydraulic conductivity and hydraulic gradients. Field monitoring in time and space is therefore indispensible for assessing the variability of groundwater-surface water interaction. Not only the complexity of the examined processes demand novel data processing and characterization tools, the amount of acquired data also urges for new modeling tools. These tools should be easily applicable, allow for a fast computation, and utilize the maximum amount of available data for detailed analysis, including uncertainties. Such analytical tools should be combined with modern field equipment, data processing tools, geographical information systems and geostatistics for best results. A simple and cost effective methodology to estimate groundwater-surface water interaction is the use of temperature as an environmental tracer (ANDERSON, 2005). LPML (VANDERSTEEN et al., 2014) is one of the most advanced analytical 1D coupled water flow and heat transport models, combining a local polynomial method with a maximum likelihood estimator. It is flexible, fast and able to create time series of exchange fluxes, as well as model quality and parameter uncertainty. LPML determines frequency response functions from measured temperature time series and an analytical model, and applies a non-linear optimization technique. With this tool the variability of groundwater-surface water interaction of the Belgian stream Slootbeek was assessed. Multilevel temperature sensors were placed in seven locations to obtain temperature-time series. Located at the streambed top and at six depths below, several months worth of data was collected and analyzed. Results identified a high spatial and temporal variability of

  19. Kinetics of the melting front movement in process of centrifugal induction surfacing of powder material with nanoscale modificaters

    Science.gov (United States)

    Sasnouski, I.; Kurylionak, A.

    2018-03-01

    For solving the problem of improving the powder coatings modified by nanostructure components obtained by induction surfacing method tribological characteristics it is necessary to study the kinetics of the powdered layer melting and define the minimum time of melting. For powdered layer predetermined temperature maintenance at sintering mode stage it is required to determine the temperature difference through blank thickness of the for one hundred-day of the define the warm-up swing on of the stocking up by solving the thermal conductivity stationary problem for quill (hollow) cylinder with internal heat source. Herewith, since in practice thickness of the cylinder wall is much less then its diameter and the temperature difference is comparatively small, the thermal conductivity dependence upon the temperature can be treated as negligible. As it was shown by our previous studies, in the induction heating process under powdered material centrifugal surfacing (i.e. before achieving the melting temperature) the temperature distribution in powdered layer thickness may be considered even. Hereinafter, considering the blank part induction heating process quasi-stationarity under Fo big values, it is possible to consider its internal surface heating as developing with constant velocity. As a result of development the melting front movement mathematical model in a powdered material with nanostructure modifiers the minimum surfacing time is defined. It allows to minimize negative impact of thermal influence on formation of applied coating structure, to raise productivity of the process, to lower power inputs and to ensure saving of nonferrous and high alloys by reducing the allowance for machining. The difference of developed mathematical model of melting front movement from previously known is that the surface temperature from which the heat transfer occures is a variable and varies with a time after the linear law.

  20. Fabrication of a superhydrophobic surface with fungus-cleaning properties on brazed aluminum for industrial application in heat exchangers

    Science.gov (United States)

    Lee, Jeong-Won; Hwang, Woonbong

    2018-06-01

    Extensive research has been carried out concerning the application of superhydrophobic coating in heat exchangers, but little is known about the application of this technique to brazed aluminum heat exchangers (BAHEs). In this work, we describe a new superhydrophobic coating method, which is suitable for BAHE use on an industrial scale. We first render the BAHE superhydrophobic by fabricating micro/nanostructures using solution dipping followed by fluorination. After the complete removal of the silicon residue, we verify using surface analysis that the BAHE surface is perfectly superhydrophobic. We also studied the fungus-cleaning properties of the superhydrophobic surface by growing fungus for 4 weeks in a moist environment on BAHE fins with and without superhydrophobic coating. We observed that, whereas the fungus grown on the untreated fins is extremely difficult to remove, the fungus on the fins with the superhydrophobic coating can be removed easily with only a modest amount of water. We also found that the coated BAHE fins exhibit excellent resistance to moisture. The superhydrophobic coating method that we propose is therefore expected to have a major impact in the heating, ventilating and air conditioning industry market.

  1. Atmospheric and Surface-Condition Effects on CO2 Exchange in the Liaohe Delta Wetland, China

    Directory of Open Access Journals (Sweden)

    Qingyu Jia

    2017-10-01

    Full Text Available The eddy covariance method was used to study the CO2 budget of the Liaohe Delta reed wetland in northern China during 2012–2015. The changes in environmental factors (including meteorology, vegetation, hydrology, and soil were analyzed simultaneously. The change in the trend of the CO2 concentration in the reed wetland was similar to global changes over the four years. The average annual CO2 accumulation was 2.037 kg·CO2·m−2, ranging from 1.472 to 2.297 kg·CO2·m−2. The seasonal characteristics of the CO2 exchange included high CO2 absorption in June and July, and high emissions in April and from September to October, with the highest emissions in July 2015. The average temperatures from 2013 to 2015 were higher than the 50-year average, largely due to increased temperatures in winter. Precipitation was below the 50-year average, mainly because of low precipitation in summer. The average wind speed was less than the 50-year average, and sunshine duration decreased each year. The CO2 exchange and environmental factors had a degree of correlation or consistency. The contribution of meteorology, vegetation, hydrology, and soil to the CO2 budget was analyzed using the partial least squares method. Water and soil temperature had a greater effect on the CO2 exchange variability. The regression equation of the CO2 budget was calculated using the significant contributing factors, including temperature, precipitation, relative humidity, water-table level, salinity, and biomass. The model fit explained more than 70% of the CO2 exchange, and the simulation results were robust.

  2. Surface polyPEGylation of Eu3+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    Science.gov (United States)

    Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-03-01

    The Eu3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.

  3. Surface polyPEGylation of Eu{sup 3+} doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Guangjian; Liu, Meiying [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Heng, Chunning [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (China); Huang, Qiang; Mao, Liucheng; Huang, Hongye [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Hui, Junfeng [Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and The Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China)

    2017-03-31

    Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu{sup 3+} doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu{sup 3+} doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface

  4. Surface polyPEGylation of Eu"3"+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-01-01

    Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu"3"+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu"3"+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated

  5. A continuous-flow denuder for the measurement of ambient concentrations and surface-exchange fluxes of ammonia

    Science.gov (United States)

    Wyers, G. P.; Otjes, R. P.; Slanina, J.

    A new diffusion denuder is described for the continuous measurement of atmospheric ammonia. Ammonia is collected in an absorption solution in a rotating denuder, separated from interfering compounds by diffusion through a semi-permeable membrane and detected by conductometry. The method is free from interferences by other atmospheric gases, with the exception of volatile amines. The detection limit is 6 ng m -3 for a 30-min integration time. This compact instrument is fully automated and suited for routine deployment in field studies. The precision is sufficiently high for micrometeorological studies of air-surface exchange of ammonia.

  6. Numerical analysis of one-dimensional temperature data for groundwater/surface-water exchange with 1DTempPro

    Science.gov (United States)

    Voytek, E. B.; Drenkelfuss, A.; Day-Lewis, F. D.; Healy, R. W.; Lane, J. W.; Werkema, D. D.

    2012-12-01

    Temperature is a naturally occurring tracer, which can be exploited to infer the movement of water through the vadose and saturated zones, as well as the exchange of water between aquifers and surface-water bodies, such as estuaries, lakes, and streams. One-dimensional (1D) vertical temperature profiles commonly show thermal amplitude attenuation and increasing phase lag of diurnal or seasonal temperature variations with propagation into the subsurface. This behavior is described by the heat-transport equation (i.e., the convection-conduction-dispersion equation), which can be solved analytically in 1D under certain simplifying assumptions (e.g., sinusoidal or steady-state boundary conditions and homogeneous hydraulic and thermal properties). Analysis of 1D temperature profiles using analytical models provides estimates of vertical groundwater/surface-water exchange. The utility of these estimates can be diminished when the model assumptions are violated, as is common in field applications. Alternatively, analysis of 1D temperature profiles using numerical models allows for consideration of more complex and realistic boundary conditions. However, such analyses commonly require model calibration and the development of input files for finite-difference or finite-element codes. To address the calibration and input file requirements, a new computer program, 1DTempPro, is presented that facilitates numerical analysis of vertical 1D temperature profiles. 1DTempPro is a graphical user interface (GUI) to the USGS code VS2DH, which numerically solves the flow- and heat-transport equations. Pre- and post-processor features within 1DTempPro allow the user to calibrate VS2DH models to estimate groundwater/surface-water exchange and hydraulic conductivity in cases where hydraulic head is known. This approach improves groundwater/ surface-water exchange-rate estimates for real-world data with complexities ill-suited for examination with analytical methods. Additionally, the code

  7. Kinetics and mechanism of heterogeneous oxidation of sulfur dioxide by ozone on surface of calcium carbonate

    Directory of Open Access Journals (Sweden)

    L. Li

    2006-01-01

    Full Text Available Sulfate particles play a key role in the air quality and the global climate, but the heterogeneous formation mechanism of sulfates on surfaces of atmospheric particles is not well established. Carbonates, which act as a reactive component in mineral dust due to their special chemical properties, may contribute significantly to the sulfate formation by heterogeneous processes. This paper presents a study on the oxidation of SO2 by O3 on CaCO3 particles. Using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS, the formation of sulfite and sulfate on the surface was identified, and the roles of O3 and water in oxidation processes were determined. The results showed that in the presence of O3, SO2can be oxidized to sulfate on the surface of CaCO3 particles. The reaction is first order in SO2 and zero order in O3. The reactive uptake coefficient for SO2 [(0.6–9.8×1014 molecule cm-3] oxidation by O3 [(1.2–12×1014 molecule cm-3] was determined to be (1.4±0.3×10-7 using the BET area as the reactive area and (7.7±1.6×10-4 using the geometric area. A two-stage mechanism that involves adsorption of SO2 followed by O3 oxidation is proposed and the adsorption of SO2 on the CaCO3 surface is the rate-determining step. The proposed mechanism can well explain the experiment results. The atmospheric implications were explored based on a box model calculation. It was found that the heterogeneous reaction might be an important pathway for sulfate formation in the atmosphere.

  8. Kinetics of exchange reaction between neodymium(3) transcyclohexanediaminetetraacetate and europium(3)- and holmium(3) aquo-ions in the H/sub 2/O and D/sub 2/O solutions

    Energy Technology Data Exchange (ETDEWEB)

    Nikitenko, S.I.; Martynenko, L.I.; Pechurova, N.I.; Spitsyn, V.I. (Moskovskij Gosudarstvennyj Univ. (USSR))

    1983-10-01

    The exchange reaction between central ions in the NdD/sup -/Ln'/sup 3 +/ systems, where Ln'/sup 3 +/ is a substituting cation (Eu/sup 3 +/ and Ho/sup 3 +/, D/sup 4/=cyclohexanediaminetetraacetate) is studied and the electrophilic substitution mechanism is considered. To study the kinetic isotope effects, the reagents have been solved in heavy water containing 99.9% D/sub 2/O. The electrophilic substitution in the indicated systems proceeds through the dissociative mechanism catalyzed by protons and via the spontaneous dissociation mechanism. The exchange via the acid-catalyzed mechanism is limited by the intermediate protonated complex decay. The associative mechanism of the electrophilic exchange in the studied systems is not realized.

  9. Thermodynamics and kinetics of reduction and species conversion at a hydrophobic surface for mitochondrial cytochromes c and their cardiolipin adducts

    International Nuclear Information System (INIS)

    Ranieri, Antonio; Di Rocco, Giulia; Millo, Diego; Battistuzzi, Gianantonio; Bortolotti, Carlo A.; Lancellotti, Lidia; Borsari, Marco; Sola, Marco

    2015-01-01

    Highlights: • Cytochrome c and its adduct with cardiolipin can be immobilized on a hydrophobic SAM. • Adsorbed cytochrome c and its adduct undergo extensive unfolding and axial ligand substitution. • An equilibrium between a six-coordinated and a five-coordinated form is observed in both cases. • The reduced five-coordinated form is stabilized by cardiolipin binding. • Immobilized cytochrome c exchanges electrons more slowly upon cardiolipin binding. - Abstract: Cytochrome c (cytc) and its adduct with cardiolipin (CL) were immobilized on a hydrophobic SAM-coated electrode surface yielding a construct which mimics the environment experienced by the complex at the inner mitochondrial membrane where it plays a role in cell apoptosis. Under these conditions, both species undergo an equilibrium between a six-coordinated His/His-ligated and a five-coordinated His/- ligated forms stable in the oxidized and in the reduced state, respectively. The thermodynamics of the oxidation-state dependent species conversion were determined by temperature-dependent diffusionless voltammetry experiments. CL binding stabilizes the immobilized reduced His/- ligated form of cytc which was found previously to catalytically reduce dioxygen. Here, this adduct is also found to show pseudoperoxidase activity, catalysing reduction of hydrogen peroxide. These effects would impart CL with an additional role in the cytc-mediated peroxidation leading to programmed cell death. Moreover, immobilized cytc exchanges electrons more slowly upon CL binding possibly due to changes in solvent reorganization effects at the protein-SAM interface

  10. Realistic multisite lattice-gas modeling and KMC simulation of catalytic surface reactions: Kinetics and multiscale spatial behavior for CO-oxidation on metal (1 0 0) surfaces

    Science.gov (United States)

    Liu, Da-Jiang; Evans, James W.

    2013-12-01

    A realistic molecular-level description of catalytic reactions on single-crystal metal surfaces can be provided by stochastic multisite lattice-gas (msLG) models. This approach has general applicability, although in this report, we will focus on the example of CO-oxidation on the unreconstructed fcc metal (1 0 0) or M(1 0 0) surfaces of common catalyst metals M = Pd, Rh, Pt and Ir (i.e., avoiding regimes where Pt and Ir reconstruct). These models can capture the thermodynamics and kinetics of adsorbed layers for the individual reactants species, such as CO/M(1 0 0) and O/M(1 0 0), as well as the interaction and reaction between different reactant species in mixed adlayers, such as (CO + O)/M(1 0 0). The msLG models allow population of any of hollow, bridge, and top sites. This enables a more flexible and realistic description of adsorption and adlayer ordering, as well as of reaction configurations and configuration-dependent barriers. Adspecies adsorption and interaction energies, as well as barriers for various processes, constitute key model input. The choice of these energies is guided by experimental observations, as well as by extensive Density Functional Theory analysis. Model behavior is assessed via Kinetic Monte Carlo (KMC) simulation. We also address the simulation challenges and theoretical ramifications associated with very rapid diffusion and local equilibration of reactant adspecies such as CO. These msLG models are applied to describe adsorption, ordering, and temperature programmed desorption (TPD) for individual CO/M(1 0 0) and O/M(1 0 0) reactant adlayers. In addition, they are also applied to predict mixed (CO + O)/M(1 0 0) adlayer structure on the nanoscale, the complete bifurcation diagram for reactive steady-states under continuous flow conditions, temperature programmed reaction (TPR) spectra, and titration reactions for the CO-oxidation reaction. Extensive and reasonably successful comparison of model predictions is made with experimental

  11. Simulation of surface crack initiation induced by slip localization and point defects kinetics

    International Nuclear Information System (INIS)

    Sauzay, Maxime; Liu, Jia; Rachdi, Fatima

    2014-01-01

    Crack initiation along surface persistent slip bands (PSBs) has been widely observed and modelled. Nevertheless, from our knowledge, no physically-based fracture modelling has been proposed and validated with respect to the numerous recent experimental data showing the strong relationship between extrusion and microcrack initiation. The whole FE modelling accounts for: - localized plastic slip in PSBs; - production and annihilation of vacancies induced by cyclic slip. If temperature is high enough, point defects may diffuse in the surrounding matrix due to large concentration gradients, allowing continuous extrusion growth in agreement with Polak's model. At each cycle, the additional atoms diffusing from the matrix are taken into account by imposing an incremental free dilatation; - brittle fracture at the interfaces between PSBs and their surrounding matrix which is simulated using cohesive zone modelling. Any inverse fitting of parameter is avoided. Only experimental single crystal data are used such as hysteresis loops and resistivity values. Two fracture parameters are required: the {111} surface energy which depends on environment and the cleavage stress which is predicted by the universal binding energy relationship. The predicted extrusion growth curves agree rather well with the experimental data published for copper and the 316L steel. A linear dependence with respect to PSB length, thickness and slip plane angle is predicted in agreement with recent AFM measurement results. Crack initiation simulations predict fairly well the effects of PSB length and environment for copper single and poly-crystals. (authors)

  12. Direct measurement of the adsorption kinetics of 2-Mercaptobenzothiazole on a microcrystalline copper surface

    Energy Technology Data Exchange (ETDEWEB)

    Ramirez-Cano, J. A.; Veleva, L.

    2016-05-01

    The adsorption on copper of 2-Mercaptobenzothiazole (2-MBT), a heterocyclic compound member of the tiazole family, has been investigated at different concentrations (1x10{sup -}1 to 1x10{sup -}6 M) in water, employing the Electrochemical Quartz Crystal Microbalance (EQCM). The frequency response over time was obtained for each concentration, showing a defined exponential behavior at higher concentrations (1x10{sup -}1, 1x10{sup -}2 and 1x10{sup -}3 M), which was filed to the Langmuir adsorption isotherm with a good correlation coefficients (R{sup 2}=0.91 to 0.98) Surface coverage (θ) was calculated and found to be in the order of 0.50 to 0.01 for 2-MBT high concentrations. The free energy of adsorption was ΔG{sub a}ds=-5.59 kJ mol{sup -}1, corresponding to physisorption process, probably of electrostatic nature of the interaction between 2-MBT and copper surface in aqueous solution. (Author)

  13. The surface oxidation kinetics of zirconium-niobium alloys and aα-Fe with prevailing cubical texture

    International Nuclear Information System (INIS)

    Mukhambetov, D.G.; Kargin, D.B.; Chalaya, O. V.; Berber, N.N.

    2002-01-01

    It is known, that the kinetics of oxidation of zirconium at formed heating is characterized by two consecutive stages. At the initial stage the thin protecting film will be derived. The relation of its depth from time h (t) is described predominantly by parabolic law. Some time later there can be a transition to the linear law of oxidation. The time moment divided these areas on the kinetic relation is called as a point of break. The film is formed at the second stage, has a developed grid of pores or cracks, can be flake away and be crumbled by losing its protective properties. At the oxidation of the surface shells of the heat generating elements and the technological channels of atomic boilers both stages are proceeded simultaneously. This phenomenon is called modular corrosion. Its consequences can be dangerous for the equipment. Its mechanism is not clear till now. Similar dependencies h(t), with the break point, beginning from which the thin film is transformed into the thick one were found by us at the oxidation α-Fe with prevailing cubical texture. The task of the work was to study the oxide film growth laws in order to clarify the mechanisms of transition of the thin film into the oxide layer on the α-Fe surface and Zr-Nb alloy modular corrosion emergence. Low-carbonate steel with contents 99.43 % of α-Fe was used as a model object of our research. In the texture of the steel surface planar direction [100] was prevalent. Its part accounted for about 40 %. The isothermal air oxidation was carried out in the interval of 450-500 deg. C . Phase composition of the film was determined with X-ray diffraction. The mathematical treatment of the dependencies h(t) obtained by experiment showed that the kinetics of the film growth can be conditionally divided into 4-stages. The initial stage is described by function logarithmic function, the other stages - by the power mode h n =A n ·t, namely, the second stage - is described by function close to cubical (n≅3

  14. Eddy covariance measurement of the spatial heterogeneity of surface energy exchanges over Heron Reef, Great Barrier Reef, Australia

    Science.gov (United States)

    MacKellar, M.; McGowan, H. A.; Phinn, S. R.

    2011-12-01

    Coral reefs cover 2.8 to 6.0 x 105 km2 of the Earth's surface and are warm, shallow regions that are believed to contribute enhanced sensible and latent heat to the atmosphere, relative to the surrounding ocean. To predict the impact of climate variability on coral reefs and their weather and climate including cloud, winds, rainfall patterns and cyclone genesis, accurate parameterisation of air-sea energy exchanges over coral reefs is essential. This is also important for the parameterisation and validation of regional to global scale forecast models to improve prediction of tropical and sub-tropical marine and coastal weather. Eddy covariance measurements of air-sea fluxes over coral reefs are rare due to the complexities of installing instrumentation over shallow, tidal water. Consequently, measurements of radiation and turbulent flux data for coral reefs have been captured remotely (satellite data) or via single measurement sites downwind of coral reefs (e.g. terrestrial or shipboard instrumentation). The resolution of such measurements and those that have been made at single locations on reefs may not capture the spatial heterogeneity of surface-atmosphere energy exchanges due to the different geomorphic and biological zones on coral reefs. Accordingly, the heterogeneity of coral reefs with regard to substrate, benthic communities and hydrodynamic processes are not considered in the characterization of the surface radiation energy flux transfers across the water-atmosphere interface. In this paper we present a unique dataset of concurrent in situ eddy covariance measurements made on instrumented pontoons of the surface energy balance over different geomorphic zones of a coral reef (shallow reef flat, shallow and deep lagoons). Significant differences in radiation transfers and air-sea turbulent flux exchanges over the reef were highlighted, with higher Bowen ratios over the shallow reef flat. Increasing wind speed was shown to increase flux divergence between

  15. Electrical resistivity dynamics beneath a fractured sedimentary bedrock riverbed in response to temperature and groundwater–surface water exchange

    Directory of Open Access Journals (Sweden)

    C. M. Steelman

    2017-06-01

    Full Text Available Bedrock rivers occur where surface water flows along an exposed rock surface. Fractured sedimentary bedrock can exhibit variable groundwater residence times, anisotropic flow paths, and heterogeneity, along with diffusive exchange between fractures and rock matrix. These properties of the rock will affect thermal transients in the riverbed and groundwater–surface water exchange. In this study, surface electrical methods were used as a non-invasive technique to assess the scale and temporal variability of riverbed temperature and groundwater–surface water interaction beneath a sedimentary bedrock riverbed. Conditions were monitored at a semi-daily to semi-weekly interval over a full annual period that included a seasonal freeze–thaw cycle. Surface electromagnetic induction (EMI and electrical resistivity tomography (ERT methods captured conditions beneath the riverbed along a pool–riffle sequence of the Eramosa River in Canada. Geophysical datasets were accompanied by continuous measurements of aqueous specific conductance, temperature, and river stage. Time-lapse vertical temperature trolling within a lined borehole adjacent to the river revealed active groundwater flow zones along fracture networks within the upper 10 m of rock. EMI measurements collected during cooler high-flow and warmer low-flow periods identified a spatiotemporal riverbed response that was largely dependent upon riverbed morphology and seasonal groundwater temperature. Time-lapse ERT profiles across the pool and riffle sequence identified seasonal transients within the upper 2 and 3 m of rock, respectively, with spatial variations controlled by riverbed morphology (pool versus riffle and dominant surficial rock properties (competent versus weathered rock rubble surface. While the pool and riffle both exhibited a dynamic resistivity through seasonal cooling and warming cycles, conditions beneath the pool were more variable, largely due to the formation of river

  16. Ge interactions on HfO2 surfaces and kinetically driven patterning of Ge nanocrystals on HfO2

    International Nuclear Information System (INIS)

    Stanley, Scott K.; Joshi, Sachin V.; Banerjee, Sanjay K.; Ekerdt, John G.

    2006-01-01

    Germanium interactions are studied on HfO 2 surfaces, which are prepared through physical vapor deposition (PVD) and by atomic layer deposition. X-ray photoelectron spectroscopy and temperature-programed desorption are used to follow the reactions of germanium on HfO 2 . Germanium chemical vapor deposition at 870 K on HfO 2 produces a GeO x adhesion layer, followed by growth of semiconducting Ge 0 . PVD of 0.7 ML Ge (accomplished by thermally cracking GeH 4 over a hot filament) also produces an initial GeO x layer, which is stable up to 800 K. PVD above 2.0 ML deposits semiconducting Ge 0 . Temperature programed desorption experiments of ∼1.0 ML Ge from HfO 2 at 400-1100 K show GeH 4 desorption below 600 K and GeO desorption above 850 K. These results are compared to Ge on SiO 2 where GeO desorption is seen at 550 K. Exploiting the different reactivity of Ge on HfO 2 and SiO 2 allows a kinetically driven patterning scheme for high-density Ge nanoparticle growth on HfO 2 surfaces that is demonstrated

  17. Experimental calibration and validation of sewer/surface flow exchange equations in steady and unsteady flow conditions

    Science.gov (United States)

    Rubinato, Matteo; Martins, Ricardo; Kesserwani, Georges; Leandro, Jorge; Djordjević, Slobodan; Shucksmith, James

    2017-09-01

    The linkage between sewer pipe flow and floodplain flow is recognised to induce an important source of uncertainty within two-dimensional (2D) urban flood models. This uncertainty is often attributed to the use of empirical hydraulic formulae (the one-dimensional (1D) weir and orifice steady flow equations) to achieve data-connectivity at the linking interface, which require the determination of discharge coefficients. Because of the paucity of high resolution localised data for this type of flows, the current understanding and quantification of a suitable range for those discharge coefficients is somewhat lacking. To fulfil this gap, this work presents the results acquired from an instrumented physical model designed to study the interaction between a pipe network flow and a floodplain flow. The full range of sewer-to-surface and surface-to-sewer flow conditions at the exchange zone are experimentally analysed in both steady and unsteady flow regimes. Steady state measured discharges are first analysed considering the relationship between the energy heads from the sewer flow and the floodplain flow; these results show that existing weir and orifice formulae are valid for describing the flow exchange for the present physical model, and yield new calibrated discharge coefficients for each of the flow conditions. The measured exchange discharges are also integrated (as a source term) within a 2D numerical flood model (a finite volume solver to the 2D Shallow Water Equations (SWE)), which is shown to reproduce the observed coefficients. This calibrated numerical model is then used to simulate a series of unsteady flow tests reproduced within the experimental facility. Results show that the numerical model overestimated the values of mean surcharge flow rate. This suggests the occurrence of additional head losses in unsteady conditions which are not currently accounted for within flood models calibrated in steady flow conditions.

  18. Reaction kinetic model of the surface-mediated formation of PCDD/F from pyrolysis of 2-chlorophenol on a CuP/Silica suface

    Energy Technology Data Exchange (ETDEWEB)

    Lomnicki, S.; Khachatryan, L.; Dellinger, B. [Louisiana State Univ., Baton Rouge (United States). Dept. of Chemistry

    2004-09-15

    One of the major challenges in developing predictive models of the surface mediated pollutant formation and fuel combustion is the construction of reliable reaction kinetic mechanisms and models. While the homogeneous, gas-phase chemistry of various light fuels such as hydrogen and methane is relatively well-known large uncertainties exist in the reaction paths of surface mediated reaction mechanisms for even these very simple species. To date, no detailed kinetic consideration of the surface mechanisms of formation of complex organics such as PCDD/F have been developed. In addition to the complexity of the mechanism, a major difficulty is the lack of reaction kinetic parameters (pre-exponential factor and activation energy) of surface reactions, Consequently, numerical studies of the surface-mediated formation of PCDD/F have often been incorporated only a few reactions. We report the development of a numerical multiple-step surface model based on experimental data of surface mediated (5% CuO/SiO2) conversion of 2-monochlorphenol (2-MCP) to PCDD/F under pyrolytic or oxidative conditions. A reaction kinetic model of the catalytic conversion of 2-MCP on the copper oxide catalyst under pyrolytic conditions was developed based on a detailed multistep surface reaction mechanism developed in our laboratory. The performance of the chemical model is assessed by comparing the numerical predictions with experimental measurements. SURFACE CHEMKIN (version 3.7.1) software was used for modeling. Our results confirm the validity of previously published mechanism of the reaction and provides new insight concerning the formation of PCDD/F formation in combustion processes. This model successfully explains the high yields of PCDD/F at low temperatures that cannot be explained using a purely gas-phase mode.

  19. Adsorption of chromium(VI) and Rhodamine B by surface modified tannery waste: Kinetic, mechanistic and thermodynamic studies

    Energy Technology Data Exchange (ETDEWEB)

    Anandkumar, J. [Centre for the Environment, Indian Institute of Technology Guwahati, Guwahati 781039, Assam (India); Mandal, B., E-mail: bpmandal@iitg.ernet.in [Department of Chemical Engineering, Indian Institute of Technology, Guwahati 781039, Assam (India)

    2011-02-28

    In this study, various activation methods have been employed to examine the potential reuse of tannery residual biomass (TRB) obtained from vegetable tanning process for the removal of Cr(VI) and Rhodamine B (RB) from aqueous solution. The maximum BET surface area (10.42 m{sup 2}/g), honey comb pore distribution and uptake of both Cr(VI) and RB were achieved when only 3-fold volume of HCl was used to activate the biomass. The pH and temperature experiment showed that they have considerable impact on the adsorption capacity of the used adsorbent. The presence of other ions (Na{sup +}, Ca{sup 2+} and NH{sub 4}{sup +}) significantly reduces the metal uptake but marginal enhancement in the dye removal was observed when Na{sup +} and NH{sub 4}{sup +} ions were present in the solution. The equilibrium data fitted satisfactorily with the Langmuir model and monolayer sorption capacity obtained as 177-217 and 213-250 mg/g for Cr(VI) and RB at 30-50 deg. C, respectively. The sorption kinetics was found to follow the pseudo-second-order kinetic model. The increase in adsorption capacity for both metal and dye with increase in temperature indicates that the uptake was endothermic in nature. The results indicate that the HCl modified TRB (A-TRB) could be employed as a low cost adsorbent for the removal of both Cr(VI) and RB from the aqueous solution including industrial wastewater.

  20. Photolysis of polycyclic aromatic hydrocarbons (PAHs) on Fe3+-montmorillonite surface under visible light: Degradation kinetics, mechanism, and toxicity assessments.

    Science.gov (United States)

    Zhao, Song; Jia, Hanzhong; Nulaji, Gulimire; Gao, Hongwei; Wang, Fu; Wang, Chuanyi

    2017-10-01

    Photochemical behavior of various polycyclic aromatic hydrocarbons (PAHs) on Fe 3+ -modified montmorillonite was explored to determine their potential kinetics, pathways, and mechanism under visible light. Depending on the type of PAH molecules, the transformation rate follows the order of benzo[a]pyrene ≈ anthracene > benzo[a]anthracene > phenanthrene. Quantum simulation results confirm the crucial role of "cation-π" interaction between Fe 3+ and PAHs on their transformation kinetics. Primary intermediates, including quinones, ring-opening products and benzene derivatives, were identified by gas chromatography-mass spectrometer (GC-MS), and the possible photodegradation pathway of benzo[a]pyrene was proposed. Meanwhile, radical intermediates, such as reactive oxygen species (ROS) and free organic radicals, were detected by electron paramagnetic resonance (EPR) technique. The photolysis of selected PAHs, such as anthracene and benzo[a]pyrene, on clay surface firstly occurs by electron transfer from PAHs to Fe 3+ -montmorillonite, followed by degradation involving photo-induced ROS such as ·OH and ·O 2 - . To investigate the acute toxicity of photolysis products, the Microtox ® toxicity test was performed during the photodegradation processes of various PAHs. As a result, the photo-irradiation initially induces increased toxicity by generating reactive intermediates, such as free organic radicals, and then the toxicity gradually decreases with increasing of reaction time. Overall, the present study provides useful information to understand the fate and photo-transformation of PAHs in contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. The effect of surface roughness on the heat exchange and pressure-drop coefficients

    International Nuclear Information System (INIS)

    Malherbe, J.M.

    1963-02-01

    The effect of various types of roughness on the wall of an axial tube in an annular space of 15-25 mm cooled by an air-flow has been studied in the case of steady turbulence. Roughness of the type 'disrupter of the boundary layer' was set up using triangular threads of 0.2 to 0.4 mm thickness machined in the tube itself, or brass or glass wire wound on a smooth tube. Tests were also carried out using the roughness provided by regularly spaced pyramids 0.4 mm high. The results obtained showed that the heat exchange increased because of the presence of this roughness. A maximum in the heat exchange and pressure-drop coefficients was observed when the pitch equals about eight times the height of the thread. An analytical method has been developed and experiments have been carried out in which the two walls of the annular space were heated in such a way as to transmit unequal heat flows. The region considered is limited to Reynolds's numbers of between 5 X 10 3 and 5 x 10 4 and wall temperatures of under 250 deg C. (author) [fr

  2. Air-surface exchange measurements of gaseous elemental mercury over naturally enriched and background terrestrial landscapes in Australia

    Directory of Open Access Journals (Sweden)

    G. C. Edwards

    2013-05-01

    Full Text Available This paper presents the first gaseous elemental mercury (GEM air-surface exchange measurements obtained over naturally enriched and background (−1 Hg terrestrial landscapes in Australia. Two pilot field studies were carried out during the Australian autumn and winter periods at a copper-gold-cobalt-arsenic-mercury mineral field near Pulganbar, NSW. GEM fluxes using a dynamic flux chamber approach were measured, along with controlling environmental parameters over three naturally enriched and three background substrates. The enriched sites results showed net emission to the atmosphere and a strong correlation between flux and substrate Hg concentration, with average fluxes ranging from 14 ± 1 ng m−2 h−1 to 113 ± 6 ng m−2 h−1. Measurements at background sites showed both emission and deposition. The average Hg flux from all background sites showed an overall net emission of 0.36 ± 0.06 ng m−2 h−1. Fluxes show strong relationships with temperature, radiation, and substrate parameters. A compensation point of 2.48, representative of bare soils was determined. For periods of deposition, dry deposition velocities ranged from 0.00025 cm s−1 to 0.0083 cm s−1 with an average of 0.0041 ± 0.00018 cm s−1, representing bare soil, nighttime conditions. Comparison of the Australian data to North American data suggests the need for Australian-specific mercury air-surface exchange data representative of Australia's unique climatic conditions, vegetation types, land use patterns and soils.

  3. Improving the corrosion resistance of proton exchange membrane fuel cell carbon supports by pentafluorophenyl