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Sample records for oxidation reaction dynamics

  1. Molecular Interactions and Reaction Dynamics in Supercritical Water Oxidation

    National Research Council Canada - National Science Library

    Johnston, K

    1998-01-01

    .... From UV-vis spectroscopic measurements and molecular dynamics simulation of chemical equilibria, we have shown that density effects on broad classes of reactions may be explained in terms of changes...

  2. Dynamics of activity free radical oxidation reactions in students with cerebral palsy results over the course of the educational process

    Directory of Open Access Journals (Sweden)

    Makarova E.V.

    2012-12-01

    Full Text Available The dynamics of changes activity of reactions is studied freely radical oxidize for students with the consequences of child's cerebral paralysis. 20 students took part in an experiment. Found that the course of study they have more active free radical oxidation reactions and decreases the activity of antiradical protection. Given the use of additional physical activity in aerobic training indicators intracellular antioxidant defense system increased, decreased content of reaction products of lipid peroxidation. However, increased rates of maximum oxygen consumption and increased tolerance of students with cerebral palsy to the consequences of physical activity. It is set that the pathological changes of metabolism for students ground the necessity of application of the differentiated physical loadings. The optimum forms of physical rehabilitation of the aerobic training is the dosed walking, medical swimming, dosed after distance, sometimes and by the corner of getting up pedestrian ascents. Loading is increased due to a volume, but not intensity of exercises.

  3. Isotopes in oxidation reactions

    International Nuclear Information System (INIS)

    Stewart, R.

    1976-01-01

    The use of isotopes in the study of organic oxidation mechanisms is discussed. The help provided by tracer studies to demonstrate the two-equivalent path - hydride transfer, is illustrated by the examples of carbonium oxidants and the Wacker reaction. The role of kinetic isotope effects in the study of the scission of carbon-hydrogen bonds is illustrated by hydride abstraction, hydrogen atom abstraction, proton abstraction and quantum mechanical tunnelling. Isotopic studies on the oxidation of alcohols, carbonyl compounds, amines and hydrocarbons are discussed. The role of isotopes in the study of biochemical oxidation is illustrated with a discussion on nicotinamide and flavin coenzymes. (B.R.H.)

  4. Hydrogen incorporation and radiation induced dynamics in metal-oxide-silicon structures. A study using nuclear reaction analysis

    International Nuclear Information System (INIS)

    Briere, M.A.

    1993-07-01

    Resonant nuclear reaction analysis, using the 1 H( 15 N, αγ) 12 C reaction at 6.4 MeV, has been successfully applied to the investigation of hydrogen incorporation and radiation induced migration in metal-oxide-silicon structures. A preliminary study of the influence of processing parameters on the H content of thermal oxides, with and without gate material present, has been performed. It is found that the dominant source of hydrogen in Al gate devices and dry oxides is often contamination, likely in the form of adsorbed water vapor, formed upon exposure to room air after removal from the oxidation furnace. Concentrations of hydrogen in the bulk oxide as high as 3 10 20 cm -3 (Al gate), and as low as 1 10 18 cm -3 (poly Si-gate) have been observed. Hydrogen accumulation at the Si-SiO 2 interface has been reproducibly demonstrated for as-oxidized samples, as well as for oxides exposed to H 2 containing atmospheres during subsequent thermal processing. The migration of hydrogen, from the bulk oxide to the silicon-oxide interface during NRA, has been observed and intensively investigated. A direct correlation between the hydrogen content of the bulk oxide and the radiation generated oxide charges and interface states is presented. These data provide strong support for the important role of hydrogen in determining the radiation sensitivity of electronic devices. (orig.)

  5. Photochemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Moore, B.C. [Lawrence Berkeley Laboratory, Livermore, CA (United States)

    1993-12-01

    The purpose of the program is to develop a fundamental understanding of unimolecular and bimolecular reaction dynamics with application in combustion and energy systems. The energy dependence in ketene isomerization, ketene dissociation dynamics, and carbonyl substitution on organometallic rhodium complexes in liquid xenon have been studied. Future studies concerning unimolecular processes in ketene as well as energy transfer and kinetic studies of methylene radicals are discussed.

  6. Study of the dynamics of the MoO2-Mo2C system for catalytic partial oxidation reactions

    Science.gov (United States)

    Cuba Torres, Christian Martin

    On a global scale, the energy demand is largely supplied by the combustion of non-renewable fossil fuels. However, their rapid depletion coupled with environmental and sustainability concerns are the main drivers to seek for alternative energetic strategies. To this end, the sustainable generation of hydrogen from renewable resources such as biodiesel would represent an attractive alternative solution to fossil fuels. Furthermore, hydrogen's lower environmental impact and greater independence from foreign control make it a strong contender for solving this global problem. Among a wide variety of methods for hydrogen production, the catalytic partial oxidation offers numerous advantages for compact and mobile fuel processing systems. For this reaction, the present work explores the versatility of the Mo--O--C catalytic system under different synthesis methods and reforming conditions using methyl oleate as a surrogate biodiesel. MoO2 exhibits good catalytic activity and exhibits high coke-resistance even under reforming conditions where long-chain oxygenated compounds are prone to form coke. Moreover, the lattice oxygen present in MoO2 promotes the Mars-Van Krevelen mechanism. Also, it is introduced a novel beta-Mo2C synthesis by the in-situ formation method that does not utilize external H2 inputs. Herein, the MoO 2/Mo2C system maintains high catalytic activity for partial oxidation while the lattice oxygen serves as a carbon buffer for preventing coke formation. This unique feature allows for longer operation reforming times despite slightly lower catalytic activity compared to the catalysts prepared by the traditional temperature-programmed reaction method. Moreover, it is demonstrated by a pulse reaction technique that during the phase transformation of MoO2 to beta-Mo2C, the formation of Mo metal as an intermediate is not responsible for the sintering of the material wrongly assumed by the temperature-programmed method.

  7. Ion-Molecule Reaction Dynamics.

    Science.gov (United States)

    Meyer, Jennifer; Wester, Roland

    2017-05-05

    We review the recent advances in the investigation of the dynamics of ion-molecule reactions. During the past decade, the combination of single-collision experiments in crossed ion and neutral beams with the velocity map ion imaging detection technique has enabled a wealth of studies on ion-molecule reactions. These methods, in combination with chemical dynamics simulations, have uncovered new and unexpected reaction mechanisms, such as the roundabout mechanism and the subtle influence of the leaving group in anion-molecule nucleophilic substitution reactions. For this important class of reactions, as well as for many fundamental cation-molecule reactions, the information obtained with crossed-beam imaging is discussed. The first steps toward understanding micro-solvation of ion-molecule reaction dynamics are presented. We conclude with the presentation of several interesting directions for future research.

  8. Oxidation dynamics of aluminum nanorods

    Energy Technology Data Exchange (ETDEWEB)

    Li, Ying [Argonne Leadership Computing Facility, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Kalia, Rajiv K.; Nakano, Aiichiro; Vashishta, Priya [Collaboratory for Advanced Computing and Simulations, Department of Physics and Astronomy, Department of Chemical Engineering and Materials Science, Department of Computer Science, University of Southern California, Los Angeles, California 90089-0242 (United States)

    2015-02-23

    Aluminum nanorods (Al-NRs) are promising fuels for pyrotechnics due to the high contact areas with oxidizers, but their oxidation mechanisms are largely unknown. Here, reactive molecular dynamics simulations are performed to study thermally initiated burning of oxide-coated Al-NRs with different diameters (D = 26, 36, and 46 nm) in oxygen environment. We found that thinner Al-NRs burn faster due to the larger surface-to-volume ratio. The reaction initiates with the dissolution of the alumina shell into the molten Al core to generate heat. This is followed by the incorporation of environmental oxygen atoms into the resulting Al-rich shell, thereby accelerating the heat release. These results reveal an unexpectedly active role of the alumina shell as a “nanoreactor” for oxidation.

  9. Dynamic effects in fragmentation reactions

    International Nuclear Information System (INIS)

    Bertsch, G. F.; Esbensen, H.

    2002-01-01

    Fragmentation reactions offer a useful tool to study the spectroscopy of halo nuclei, but the large extent of the halo wave function makes the reaction theory more difficult. The simple reaction models based on the eikonal approximation for the nuclear interaction or first-order perturbation theory for the Coulomb interaction have systematic errors that they investigate here, comparing to the predictions of complete dynamical calculations. They find that stripping probabilities are underpredicted by the eikonal model, leading to extracted spectroscopy strengths that are two large. In contrast, the Coulomb excitation is overpredicted by the simple theory. They attribute this to a screening effect, as is well known in the Barkas effect on stopping powers. The errors decrease with beam energy as E(sub beam)(sup -1), and are not significant at beam energies above 50 MeV/u. At lower beam energies, the effects should be taken into account when extracting quantitative spectroscopic strengths

  10. Uranium oxidation: characterization of oxides formed by reaction with water

    International Nuclear Information System (INIS)

    Fuller, E.L. Jr.; Smyrl, N.R.; Condon, J.B.; Eager, M.H.

    1983-01-01

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures

  11. Heterogeneous Metal Catalysts for Oxidation Reactions

    Directory of Open Access Journals (Sweden)

    Md. Eaqub Ali

    2014-01-01

    Full Text Available Oxidation reactions may be considered as the heart of chemical synthesis. However, the indiscriminate uses of harsh and corrosive chemicals in this endeavor are threating to the ecosystems, public health, and terrestrial, aquatic, and aerial flora and fauna. Heterogeneous catalysts with various supports are brought to the spotlight because of their excellent capabilities to accelerate the rate of chemical reactions with low cost. They also minimize the use of chemicals in industries and thus are friendly and green to the environment. However, heterogeneous oxidation catalysis are not comprehensively presented in literature. In this short review, we clearly depicted the current state of catalytic oxidation reactions in chemical industries with specific emphasis on heterogeneous catalysts. We outlined here both the synthesis and applications of important oxidation catalysts. We believe it would serve as a reference guide for the selection of oxidation catalysts for both industries and academics.

  12. Graphite Oxidation Thermodynamics/Reactions

    International Nuclear Information System (INIS)

    Propp, W.A.

    1998-01-01

    The vulnerability of graphite-matrix spent nuclear fuel to oxidation by the ambient atmosphere if the fuel canister is breached was evaluated. Thermochemical and kinetic data over the anticipated range of storage temperatures (200 to 400 C) were used to calculate the times required for a total carbon mass loss of 1 mgcm-2 from a fuel specimen. At 200 C, the time required to produce even this small loss is large, 900,000 yr. However, at 400 C the time required is only 1.9 yr. The rate of oxidation at 200 C is negligible, and the rate even at 400 C is so small as to be of no practical consequence. Therefore, oxidation of the spent nuclear fuel upon a loss of canister integrity is not anticipated to be a concern based upon the results of this study

  13. Oxidation reactions of bilirubin in aqueous solutions

    International Nuclear Information System (INIS)

    Mohan, Hari; Gopinathan, C.

    1990-01-01

    The radical cation of bilirubin (BR) has been tentatively identified as a transient intermediate in the reactions of BR with different oxidizing species such as Br 2 - , I 2 - and CH 3 I . OH. The rate constants for these reactions have been determined as 2.4 x 10 9 , l.0 x 10 9 and 2.7 x 10 9 dm 3 mol -1 s -1 , respectively. Biliverdin is likely to be among the stable products formed on oxidation of BR by these oxidizing species. (author)

  14. Reaction rate oscillations during catalytic CO oxidation: A brief overview

    Science.gov (United States)

    Tsotsis, T. T.; Sane, R. C.

    1987-01-01

    It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.

  15. Heterogeneously Catalyzed Oxidation Reactions Using Molecular Oxygen

    DEFF Research Database (Denmark)

    Beier, Matthias Josef

    Heterogeneously catalyzed selective oxidation reactions have attracted a lot of attention in recent time. The first part of the present thesis provides an overview over heterogeneous copper and silver catalysts for selective oxidations in the liquid phase and compared the performance and catalytic...... that both copper and silver can function as complementary catalyst materials to gold showing different catalytic properties and being more suitable for hydrocarbon oxidation reactions. Potential opportunities for future research were outlined. In an experimental study, the potential of silver as a catalyst...... revealed that all catalysts were more active in combination with ceria nanoparticles and that under the tested reaction conditions silver was equally or even more efficient than the gold catalysts. Calcination at 900 °C of silver on silica prepared by impregnation afforded a catalyst which was used...

  16. Effective dynamics along given reaction coordinates, and reaction rate theory.

    Science.gov (United States)

    Zhang, Wei; Hartmann, Carsten; Schütte, Christof

    2016-12-22

    In molecular dynamics and related fields one considers dynamical descriptions of complex systems in full (atomic) detail. In order to reduce the overwhelming complexity of realistic systems (high dimension, large timescale spread, limited computational resources) the projection of the full dynamics onto some reaction coordinates is examined in order to extract statistical information like free energies or reaction rates. In this context, the effective dynamics that is induced by the full dynamics on the reaction coordinate space has attracted considerable attention in the literature. In this article, we contribute to this discussion: we first show that if we start with an ergodic diffusion process whose invariant measure is unique then these properties are inherited by the effective dynamics. Then, we give equations for the effective dynamics, discuss whether the dominant timescales and reaction rates inferred from the effective dynamics are accurate approximations of such quantities for the full dynamics, and compare our findings to results from approaches like Mori-Zwanzig, averaging, or homogenization. Finally, by discussing the algorithmic realization of the effective dynamics, we demonstrate that recent algorithmic techniques like the "equation-free" approach and the "heterogeneous multiscale method" can be seen as special cases of our approach.

  17. Effect of Si on the oxidation reaction of α-Ti(0 0 0 1) surface: ab initio molecular dynamics study.

    Science.gov (United States)

    Bhattacharya, Somesh Kr; Sahara, Ryoji; Ueda, Kyosuke; Narushima, Takayuki

    2017-01-01

    We present our ab initio molecular dynamics (MD) study of the effect of Si on the oxidation of α-Ti(0   0   0   1) surfaces. We varied the Si concentration in the first layer of the surface from 0 to 25 at.% and the oxygen coverage ( θ ) on the surface was varied up to 1 monolayer (ML). The MD was performed at 300, 600 and 973 K. For θ  = 0.5 ML, oxygen penetration into the slab was not observed after 16 ps of MD at 973 K while for θ  > 0.5 ML, oxygen penetration into the Ti slab was observed even at 300 K. From Bader charge analysis, we confirmed the formation of the oxide layer on the surface of the Ti slab. At higher temperatures, the Si atoms diffused from the first layer to the interior of the slab, while the Ti atoms moved from second layer to the first layer. The pair correlation function shows the formation of a disordered Ti-O network during the initial stage of oxidation. Si was found to have a strong influence on the penetration of oxygen in the Ti slab at high temperatures.

  18. Dynamics of traveling reaction pulses

    International Nuclear Information System (INIS)

    Dovzhenko, A. Yu.; Rumanov, E. N.

    2007-01-01

    The growth of activator losses is accompanied by the decay of a traveling reaction pulse. In a ring reactor, this propagation threshold is present simultaneously with a threshold related to the ring diameter. The results of numerical experiments with pulses of an exothermal reaction reveal the transition from pulse propagation to a homogeneous hot regime, established regimes with periodic variations of the pulse velocity, and oscillatory decay of the pulse. When the medium becomes 'bistable' as a result of the variation in parameters, this factor does not prevent the propagation of pulses, but leads to changes in the pulse structure

  19. Molecular dynamics simulation of a chemical reaction

    International Nuclear Information System (INIS)

    Gorecki, J.; Gryko, J.

    1988-06-01

    Molecular dynamics is used to study the chemical reaction A+A→B+B. It is shown that the reaction rate constant follows the Arrhenius law both for Lennard-Jones and hard sphere interaction potentials between substrate particles. A. For the denser systems the reaction rate is proportional to the value of the radial distribution function at the contact point of two hard spheres. 10 refs, 4 figs

  20. The oxidative burst reaction in mammalian cells depends on gravity.

    Science.gov (United States)

    Adrian, Astrid; Schoppmann, Kathrin; Sromicki, Juri; Brungs, Sonja; von der Wiesche, Melanie; Hock, Bertold; Kolanus, Waldemar; Hemmersbach, Ruth; Ullrich, Oliver

    2013-12-20

    Gravity has been a constant force throughout the Earth's evolutionary history. Thus, one of the fundamental biological questions is if and how complex cellular and molecular functions of life on Earth require gravity. In this study, we investigated the influence of gravity on the oxidative burst reaction in macrophages, one of the key elements in innate immune response and cellular signaling. An important step is the production of superoxide by the NADPH oxidase, which is rapidly converted to H2O2 by spontaneous and enzymatic dismutation. The phagozytosis-mediated oxidative burst under altered gravity conditions was studied in NR8383 rat alveolar macrophages by means of a luminol assay. Ground-based experiments in "functional weightlessness" were performed using a 2 D clinostat combined with a photomultiplier (PMT clinostat). The same technical set-up was used during the 13th DLR and 51st ESA parabolic flight campaign. Furthermore, hypergravity conditions were provided by using the Multi-Sample Incubation Centrifuge (MuSIC) and the Short Arm Human Centrifuge (SAHC). The results demonstrate that release of reactive oxygen species (ROS) during the oxidative burst reaction depends greatly on gravity conditions. ROS release is 1.) reduced in microgravity, 2.) enhanced in hypergravity and 3.) responds rapidly and reversible to altered gravity within seconds. We substantiated the effect of altered gravity on oxidative burst reaction in two independent experimental systems, parabolic flights and 2D clinostat / centrifuge experiments. Furthermore, the results obtained in simulated microgravity (2D clinorotation experiments) were proven by experiments in real microgravity as in both cases a pronounced reduction in ROS was observed. Our experiments indicate that gravity-sensitive steps are located both in the initial activation pathways and in the final oxidative burst reaction itself, which could be explained by the role of cytoskeletal dynamics in the assembly and function

  1. Probing reaction dynamics with GDR decay

    International Nuclear Information System (INIS)

    Beene, J.R.

    1994-01-01

    The giant dipole resonance (GDR) has been a prolific source of information on the physics of the nucleus. Mostly it has taught us about nuclear structure, but recently experiments have utilized the GDR as a probe of nuclear reaction dynamics. In this report two examples of such investigations are discussed involving very different reactions and probing time scales that differ by a factor of ∼10 3

  2. Raman spectroscopic study of reaction dynamics

    Science.gov (United States)

    MacPhail, R. A.

    1990-12-01

    The Raman spectra of reacting molecules in liquids can yield information about various aspects of the reaction dynamics. The author discusses the analysis of Raman spectra for three prototypical unimolecular reactions, the rotational isomerization of n-butane and 1,2-difluoroethane, and the barrierless exchange of axial and equatorial hydrogens in cyclopentane via pseudorotation. In the first two cases the spectra are sensitive to torsional oscillations of the gauche conformer, and yield estimates of the torsional solvent friction. In the case of cyclopentane, the spectra can be used to discriminate between different stochastic models of the pseudorotation dynamics, and to determine the relevant friction coefficients.

  3. Methods for forming complex oxidation reaction products including superconducting articles

    International Nuclear Information System (INIS)

    Rapp, R.A.; Urquhart, A.W.; Nagelberg, A.S.; Newkirk, M.S.

    1992-01-01

    This patent describes a method for producing a superconducting complex oxidation reaction product of two or more metals in an oxidized state. It comprises positioning at least one parent metal source comprising one of the metals adjacent to a permeable mass comprising at least one metal-containing compound capable of reaction to form the complex oxidation reaction product in step below, the metal component of the at least one metal-containing compound comprising at least a second of the two or more metals, and orienting the parent metal source and the permeable mass relative to each other so that formation of the complex oxidation reaction product will occur in a direction towards and into the permeable mass; and heating the parent metal source in the presence of an oxidant to a temperature region above its melting point to form a body of molten parent metal to permit infiltration and reaction of the molten parent metal into the permeable mass and with the oxidant and the at least one metal-containing compound to form the complex oxidation reaction product, and progressively drawing the molten parent metal source through the complex oxidation reaction product towards the oxidant and towards and into the adjacent permeable mass so that fresh complex oxidation reaction product continues to form within the permeable mass; and recovering the resulting complex oxidation reaction product

  4. Markovian dynamics on complex reaction networks

    Energy Technology Data Exchange (ETDEWEB)

    Goutsias, J., E-mail: goutsias@jhu.edu; Jenkinson, G., E-mail: jenkinson@jhu.edu

    2013-08-10

    Complex networks, comprised of individual elements that interact with each other through reaction channels, are ubiquitous across many scientific and engineering disciplines. Examples include biochemical, pharmacokinetic, epidemiological, ecological, social, neural, and multi-agent networks. A common approach to modeling such networks is by a master equation that governs the dynamic evolution of the joint probability mass function of the underlying population process and naturally leads to Markovian dynamics for such process. Due however to the nonlinear nature of most reactions and the large size of the underlying state-spaces, computation and analysis of the resulting stochastic population dynamics is a difficult task. This review article provides a coherent and comprehensive coverage of recently developed approaches and methods to tackle this problem. After reviewing a general framework for modeling Markovian reaction networks and giving specific examples, the authors present numerical and computational techniques capable of evaluating or approximating the solution of the master equation, discuss a recently developed approach for studying the stationary behavior of Markovian reaction networks using a potential energy landscape perspective, and provide an introduction to the emerging theory of thermodynamic analysis of such networks. Three representative problems of opinion formation, transcription regulation, and neural network dynamics are used as illustrative examples.

  5. Markovian dynamics on complex reaction networks

    International Nuclear Information System (INIS)

    Goutsias, J.; Jenkinson, G.

    2013-01-01

    Complex networks, comprised of individual elements that interact with each other through reaction channels, are ubiquitous across many scientific and engineering disciplines. Examples include biochemical, pharmacokinetic, epidemiological, ecological, social, neural, and multi-agent networks. A common approach to modeling such networks is by a master equation that governs the dynamic evolution of the joint probability mass function of the underlying population process and naturally leads to Markovian dynamics for such process. Due however to the nonlinear nature of most reactions and the large size of the underlying state-spaces, computation and analysis of the resulting stochastic population dynamics is a difficult task. This review article provides a coherent and comprehensive coverage of recently developed approaches and methods to tackle this problem. After reviewing a general framework for modeling Markovian reaction networks and giving specific examples, the authors present numerical and computational techniques capable of evaluating or approximating the solution of the master equation, discuss a recently developed approach for studying the stationary behavior of Markovian reaction networks using a potential energy landscape perspective, and provide an introduction to the emerging theory of thermodynamic analysis of such networks. Three representative problems of opinion formation, transcription regulation, and neural network dynamics are used as illustrative examples

  6. Reaction dynamics in polyatomic molecular systems

    Energy Technology Data Exchange (ETDEWEB)

    Miller, W.H. [Lawrence Berkeley Laboratory, CA (United States)

    1993-12-01

    The goal of this program is the development of theoretical methods and models for describing the dynamics of chemical reactions, with specific interest for application to polyatomic molecular systems of special interest and relevance. There is interest in developing the most rigorous possible theoretical approaches and also in more approximate treatments that are more readily applicable to complex systems.

  7. Unimolecular reaction dynamics of free radicals

    International Nuclear Information System (INIS)

    Terry A. Miller

    2006-01-01

    Free radical reactions are of crucial importance in combustion and in atmospheric chemistry. Reliable theoretical models for predicting the rates and products of these reactions are required for modeling combustion and atmospheric chemistry systems. Unimolecular reactions frequently play a crucial role in determining final products. The dissociations of vinyl, CH2= CH, and methoxy, CH3O, have low barriers, about 13,000 cm-1 and 8,000 cm-1, respectively. Since barriers of this magnitude are typical of free radicals these molecules should serve as benchmarks for this important class of reactions. To achieve this goal, a detailed understanding of the vinyl and methoxy radicals is required. Results for dissociation dynamics of vinyl and selectively deuterated vinyl radical are reported. Significantly, H-atom scrambling is shown not to occur in this reaction. A large number of spectroscopic experiments for CH3O and CHD2O have been performed. Spectra recorded include laser induced fluorescence (LIF), laser excited dispersed fluorescence (LEDF), fluorescence dip infrared (FDIR) and stimulated emission pumping (SEP). Such results are critical for implementing dynamics experiments involving the dissociation of methoxy

  8. Theoretical studies of chemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Schatz, G.C. [Argonne National Laboratory, IL (United States)

    1993-12-01

    This collaborative program with the Theoretical Chemistry Group at Argonne involves theoretical studies of gas phase chemical reactions and related energy transfer and photodissociation processes. Many of the reactions studied are of direct relevance to combustion; others are selected they provide important examples of special dynamical processes, or are of relevance to experimental measurements. Both classical trajectory and quantum reactive scattering methods are used for these studies, and the types of information determined range from thermal rate constants to state to state differential cross sections.

  9. Fusion dynamics in 40Ca induced reactions

    International Nuclear Information System (INIS)

    Prasad, E.; Hinde, D.J.; Williams, E.

    2017-01-01

    Synthesis of superheavy elements (SHEs) and investigation of their properties are among the most challenging research topics in modern science. A non-compound nuclear process called quasi fission is partly responsible for the very low production cross sections of SHEs. The formation and survival probabilities of the compound nucleus (CN) strongly depend on the competition between fusion and quasi fission. A clear understanding of these processes and their dynamics is required to make reliable predictions of the best reactions to synthesise new SHEs. All elements beyond Nh are produced using hot fusion reactions and beams of 48 Ca were used in most of these experiments. In this context a series of fission measurements have been carried out at the Australian National University (ANU) using 40;48 Ca beams on various targets ranging from 142 Nd to 249 Cf. Some of the 40 Ca reactions will be discussed in this symposium

  10. Molecular beam studies of reaction dynamics

    International Nuclear Information System (INIS)

    Lee, Yuan T.

    1991-03-01

    The major thrust of this research project is to elucidate detailed dynamics of simple elementary reactions that are theoretically important and to unravel the mechanism of complex chemical reactions or photochemical processes that play important roles in many macroscopic processes. Molecular beams of reactants are used to study individual reactive encounters between molecules or to monitor photodissociation events in a collision-free environment. Most of the information is derived from measurement of the product fragment energy, angular, and state distributions. Recent activities are centered on the mechanisms of elementary chemical reactions involving oxygen atoms with unsaturated hydrocarbons, the dynamics of endothermic substitution reactions, the dependence of the chemical reactivity of electronically excited atoms on the alignment of excited orbitals, the primary photochemical processes of polyatomic molecules, intramolecular energy transfer of chemically activated and locally excited molecules, the energetics of free radicals that are important to combustion processes, the infrared-absorption spectra of carbonium ions and hydrated hydronium ions, and bond-selective photodissociation through electric excitation

  11. Molecular beam studies of reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Y.T. [Lawrence Berkeley Laboratory, CA (United States)

    1993-12-01

    The major thrust of this research project is to elucidate detailed dynamics of simple elementary reactions that are theoretically important and to unravel the mechanism of complex chemical reactions or photochemical processes that play important roles in many macroscopic processes. Molecular beams of reactants are used to study individual reactive encounters between molecules or to monitor photodissociation events in a collision-free environment. Most of the information is derived from measurement of the product fragment energy, angular, and state distributions. Recent activities are centered on the mechanisms of elementary chemical reactions involving oxygen atoms with unsaturated hydrocarbons, the dynamics of endothermic substitution reactions, the dependence of the chemical reactivity of electronically excited atoms on the alignment of excited orbitals, the primary photochemical processes of polyatomic molecules, intramolecular energy transfer of chemically activated and locally excited molecules, the energetics of free radicals that are important to combustion processes, the infrared-absorption spectra of carbonium ions and hydrated hydronium ions, and bond-selective photodissociation through electric excitation.

  12. Quantum dynamics of fast chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Light, J.C. [Univ. of Chicago, IL (United States)

    1993-12-01

    The aims of this research are to explore, develop, and apply theoretical methods for the evaluation of the dynamics of gas phase collision processes, primarily chemical reactions. The primary theoretical tools developed for this work have been quantum scattering theory, both in time dependent and time independent forms. Over the past several years, the authors have developed and applied methods for the direct quantum evaluation of thermal rate constants, applying these to the evaluation of the hydrogen isotopic exchange reactions, applied wave packet propagation techniques to the dissociation of Rydberg H{sub 3}, incorporated optical potentials into the evaluation of thermal rate constants, evaluated the use of optical potentials for state-to-state reaction probability evaluations, and, most recently, have developed quantum approaches for electronically non-adiabatic reactions which may be applied to simplify calculations of reactive, but electronically adiabatic systems. Evaluation of the thermal rate constants and the dissociation of H{sub 3} were reported last year, and have now been published.

  13. Reactions of organic zinc- and cadmium elementoxides with ethylene oxide

    International Nuclear Information System (INIS)

    Dodonov, V.A.; Krasnov, Yu.N.

    1980-01-01

    Studied are reactions of triphenylmethoxy, -triphenylsiloxyethylzinc and -cadmium with ethylene oxide in ratio of 1:1. Reactions have been carried out in tolyene solutions in ampules sealed in argon atmosphere. It is found that interaction of triphenylsiloxy-, triphenylmethoxyethylcadmium and triphenylsiloxyethylzinc with ethylene oxide occurs at the metal-carbon bond with formation of implantation products. Triphenylmethoxyethylzinc reacts with ethylene oxide both at the metal-carbon and metal-oxygen bonds. Alkoxytriphenylsiloxyderivatives of zinc and cadmium are thermally instable and decompose under the conditions of reaction (130 deg C) with migration of phenyl group from silicon to zinc or cadmium, giving alkoxyphenylderivative and with bensene splitting out

  14. Green oxidations: Titanium dioxide induced tandem oxidation coupling reactions

    OpenAIRE

    Jeena, Vineet; Robinson, Ross S

    2009-01-01

    Summary The application of titanium dioxide as an oxidant in tandem oxidation type processes is described. Under microwave irradiation, quinoxalines have been synthesized in good yields from the corresponding ?-hydroxyketones.

  15. Positive patch test reactions to oxidized limonene

    DEFF Research Database (Denmark)

    Bråred Christensson, Johanna; Andersen, Klaus E; Bruze, Magnus

    2014-01-01

    to oxidized R-limonene. OBJECTIVE: To study the exposure to limonene among consecutive dermatitis patients reacting to oxidized R-limonene in an international setting, and to assess the relevance of the exposure for the patients' dermatitis. METHODS: Oxidized R-limonene 3.0% (containing limonene...... hydroperoxides at 0.33%) in petrolatum was tested in 2900 consecutive dermatitis patients in Australia, Denmark, the United Kingdom, Singapore, Spain, and Sweden. A questionnaire assessing exposure to limonene-containing products was completed. RESULTS: Overall, exposure to products containing limonene was found...

  16. Uranium oxidation: Characterization of oxides formed by reaction with water by infrared and sorption analyses

    Science.gov (United States)

    Fuller, E. L.; Smyrl, N. R.; Condon, J. B.; Eager, M. H.

    1984-04-01

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. The results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. Inert gas sorption analyses and diffuse reflectance infrared studies combined with electron microscopy prove valuable in defining the chemistry and morphology of the oxidic products and hydrated intermediates.

  17. CONTAMINANT ADSORPTION AND OXIDATION VIA FENTON REACTION

    Science.gov (United States)

    A ground water treatment process is proposed involving two cgemical processes: adsorption and oxidation. Adsorption of an organic compound onto granulated activated carbon (GAC) containing iron conveniently results in immobilizing and concentrating contaminants from the ground w...

  18. Reaction mechanisms of ruthenium tetroxide mediated oxidations of organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Froehaug, Astrid Elisabeth

    1995-12-31

    This thesis reports a study of the mechanism of ruthenium tetroxide mediated oxidations of saturated hydrocarbons, ethers, alkenes and alcohols. Several methods were used. The RuO{sub 4}-mediated oxidations of adamantane and cis-decalin were studied in CCl{sub 4}-CH{sub 3}CN-H{sub 2}O and in acetone-water. The rate of reaction was found to be moderately influenced by the polarity of the solvent. Solvent properties other than the polarity were also found to influence the reaction rates. From the oxidations of adamantane and adamantane-1,3,5,7-d{sub 4} two primary kinetic deuterium isotope effects were found. These were comparable with the deuterium isotope effects found for the analogous oxidations of cis-decalin and cis-decalin-d{sub 18}. The results seem to exclude both a one step hydride abstraction reaction mechanism and a one step concerted mechanism, as well as a scheme where two such mechanisms compete. The observations may be explained by a two step reaction mechanism consisting of a pre-equilibrium with formation of a substrate-RuO{sub 4} complex followed by a concerted rate determining reaction. The RuO{sub 4}-mediated oxidation of ethers was of kinetic second order with a small enthalpy of activation and a large negative entropy of activation. Oxidation of cyclopropylmethyl methyl ether gave methyl cyclopropanecarboxylate, no rearranged products were observed. On RuO{sub 4} oxidations in CCl{sub 4} with NaIO{sub 4} as stoichiometric oxidant, no chlorinated products were observed. Several observations not in agreement with a hydride or a hydrogen abstraction mechanism may be explained by assuming that the reaction proceeds by either a concerted reaction or by a reversible oxidative addition of the ether to RuO{sub 4} followed by a slow concerted step. 228 refs., 9 figs., 27 tabs.

  19. Some Environmentally Relevant Reactions of Cerium Oxide

    Directory of Open Access Journals (Sweden)

    Janoš Pavel

    2014-12-01

    Full Text Available Reactive forms of cerium oxide were prepared by a thermal decomposition of various precursors, namely carbonates, oxalates and citrates, commercially available nanocrystalline cerium oxide (nanoceria was involved in the study for comparison. Scanning electron microscopy (SEM and x-ray diffraction analysis (XRD were used to examine the morphology and crystallinity of the samples, respectively, whereas the Brunauer-Emmett-Teller (BET method of nitrogen adsorption was used to determine surface areas. Interactions of cerium oxide with some phosphorus-containing compounds were investigated. Some of the examined samples, especially those prepared by annealing from carbonate precursors, exhibited an outstanding ability to destroy highly toxic organophosphates, such as pesticides (parathion methyl, or nerve agents (soman, VX. There were identified some relations between the degradation efficiency of cerium oxides and their crystallinity. It was also shown that cerium oxide is able to destroy one of widely used flame retardants - triphenyl phosphate. A phosphatase-mimetic activity of various cerium oxides was examined with the aid of a standardized phosphatase test.

  20. Kinetics of transuranium element oxidation-reduction reactions in solution

    International Nuclear Information System (INIS)

    Gourisse, D.

    1966-09-01

    A review of the kinetics of U, Np, Pu, Am oxidation-reduction reactions is proposed. The relations between the different activation thermodynamic functions (compensatory effect, formal entropy of the activated complex, magnitude of reactions velocities) are considered. The effects of acidity, ionic strength deuterium and mixed solvents polarity on reactions rates are described. The effect of different anions on reactions rates are explained by variations of the reaction standard free energy and variations of the activation free energy (coulombic interactions) resulting from the complexation of dissolved species by these anions. (author) [fr

  1. Reaction of iodine oxidation by potassium permanganate in tributyl phosphate

    International Nuclear Information System (INIS)

    Khokhlov, M.L.; Legin, E.K.

    1990-01-01

    Stoichiometry was determined and kinetics of iodine oxidation by potassium permanganate in tributylphosphate was studied. Kinetic scheme, which agrees with stoichiometry and experimental kinetic equation of the reaction, is suggested. A mixture is the reaction product. It is ascertained that when the mixture is heated, thermal decomposition of iodate to iodide occurs without elementary iodine separation, which is catalyzed by polymanganate

  2. Surface Interrogation Scanning Electrochemical Microscopy for a Photoelectrochemical Reaction: Water Oxidation on a Hematite Surface.

    Science.gov (United States)

    Kim, Jae Young; Ahn, Hyun S; Bard, Allen J

    2018-03-06

    To understand the pathway of a photoelectrochemical (PEC) reaction, quantitative knowledge of reaction intermediates is important. We describe here surface interrogation scanning electrochemical microscopy for this purpose (PEC SI-SECM), where a light pulse to a photoactive semiconductor film at a given potential generates intermediates that are then analyzed by a tip generated titrant at known times after the light pulse. The improvements were demonstrated for photoelectrochemical water oxidation (oxygen evolution) reaction on a hematite surface. The density of photoactive sites, proposed to be Fe 4+ species, on a hematite surface was successfully quantified, and the photoelectrochemical water oxidation reaction dynamics were elucidated by time-dependent redox titration experiments. The new configuration of PEC SI-SECM should find expanded usage to understand and investigate more complicated PEC reactions with other materials.

  3. A network dynamics approach to chemical reaction networks

    NARCIS (Netherlands)

    van der Schaft, Abraham; Rao, S.; Jayawardhana, B.

    2016-01-01

    A treatment of chemical reaction network theory is given from the perspective of nonlinear network dynamics, in particular of consensus dynamics. By starting from the complex-balanced assumption the reaction dynamics governed by mass action kinetics can be rewritten into a form which allows for a

  4. Cuprous oxide nanoparticles dispersed on reduced graphene oxide as an efficient electrocatalyst for oxygen reduction reaction.

    Science.gov (United States)

    Yan, Xiao-Yan; Tong, Xi-Li; Zhang, Yue-Fei; Han, Xiao-Dong; Wang, Ying-Yong; Jin, Guo-Qiang; Qin, Yong; Guo, Xiang-Yun

    2012-02-11

    Cuprous oxide (Cu(2)O) nanoparticles dispersed on reduced graphene oxide (RGO) were prepared by reducing copper acetate supported on graphite oxide using diethylene glycol as both solvent and reducing agent. The Cu(2)O/RGO composite exhibits excellent catalytic activity and remarkable tolerance to methanol and CO in the oxygen reduction reaction. This journal is © The Royal Society of Chemistry 2012

  5. Reaction between vanadium trichloride oxide and hydrogen sulfide

    International Nuclear Information System (INIS)

    Yajima, Akimasa; Matsuzaki, Ryoko; Saeki, Yuzo

    1978-01-01

    The details of the reaction between vanadium trichloride oxide and hydrogen sulfide were examined at 20 and 60 0 C. The main products by the reaction were vanadium dichloride oxide, sulfur, and hydrogen chloride. In addition to these products, small amounts of vanadium trichloride, vanadium tetrachloride, disulfur dichloride, and sulfur dioxide were formed. The formations of the above-mentioned reaction products can be explained as follows: The first stage is the reaction between vanadium trichloride oxide and hydrogen sulfide, 2VOCl 3 (l) + H 2 S(g)→2VOCl 2 (s) + S(s) + 2HCl(g). Then the resulting sulfur reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + 2S(s)→2VOCl 2 (s) + S 2 Cl 2 (l). The resulting disulfur dichloride subsequently reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + S 2 Cl 2 (l)→2VCl 4 (l) + S(s) + SO 2 (g). The resulting vanadium tetrachloride reacts with the sulfur formed during the reaction, 2VCl 4 (l) + 2S(s)→2VCl 3 (s) + S 2 Cl 2 (l), and also reacts with hydrogen sulfide, 2VCl 4 (l) + H 2 S(g)→2VCl 3 (s) + S(s) + 2HCl(g). (auth.)

  6. Solid-phase vibrational redox reactions in coordinated oxides

    International Nuclear Information System (INIS)

    Kostikova, G.P.; Korol'kov, D.V.; Kostikov, Yu.P.

    1996-01-01

    The properties of multicomponent oxides (YBa 2 Cu 3 O 7-x , etc.), incorporating different valency forms of each of two (or more) different elements have been compared with the properties of the known chemical systems, where vibrational (periodic) redox-reactions are realized a fortiori. The essence of the new theoretical concept suggested consists in the following: high-T c superconductivity of the complex oxides and similar compounds originates from vibrational redox reaction proceeding in solid phase and involving different valency atoms of every element

  7. Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product

    Science.gov (United States)

    David, Dennis D.; Dee, Louis A.; Beeson, Harold D.

    1997-01-01

    Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

  8. Modeling non-adiabatic photoexcited reaction dynamics in condensed phases

    International Nuclear Information System (INIS)

    Coker, D.F.

    2003-01-01

    Reactions of photoexcited molecules, ions, and radicals in condensed phase environments involve non-adiabatic dynamics over coupled electronic surfaces. We focus on how local environmental symmetries can effect non-adiabatic coupling between excited electronic states and thus influence, in a possibly controllable way, the outcome of photo-excited reactions. Semi-classical and mixed quantum-classical non-adiabatic molecular dynamics methods, together with semi-empirical excited state potentials are used to probe the dynamical mixing of electronic states in different environments from molecular clusters, to simple liquids and solids, and photo-excited reactions in complex reaction environments such as zeolites

  9. Oxidation Protection of Porous Reaction-Bonded Silicon Nitride

    Science.gov (United States)

    Fox, D. S.

    1994-01-01

    Oxidation kinetics of both as-fabricated and coated reaction-bonded silicon nitride (RBSN) were studied at 900 and 1000 C with thermogravimetry. Uncoated RBSN exhibited internal oxidation and parabolic kinetics. An amorphous Si-C-O coating provided the greatest degree of protection to oxygen, with a small linear weight loss observed. Linear weight gains were measured on samples with an amorphous Si-N-C coating. Chemically vapor deposited (CVD) Si3N4 coated RBSN exhibited parabolic kinetics, and the coating cracked severely. A continuous-SiC-fiber-reinforced RBSN composite was also coated with the Si-C-O material, but no substantial oxidation protection was observed.

  10. Semiclassical methods in chemical reaction dynamics

    International Nuclear Information System (INIS)

    Keshavamurthy, S.

    1994-12-01

    Semiclassical approximations, simple as well as rigorous, are formulated in order to be able to describe gas phase chemical reactions in large systems. We formulate a simple but accurate semiclassical model for incorporating multidimensional tunneling in classical trajectory simulations. This model is based on the existence of locally conserved actions around the saddle point region on a multidimensional potential energy surface. Using classical perturbation theory and monitoring the imaginary action as a function of time along a classical trajectory we calculate state-specific unimolecular decay rates for a model two dimensional potential with coupling. Results are in good comparison with exact quantum results for the potential over a wide range of coupling constants. We propose a new semiclassical hybrid method to calculate state-to-state S-matrix elements for bimolecular reactive scattering. The accuracy of the Van Vleck-Gutzwiller propagator and the short time dynamics of the system make this method self-consistent and accurate. We also go beyond the stationary phase approximation by doing the resulting integrals exactly (numerically). As a result, classically forbidden probabilties are calculated with purely real time classical trajectories within this approach. Application to the one dimensional Eckart barrier demonstrates the accuracy of this approach. Successful application of the semiclassical hybrid approach to collinear reactive scattering is prevented by the phenomenon of chaotic scattering. The modified Filinov approach to evaluating the integrals is discussed, but application to collinear systems requires a more careful analysis. In three and higher dimensional scattering systems, chaotic scattering is suppressed and hence the accuracy and usefulness of the semiclassical method should be tested for such systems

  11. Semiclassical methods in chemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Keshavamurthy, Srihari [Univ. of California, Berkeley, CA (United States)

    1994-12-01

    Semiclassical approximations, simple as well as rigorous, are formulated in order to be able to describe gas phase chemical reactions in large systems. We formulate a simple but accurate semiclassical model for incorporating multidimensional tunneling in classical trajectory simulations. This model is based on the existence of locally conserved actions around the saddle point region on a multidimensional potential energy surface. Using classical perturbation theory and monitoring the imaginary action as a function of time along a classical trajectory we calculate state-specific unimolecular decay rates for a model two dimensional potential with coupling. Results are in good comparison with exact quantum results for the potential over a wide range of coupling constants. We propose a new semiclassical hybrid method to calculate state-to-state S-matrix elements for bimolecular reactive scattering. The accuracy of the Van Vleck-Gutzwiller propagator and the short time dynamics of the system make this method self-consistent and accurate. We also go beyond the stationary phase approximation by doing the resulting integrals exactly (numerically). As a result, classically forbidden probabilties are calculated with purely real time classical trajectories within this approach. Application to the one dimensional Eckart barrier demonstrates the accuracy of this approach. Successful application of the semiclassical hybrid approach to collinear reactive scattering is prevented by the phenomenon of chaotic scattering. The modified Filinov approach to evaluating the integrals is discussed, but application to collinear systems requires a more careful analysis. In three and higher dimensional scattering systems, chaotic scattering is suppressed and hence the accuracy and usefulness of the semiclassical method should be tested for such systems.

  12. Some reactions of oxidizing radicals with enzymes in aqueous solution

    International Nuclear Information System (INIS)

    Cundall, R.B.; Bisby, R.H.; Hoe, S.T.; Sims, H.E.; Anderson, R.F.

    1979-01-01

    A range of oxidizing radicals including some inorganic radical anions and the superoxide radical, can be generated by radiolysis of aqueous solutions. These radicals are more selective in their reactions with amino acids than the hydroxyl radical. Factors controlling the apparent reactivity of radical anions with proteins, such as free radical equilibria and ion-binding, are described. The superoxide radical inactivates papain by reaction with the cysteine residue. This reaction has been studied in solutions subjected to radiations of varying linear energy transfer. (Auth.)

  13. Lattice dynamics of lithium oxide

    Indian Academy of Sciences (India)

    Abstract. Li2O finds several important technological applications, as it is used in solid- state batteries, can be used as a blanket breeding material in nuclear fusion reactors, etc. Li2O exhibits a fast ion phase, characterized by a thermally induced dynamic disorder in the anionic sub-lattice of Li+, at elevated temperatures ...

  14. Theoretical investigation of the reaction of Mn+ with ethylene oxide.

    Science.gov (United States)

    Li, Yuanyuan; Guo, Wenyue; Zhao, Lianming; Liu, Zhaochun; Lu, Xiaoqing; Shan, Honghong

    2012-01-12

    The potential energy surfaces of Mn(+) reaction with ethylene oxide in both the septet and quintet states are investigated at the B3LYP/DZVP level of theory. The reaction paths leading to the products of MnO(+), MnO, MnCH(2)(+), MnCH(3), and MnH(+) are described in detail. Two types of encounter complexes of Mn(+) with ethylene oxide are formed because of attachments of the metal at different sites of ethylene oxide, i.e., the O atom and the CC bond. Mn(+) would insert into a C-O bond or the C-C bond of ethylene oxide to form two different intermediates prior to forming various products. MnO(+)/MnO and MnH(+) are formed in the C-O activation mechanism, while both C-O and C-C activations account for the MnCH(2)(+)/MnCH(3) formation. Products MnO(+), MnCH(2)(+), and MnH(+) could be formed adiabatically on the quintet surface, while formation of MnO and MnCH(3) is endothermic on the PESs with both spins. In agreement with the experimental observations, the excited state a(5)D is calculated to be more reactive than the ground state a(7)S. This theoretical work sheds new light on the experimental observations and provides fundamental understanding of the reaction mechanism of ethylene oxide with transition metal cations.

  15. An investigation of oxidation products and SOA yields from OH + pesticide reactions

    Science.gov (United States)

    Murschell, T.; Friedman, B.; Link, M.; Farmer, D.

    2016-12-01

    Pesticides are used globally in agricultural and residential areas. After application and/or volatilization from a surface, these compounds can be transported over long distances in the atmosphere. However, their chemical fate, including oxidation and gas-particle partitioning in the atmosphere, is not well understood. We present gas and particle measurements of oxidation products from pesticide + OH reactions using a dynamic solution injection system coupled to an Oxidative Flow Reactor. Products were detected with a High Resolution Time of Flight Iodide Chemical Mass Spectrometer (HR-ToF-CIMS) and a Size Mobility Particle Scanner (SMPS). The OFR allows pesticides to react with variable OH radical exposures, ranging from the equivalent of one day to a full week of atmospheric oxidative aging. In this work, we explore pesticide oxidation products from reaction with OH and ozone, and compare those products to photolysis reactions. Pesticides of similar chemical structures were explored, including acetochlor / metolachlor and permethrin / cypermethrin, to explore mechanistic differences. We present chemical parameters including average product oxidation state, average oxygen to carbon ratio, and potential secondary organic aerosol formation for each of these compounds.

  16. SiO mass spectrometry and Si-2p photoemission spectroscopy for the study of oxidation reaction dynamics of Si(001) surface by supersonic O sub 2 molecular beams under 1000K

    CERN Document Server

    Teraoka, Y; Moritani, K

    2003-01-01

    The Si sup 1 sup 8 O desorption yield was measured in the Si(001) surface temperature region from 900K to 1300K at the sup 1 sup 8 O sub 2 incident energies of 0.7eV, 2.2eV and 3.3eV. The Si sup 1 sup 8 O desorption yield in a surface temperature region higher than 1000K increased with increasing incident energy, indicating the incident-energy-induced oxidation and the variation of angular distribution of Si sup 1 sup 8 O desorption. Inversely, the Si sup 1 sup 8 O desorption yield decreased with increasing incident energy in the region from 900K to 1000K, indicating the coexistence of the passive and the active oxidation. In order to clarify the reaction mechanisms of the later phenomenon, real-time in-situ Si-2p photoemission spectroscopy has been performed. The obtained Si-2p spectra showed the variation of the oxide-nuclei quality from the sub-oxide-rich structure to the SiO sub 2 -rich structure. The formation of the SiO sub 2 structure suppresses the SiO desorption due to the enhanced O sub 2 sticking a...

  17. Gas phase reactions of nitrogen oxides with olefins

    Energy Technology Data Exchange (ETDEWEB)

    Altshuller, A P; Cohen, I

    1961-01-01

    The nature of the condensation products formed in the gas phase reactions of nitrogen dioxide and nitric oxide with pentene-1, 2-methylbutene-2, and 2-methylbutadiene-1,3 was investigated. The reactants were combined at partial pressures in the range of 0.1 to 2.5 mm with the total pressure at one atmosphere. The products were determined by infrared and ultraviolet spectroscopy and colorimetry. The condensates included primary and secondary nitro compounds and alkyl nitrates. Strong hydroxyl and single bond carbon to oxygen stretching vibrations indicate the presence of either nitroalcohols or simple aliphatic alcohols formed through oxidation reactions. Carbonyl stretching frequencies observable in some of the reactions support the conclusion that a portion of the reactants disappear by oxidation rather than by nitration processes. The available results do not indicate the presence of appreciable amounts of tert.-nitro compounds, conjugated nitro-olefins, or gem-dinitro-alkanes. The reactivities of the olefins with the nitrogen oxides are in the decreasing order: 2-methyl-butadiene-1,3, 2-methylbutene-2, pentene-1. 20 references.

  18. Kinetics of the gas-phase tritium oxidation reaction

    International Nuclear Information System (INIS)

    Failor, R.A.

    1989-01-01

    Homogeneous gas-phase kinetics of tritium oxidation (2T 2 + O 2 →2T 2 O) have been studied with a model that accounts explicitly for radiolysis of the major species and the kinetics of the subsequent reactions of ionic, excited-state, and neutral species. Results from model calculations are given for 10 -4 -1.0 mol% T 2 in O 2 (298 K, 1 atm). As the reaction evolves three different mechanisms control T 2 O production, each with a different overall rate expression and a different order with respect to the T 2 concentration. The effects of self-radiolysis of pure T 2 on the tritium oxidation reaction were calculated. Tritium atoms, the primary product of T 2 self-radiolysis, altered the oxidation mechanism only during the first few seconds following the initiation of the T 2 -O 2 reaction. Ozone, an important intermediate in T 2 oxidation, was monitored in-situ by U.V. absorption spectroscopy for 0.01-1.0 mol% T 2 an 1 atm O 2 . The shape of the experimental ozone time profile agreed with the model predictions. As predicted, the measured initial rate of ozone production varied linearly with initial T 2 concentration ([T 2 ] 0.6 o ), but at an initial rate one-third the predicted value. The steady-state ozone concentration ([O 3 ]ss) was predicted to be dependent on [T 2 ] 0.3 o , but the measured value was [T 2 ] 0.6 o , resulting in four times higher [O 3 ]ss than predicted for a 1.0% T 2 -O 2 mixture. Adding H 2 to the T 2 -O 2 mixture, to provide insight into the differences between the radiolytic and chemical behavior of the tritium, produced a greater decrease in [O 3 ]ss than predicted. Adjusting the reaction cell surface-to-volume ratio showed implications of minor surface removal of ozone

  19. Kinetic and reaction pathways of methanol oxidation on platinum

    International Nuclear Information System (INIS)

    McCabe, R.W.; McCready, D.F.

    1986-01-01

    Methanol oxidation kinetics were measured on Pt wires in a flow reactor at pressures between 30 and 130 Pa. The kinetics were measured as a function of oxygen-to-methanol equivalence ratio phi and wire temperature. In methanol-lean feeds (phi 2 CO, CO 2 , and H 2 O were the only products; in methanol-rich feeds (phi > 1), CO, H 2 , H 2 CO, CO 2 , and H 2 O were observed. Experiments with 18 O 2 showed that the principal methanol oxidation pathway does not involve C-O bond dissociation. However, the 18 O 2 experiments, together with other features of the methanol oxidation data, also provided evidence for a minor oxidation pathway (accounting for less than 1% of the product CO 2 ) which proceeds through a carbon intermediate. A mathematical model is presented which describes the principal CH 3 OH oxidation pathway as a series reaction involving adsorbed H 2 CO and CO intermediates. Consistent with experimental results, the model predicts that inhibition by adsorbed CO should be weaker for CH 3 OH and H 2 CO oxidation than for CO oxidation. 34 references, 10 figures, 2 tables

  20. Pulse radiolysis study on oxidation reactions of gallic acid

    International Nuclear Information System (INIS)

    Dwibedy, P.; Dey, G.R.; Naik, D.B.; Kishore, Kamal

    1998-01-01

    Reactions of OH . /O - and other oxidising radicals viz. N 3 . , Br 2 .- , Cl 2 .- with gallic acid (GA) have been studied at various pHs. At pH 6.8, OH . radicals react with GA giving an adduct which in turn reacts with the parent GA to give a dimeric species. At pH 9.7, the initial OH adduct formed is able to oxidize GA to give a semi-oxidised species. At pH 12 and ∼ 13.6, OH . /O .- radicals directly bring about oxidation of GA. (author)

  1. Photocatalytic oxidation dynamics of acetone on TiO2: tight-binding quantum chemical molecular dynamics study

    International Nuclear Information System (INIS)

    Lv Chen; Wang Xiaojing; Agalya, Govindasamy; Koyama, Michihisa; Kubo, Momoji; Miyamoto, Akira

    2005-01-01

    The clarification of the excited states dynamics on TiO 2 surface is important subject for the design of the highly active photocatalysts. In the present study, we applied our novel tight-binding quantum chemical molecular dynamics method to the investigation on the photocatalytic oxidation dynamics of acetone by photogenerated OH radicals on the hydrated anatase TiO 2 surface. The elucidated photocatalytic reaction mechanism strongly supports the previous experimental proposal and finally the effectiveness of our new approach for the clarification of the photocatalytic reaction dynamics employing the large simulation model was confirmed

  2. Electromagnetic Reactions and Few-Nucleon Dynamics

    Directory of Open Access Journals (Sweden)

    Bacca Sonia

    2014-03-01

    Full Text Available We present an update on recent theoretical studies of electromagnetic reactions obtained by using the Lorentz integral transform method. The 4He nucleus will be the main focus of this report: results for the photo-disintegration and the electro-disintegration processes will be shown, as well as a recent calculation of polarizability effects in muonic atoms. We also discuss the exciting possibility to investigate inelastic reactions for mediummass nuclei in coupled-cluster theory, highlighted by the recent application to the 16O photo-nuclear cross section.

  3. Molecular dynamics for reactions of heterogeneous catalysis

    NARCIS (Netherlands)

    Jansen, A.P.J.; Brongersma, H.H.; Santen, van R.A.

    1991-01-01

    An overview is given of Molecular Dynamics, and numerical integration techniques, system initialization, boundary conditions, force representation, statistics, system size, and simulations duration are discussed. Examples from surface science are used to illustrate the pros and cons of the method.

  4. Dynamic CT of tuberculous meningeal reactions

    International Nuclear Information System (INIS)

    Jinkins, J.R.

    1987-01-01

    The technique of intravenous dynamic cranial computed tomography has been applied to the patient population at this location in Saudi Arabia with meningeal tuberculosis. The various manifestations and sequelae including meningitis, arteritis, infarct, and true meningeal tuberculomata all have characteristic if not specific appearances. The dynamic study enhances an otherwise static examination and reveals a great deal about the pathophysiology of tuberculosis involving the cerebral meningeal surfaces. (orig.)

  5. Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants.

    Science.gov (United States)

    Zhang, Linyao; Yang, Li; Zhao, Yijun; Zhang, Jiaxu; Feng, Dongdong; Sun, Shaozeng

    2017-07-06

    The water dilute oxy-fuel combustion is a clean combustion technology for near-zero emission power; and the presence of water molecule could have both kinetic and dynamic effects on combustion reactions. The reaction OH + CO → CO 2 + H, one of the most important elementary reactions, has been investigated by extensive electronic structure calculations. And the effects of a single water molecule on CO oxidation have been studied by considering the preformed OH(H 2 O) complex reacts with CO. The results show little change in the reaction pathways, but the additional water molecule actually increases the vibrationally adiabatic energy barriers (V a G ). Further thermal rate constant calculations in the temperature range of 200 to 2000 K demonstrate that the total low-pressure limit rate constant for the water assisted OH(H 2 O) + CO → CO 2 + H 2 O + H reaction is 1-2 orders lower than that of the water unassisted one, which is consistent with the change of V a G . Therefore, the hydrated radical OH(H 2 O) would actually slow down the oxidation of CO. Meanwhile, comparisons show that the M06-2X/aug-cc-pVDZ method gives a much better estimation in energy and thus is recommended to be employed for direct dynamics simulations.

  6. The oxidative burst reaction in mammalian cells depends on gravity

    OpenAIRE

    Adrian, A; Schoppmann, K; Sromicki, J; Brungs, S; von der Wiesche, M; Hock, B; Kolanus, W; Hemmersbach, R; Ullrich, O

    2013-01-01

    Gravity has been a constant force throughout the Earth's evolutionary history. Thus, one of the fundamental biological questions is if and how complex cellular and molecular functions of life on Earth require gravity. In this study, we investigated the influence of gravity on the oxidative burst reaction in macrophages, one of the key elements in innate immune response and cellular signaling. An important step is the production of superoxide by the NADPH oxidase, which is rapidly converted to...

  7. Reaction pathways for catalytic gas-phase oxidation of glycerol over mixed metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Suprun, W.; Glaeser, R.; Papp, H. [Leipzig Univ. (Germany). Inst. of Chemical Technology

    2011-07-01

    Glycerol as a main by-product from bio-diesel manufacture is a cheap raw material with large potential for chemical or biochemical transformations to value-added C3-chemicals. One possible way of glycerol utilization involves its catalytic oxidation to acrylic acid as an alternative to petrochemical routes. However, this catalytic conversion exhibits various problems such as harsh reaction conditions, severe catalyst coking and large amounts of undesired by-products. In this study, the reaction pathways for gas-phase conversion of glycerol over transition metal oxides (Mo, V und W) supported on TiO{sub 2} and SiO{sub 2} were investigated by two methods: (i) steady state experiments of glycerol oxidation and possible reactions intermediates, i.e., acrolein, 3-hydroxy propionaldehyde and acetaldehyde, and (ii) temperature-programmed surface reaction (TPSR) studies of glycerol conversion in the presence and in the absence of gas-phase oxygen. It is shown that the supported W-, V and Mo-oxides possess an ability to catalyze the oxidation of glycerol to acrylic acid. These investigations allowed us to gain a deeper insight into the reaction mechanism. Thus, based on the obtained results, three possible reactions pathways for the selective oxidation of glycerol to acrylic acid on the transition metal-containing catalysts are proposed. The major pathways in presence of molecular oxygen are a fast successive destructive oxidation of glycerol to CO{sub x} and the dehydration of glycerol to acrolein which is a rate-limiting step. (orig.)

  8. Testing string dynamics in lepton nucleus reactions

    International Nuclear Information System (INIS)

    Gyulassy, M.; Pluemer, M.

    1989-10-01

    The sensitivity of nuclear attenuation of 10-100 GeV lepton nucleus (ell A) reactions to space-time aspects of hadronization is investigated within the context of the Lund string model. We consider two mechanisms for attenuation in a nucleus: final state cascading and string flip excitations. Implications for the evolution of the energy density in nuclear collisions are discussed. 16 refs., 10 figs

  9. Covalently Bonded Chitosan on Graphene Oxide via Redox Reaction

    Directory of Open Access Journals (Sweden)

    Víctor M. Castaño

    2013-03-01

    Full Text Available Carbon nanostructures have played an important role in creating a new field of materials based on carbon. Chemical modification of carbon nanostructures through grafting has been a successful step to improve dispersion and compatibility in solvents, with biomolecules and polymers to form nanocomposites. In this sense carbohydrates such as chitosan are extremely valuable because their functional groups play an important role in diversifying the applications of carbon nanomaterials. This paper reports the covalent attachment of chitosan onto graphene oxide, taking advantage of this carbohydrate at the nanometric level. Grafting is an innovative route to modify properties of graphene, a two-dimensional nanometric arrangement, which is one of the most novel and promising nanostructures. Chitosan grafting was achieved by redox reaction using different temperature conditions that impact on the morphology and features of graphene oxide sheets. Transmission Electron Microscopy, Fourier Transform Infrared, Raman and Energy Dispersive spectroscopies were used to study the surface of chitosan-grafted-graphene oxide. Results show a successful modification indicated by the functional groups found in the grafted material. Dispersions of chitosan-grafted-graphene oxide samples in water and hexane revealed different behavior due to the chemical groups attached to the graphene oxide sheet.

  10. Positive patch test reactions to oxidized limonene: exposure and relevance.

    Science.gov (United States)

    Bråred Christensson, Johanna; Andersen, Klaus E; Bruze, Magnus; Johansen, Jeanne D; Garcia-Bravo, Begoña; Gimenez Arnau, Ana; Goh, Chee-Leok; Nixon, Rosemary; White, Ian R

    2014-11-01

    R-Limonene is a common fragrance terpene found in domestic and industrial products. R-Limonene autoxidizes on air exposure, and the oxidation products can cause contact allergy. In a recent multicentre study, 5.2% (range 2.3-12.1%) of 2900 patients showed a positive patch test reaction to oxidized R-limonene. To study the exposure to limonene among consecutive dermatitis patients reacting to oxidized R-limonene in an international setting, and to assess the relevance of the exposure for the patients' dermatitis. Oxidized R-limonene 3.0% (containing limonene hydroperoxides at 0.33%) in petrolatum was tested in 2900 consecutive dermatitis patients in Australia, Denmark, the United Kingdom, Singapore, Spain, and Sweden. A questionnaire assessing exposure to limonene-containing products was completed. Overall, exposure to products containing limonene was found and assessed as being probably relevant for the patients' dermatitis in 36% of the limonene-allergic patients. In Barcelona and Copenhagen, > 70% of the patients were judged to have had an exposure to limonene assessed as relevant. Oxidized R-limonene is a common fragrance allergen, and limonene was frequently found in the labelling on the patients' products, and assessed as relevant for the patients' dermatitis. A large number of domestic and occupational sources for contact with R-limonene were identified. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  11. NATO Advanced Study Institute on Advances in Chemical Reaction Dynamics

    CERN Document Server

    Capellos, Christos

    1986-01-01

    This book contains the formal lectures and contributed papers presented at the NATO Advanced Study Institute on. the Advances in Chemical Reaction Dynamics. The meeting convened at the city of Iraklion, Crete, Greece on 25 August 1985 and continued to 7 September 1985. The material presented describes the fundamental and recent advances in experimental and theoretical aspects of, reaction dynamics. A large section is devoted to electronically excited states, ionic species, and free radicals, relevant to chemical sys­ tems. In addition recent advances in gas phase polymerization, formation of clusters, and energy release processes in energetic materials were presented. Selected papers deal with topics such as the dynamics of electric field effects in low polar solutions, high electric field perturbations and relaxation of dipole equilibria, correlation in picosecond/laser pulse scattering, and applications to fast reaction dynamics. Picosecond transient Raman spectroscopy which has been used for the elucidati...

  12. Analysis of Brownian Dynamics Simulations of Reversible Bimolecular Reactions

    KAUST Repository

    Lipková, Jana

    2011-01-01

    A class of Brownian dynamics algorithms for stochastic reaction-diffusion models which include reversible bimolecular reactions is presented and analyzed. The method is a generalization of the λ-bcȳ model for irreversible bimolecular reactions which was introduced in [R. Erban and S. J. Chapman, Phys. Biol., 6(2009), 046001]. The formulae relating the experimentally measurable quantities (reaction rate constants and diffusion constants) with the algorithm parameters are derived. The probability of geminate recombination is also investigated. © 2011 Society for Industrial and Applied Mathematics.

  13. Transverse flow reactor studies of the dynamics of radical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Macdonald, R.G. [Argonne National Laboratory, IL (United States)

    1993-12-01

    Radical reactions are in important in combustion chemistry; however, little state-specific information is available for these reactions. A new apparatus has been constructed to measure the dynamics of radical reactions. The unique feature of this apparatus is a transverse flow reactor in which an atom or radical of known concentration will be produced by pulsed laser photolysis of an appropriate precursor molecule. The time dependence of individual quantum states or products and/or reactants will be followed by rapid infrared laser absorption spectroscopy. The reaction H + O{sub 2} {yields} OH + O will be studied.

  14. Ionic Conductivity and its Role in Oxidation Reactions

    Science.gov (United States)

    Tamimi, Mazin Abdulla

    In the field of solid oxide fuel cells (SOFCs), a substantial portion of research is focused on the ability of some oxide materials to conduct oxygen anions through their structure. For electrolytes, the benefits of improving bulk transport of ions are obvious: decrease the resistive losses of the electrolyte, and device efficiency goes up and higher power densities are possible. Even for cathode materials, better bulk ion transport leads to an increase in the oxygen exchange rate at the cathode surface, and the oxygen reduction reaction at the cathode surface is the rate limiting step for SOFC operation at intermediate temperatures (500-700ºC). As operation in this regime is a key step towards lowering the manufacturing cost and increasing the lifetime of devices, much effort is spent searching for new, more conductive materials, and analyzing existing materials to discover the structure-activity relationships that influence ionic conductivity. In the first part of this work, an overview is given of the neutron powder diffraction (NPD) techniques that are used to probe the structure of the materials in later parts. In the second part, NPD was used to analyze the structures of perovskite-type cathode materials, and show that increases in bulk conductivity led to increases in the surface oxygen exchange rate of these materials. In the final part, the methods used for SOFC cathode design were applied towards the design of oxide catalysts used for certain hydrocarbon partial oxidation reactions. The reactions studied follow the Mars van Krevelen mechanism, where oxygen atoms in the catalyst are consumed as part of the reaction and are subsequently replenished by oxygen in the gas phase. Similar to SOFC cathode operation, these processes include an oxygen reduction step, so it was hypothesized that increasing the ionic conductivity of the catalysts would improve their performance, just as it does for SOFC cathode materials. While the results are preliminary, the

  15. Mechanism of catalytic action of oxide systems in reactions of aldehyde oxidation to carboxylic acids

    International Nuclear Information System (INIS)

    Andrushkevich, T.V.

    1997-01-01

    Mechanism of selective action of oxide catalysts (on the base of V 2 O 4 , MoO 3 ) of aldehyde oxidation to acids is considered, reaction acrolein oxidation to acrylic acid is taken as an example. Multistage mechanism of the process is established; it involves consequent transformation of coordination-bonded aldehyde into carbonyl-bonded aldehyde and symmetric carboxylate. Principles of active surface construction are formulated, they take into account the activity of stabilization center of concrete intermediate compound and bond energy of oxygen with surface. (author)

  16. A network dynamics approach to chemical reaction networks

    Science.gov (United States)

    van der Schaft, A. J.; Rao, S.; Jayawardhana, B.

    2016-04-01

    A treatment of a chemical reaction network theory is given from the perspective of nonlinear network dynamics, in particular of consensus dynamics. By starting from the complex-balanced assumption, the reaction dynamics governed by mass action kinetics can be rewritten into a form which allows for a very simple derivation of a number of key results in the chemical reaction network theory, and which directly relates to the thermodynamics and port-Hamiltonian formulation of the system. Central in this formulation is the definition of a balanced Laplacian matrix on the graph of chemical complexes together with a resulting fundamental inequality. This immediately leads to the characterisation of the set of equilibria and their stability. Furthermore, the assumption of complex balancedness is revisited from the point of view of Kirchhoff's matrix tree theorem. Both the form of the dynamics and the deduced behaviour are very similar to consensus dynamics, and provide additional perspectives to the latter. Finally, using the classical idea of extending the graph of chemical complexes by a 'zero' complex, a complete steady-state stability analysis of mass action kinetics reaction networks with constant inflows and mass action kinetics outflows is given, and a unified framework is provided for structure-preserving model reduction of this important class of open reaction networks.

  17. Dynamic screening in solar and stellar nuclear reactions

    Energy Technology Data Exchange (ETDEWEB)

    Daeppen, W. [Department of Physics and Astronomy, University of Southern California, Los Angeles, CA (United States); Mussack, K. [Los Alamos National Laboratory, XTD-2, Los Alamos, NM (United States)

    2012-02-15

    In the hot, dense plasma of solar and stellar interiors, Coulomb potentials are screened, resulting in increased nuclear reaction rates. Although Salpeter's approximation for static screening is widely accepted and used in stellar modeling, the question of screening in nuclear reactions was revisited in the 1990s. In particular the issue of dynamic effects was raised by Shaviv and Shaviv, who applied the techniques of molecular dynamics to the conditions in the Sun's core in order to numerically determine the effect of screening. By directly calculating the motion of ions and electrons due to Coulomb interactions, the simulations are used to compute the effect of screening without the mean-field assumption inherent in Salpeter's approximation. In the last few years, the USC group has first reproduced Shaviv and Shaviv's numerical analysis of the screening energy, showing an effect of dynamic screening. When the consequence for the reaction-rate was computed, a rather surprising resulted, which is contrary to that from static screening theory. Our calculations showed that dynamic screening does not significantly change the reaction rate from that of the bare Coulomb potential. If this can be independently confirmed, then the effects of dynamic screening are highly relevant and should be included in stellar nuclear reaction rates (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  18. Bayesian inversion analysis of nonlinear dynamics in surface heterogeneous reactions.

    Science.gov (United States)

    Omori, Toshiaki; Kuwatani, Tatsu; Okamoto, Atsushi; Hukushima, Koji

    2016-09-01

    It is essential to extract nonlinear dynamics from time-series data as an inverse problem in natural sciences. We propose a Bayesian statistical framework for extracting nonlinear dynamics of surface heterogeneous reactions from sparse and noisy observable data. Surface heterogeneous reactions are chemical reactions with conjugation of multiple phases, and they have the intrinsic nonlinearity of their dynamics caused by the effect of surface-area between different phases. We adapt a belief propagation method and an expectation-maximization (EM) algorithm to partial observation problem, in order to simultaneously estimate the time course of hidden variables and the kinetic parameters underlying dynamics. The proposed belief propagation method is performed by using sequential Monte Carlo algorithm in order to estimate nonlinear dynamical system. Using our proposed method, we show that the rate constants of dissolution and precipitation reactions, which are typical examples of surface heterogeneous reactions, as well as the temporal changes of solid reactants and products, were successfully estimated only from the observable temporal changes in the concentration of the dissolved intermediate product.

  19. Crossed molecular beam studies of unimolecular reaction dynamics

    International Nuclear Information System (INIS)

    Buss, R.J.

    1979-04-01

    The study of seven radical-molecule reactions using the crossed molecular beam technique with supersonic nozzle beams is reported. Product angular and velocity distributions were obtained and compared with statistical calculations in order to identify dynamical features of the reactions. In the reaction of chlorine and fluorine atoms with vinyl bromide, the product energy distributions are found to deviate from predictions of the statistical model. A similar effect is observed in the reaction of chlorine atoms with 1, 2 and 3-bromopropene. The reaction of oxygen atoms with ICl and CF 3 I has been used to obtain an improved value of the IO bond energy, 55.0 +- 2.0 kcal mol -1 . In all reactions studied, the product energy and angular distributions are found to be coupled, and this is attributed to a kinematic effect of the conservation of angular momentum

  20. Insight into the Reaction Mechanism of Graphene Oxide with Oxidative Free Radical

    Institute of Scientific and Technical Information of China (English)

    ZHOU Xuejiao; XU Liangyou

    2017-01-01

    Graphene oxide(GO),as an important derivative of graphene,could be considered as a super aromatic molecule decorated with a range of reactive oxygen-containing groups on its surface,which endows graphene high reactivity with other molecules.In our previous work,we demonstrated that GO sheets were cut into small pieces(graphene quantum dots,GQDs) by oxidative free radicals(hydroxyl radical HO or oxygen radical [O]) under UV irradiation.It is notable that reactions involving free radicals are influenced by reaction conditions pronouncedly.However,researches on details about reactions of GO with free radicals have not been reported thus far.In this work,the effects of different factors on the photo-Fenton reaction of GO were studied.It is demonstrated that the reaction rate is closely related to the concentration of free radicals.It is speculated that through the optimization of reaction conditions,the reaction of graphene with free radicals could carry out efficiently for further applications.

  1. The dynamics of the Hg + Br2 reaction: elucidation of the reaction mechanism for the Br exchange reaction.

    Science.gov (United States)

    Jambrina, P G; Menéndez, M; Aoiz, F J

    2017-06-28

    In spite of its importance in the Hg atmospheric chemistry, the dynamics of the Hg + Br 2 → HgBr + Br reaction is poorly understood. In this article, we have carried out a comprehensive study of the reaction mechanism of this reaction by means of quasiclassical trajectories (QCTs) on an existing ab initio potential energy surface (PES). The reaction has a non trivial dynamics, as a consequence of its large endothermicity, the presence of a deep potential well, and the competition between the Br exchange and the collision induced dissociation processes. Our calculations demonstrate that insertion is only relevant at energies just above the reaction threshold and that, at energies above 2.3 eV, HgBr formation typically takes place via a sort of frustrated dissociation. In order to compare directly with the results obtained in extensive cross molecular beam experiments for the homologous reaction with I 2 , angular distributions in the laboratory frame for Hg + Br 2 have been simulated under similar experimental conditions. The lack of agreement at the highest energies considered suggests that either the two reactions have substantially different mechanisms or that calculations on a single PES cannot account for the dynamics at those energies.

  2. Radiolytic oxidation of propane: computer modeling of the reaction scheme

    International Nuclear Information System (INIS)

    Gupta, A.K.; Hanrahan, R.J.

    1991-01-01

    The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25 o C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases. (author)

  3. Direct Reaction of Amides with Nitric Oxide To Form Diazeniumdiolates

    Science.gov (United States)

    2015-01-01

    We report the apparently unprecedented direct reaction of nitric oxide (NO) with amides to generate ions of structure R(C=O)NH–N(O)=NO–, with examples including R = Me (1a) or 3-pyridyl (1b). The sodium salts of both released NO in pH 7.4 buffer, with 37 °C half-lives of 1–3 min. As NO-releasing drug candidates, diazeniumdiolated amides would have the advantage of generating only 1 equiv of base on hydrolyzing exhaustively to NO, in contrast to their amine counterparts, which generate 2 equiv of base. PMID:25210948

  4. Gas-Solid Reaction Route toward the Production of Intermetallics from Their Corresponding Oxide Mixtures

    Directory of Open Access Journals (Sweden)

    Hesham Ahmed

    2016-08-01

    Full Text Available Near-net shape forming of metallic components from metallic powders produced in situ from reduction of corresponding pure metal oxides has not been explored to a large extent. Such a process can be probably termed in short as the “Reduction-Sintering” process. This methodology can be especially effective in producing components containing refractory metals. Additionally, in situ production of metallic powder from complex oxides containing more than one metallic element may result in in situ alloying during reduction, possibly at lower temperatures. With this motivation, in situ reduction of complex oxides mixtures containing more than one metallic element has been investigated intensively over a period of years in the department of materials science, KTH, Sweden. This review highlights the most important features of that investigation. The investigation includes not only synthesis of intermetallics and refractory metals using the gas solid reaction route but also study the reaction kinetics and mechanism. Environmentally friendly gases like H2, CH4 and N2 were used for simultaneous reduction, carburization and nitridation, respectively. Different techniques have been utilized. A thermogravimetric analyzer was used to accurately control the process conditions and obtain reaction kinetics. The fluidized bed technique has been utilized to study the possibility of bulk production of intermetallics compared to milligrams in TGA. Carburization and nitridation of nascent formed intermetallics were successfully carried out. A novel method based on material thermal property was explored to track the reaction progress and estimate the reaction kinetics. This method implies the dynamic measure of thermal diffusivity using laser flash method. These efforts end up with a successful preparation of nanograined intermetallics like Fe-Mo and Ni-W. In addition, it ends up with simultaneous reduction and synthesis of Ni-WN and Ni-WC from their oxide mixtures

  5. Reaction of hydrogen peroxide with uranium zirconium oxide solid solution - Zirconium hinders oxidative uranium dissolution

    Science.gov (United States)

    Kumagai, Yuta; Takano, Masahide; Watanabe, Masayuki

    2017-12-01

    We studied oxidative dissolution of uranium and zirconium oxide [(U,Zr)O2] in aqueous H2O2 solution to estimate (U,Zr)O2 stability to interfacial reactions with H2O2. Studies on the interfacial reactions are essential for anticipating how a (U,Zr)O2-based molten fuel may chemically degrade after a severe accident. The fuel's high radioactivity induces water radiolysis and continuous H2O2 generation. Subsequent reaction of the fuel with H2O2 may oxidize the fuel surface and facilitate U dissolution. We conducted our experiments with (U,Zr)O2 powder (comprising Zr:U mole ratios of 25:75, 40:60, and 50:50) and quantitated the H2O2 reaction via dissolved U and H2O2 concentrations. Although (U,Zr)O2 reacted more quickly than UO2, the dissolution yield relative to H2O2 consumption was far less for (U,Zr)O2 compared to that of UO2. The reaction kinetics indicates that most of the H2O2 catalytically decomposed to O2 at the surface of (U,Zr)O2. We confirmed the H2O2 catalytic decomposition via O2 production (quantitative stoichiometric agreement). In addition, post-reaction Raman scattering spectra of the undissolved (U,Zr)O2 showed no additional peaks (indicating a lack of secondary phase formation). The (U,Zr)O2 matrix is much more stable than UO2 against H2O2-induced oxidative dissolution. Our findings will improve understanding on the molten fuels and provide an insight into decommissioning activities after a severe accident.

  6. Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation

    DEFF Research Database (Denmark)

    Andersen, Martin Søgaard; Larsen, Flemming; Postma, Diederik Jan

    2001-01-01

    The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase in the inc......The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase...... in the incubation bags became depleted in O2 and enriched in CO2 and N2 and was interpreted as due to pyrite oxidation in combination with calcite dissolution. Sediment incubation provides a new method to estimate low rates of pyrite oxidation in unsaturated zone aquifer sediments. Oxidation rates of up to 9.4â10......-10 mol FeS2/gâs are measured, and the rates are only weakly correlated with the sediment pyrite content. The reactivity of pyrite, including the inhibition by FeOOH layers formed on its surface, apparently has a major effect on the rate of oxidation. The code PHREEQC 2.0 was used to calculate...

  7. Stability and dynamics of reactors with heterogeneously catalyzed reactions

    Energy Technology Data Exchange (ETDEWEB)

    Eigenberger, G [BASF A.G., Ludwigshafen am Rhein (Germany, F.R.)

    1978-12-01

    Our knowledge of causes and consequences of problems arising from instability and dynamic effects in reactors with heterogeneously catalyzed reactions has increased remarkably in recent years. Especially thermal effects, caused by the self-acceleration of an exothermic reaction in combination with heat and mass transport, are now well understood. In addition, kinetic effects, i.e. phenomena which have to be explained by the kinetic peculiarities of surface reactions, have attracted increasing interest. For both cases the state of the art will be reviewed, highlighting the physical and chemical causes of the observed phenomena.

  8. Dependence of ICF reaction dynamics on target structure

    International Nuclear Information System (INIS)

    Kumar, Kamal; Dutt, Sunil; GulI, Muntazir; Ahmad, Tauseef; Rizvi, I.A.; Ali, Sabir; Agarwal, Avinash; Kumar, R.; Chaubey, A.K.

    2016-01-01

    The projectile structure is also found responsible for the ICF reaction processes. It is found that projectile having bigger alpha cluster is more unstable towards break up. In this context, a comparative study of 12 C and 16 O ion-beams induced reactions with different targets has been done. The deduced ICF contributions for different systems have been plotted against the target charge of different targets. It is observed that target properties may also be responsible for the interplay between CF and ICF reaction dynamics

  9. Dynamics of synchrotron VUV-induced intracluster reactions

    Energy Technology Data Exchange (ETDEWEB)

    Grover, J.R. [Brookhaven National Laboratory, Upton, NY (United States)

    1993-12-01

    Photoionization mass spectrometry (PIMS) using the tunable vacuum ultraviolet radiation available at the National Synchrotron Light Source is being exploited to study photoionization-induced reactions in small van der Waals mixed complexes. The information gained includes the observation and classification of reaction paths, the measurement of onsets, and the determination of relative yields of competing reactions. Additional information is obtained by comparison of the properties of different reacting systems. Special attention is given to finding unexpected features, and most of the reactions investigated to date display such features. However, understanding these reactions demands dynamical information, in addition to what is provided by PIMS. Therefore the program has been expanded to include the measurement of kinetic energy release distributions.

  10. Porous platinum mesoflowers with enhanced activity for methanol oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhuang Lina; Wang Wenjin; Hong Feng [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China); Yang Shengchun, E-mail: ysch1209@mail.xjtu.edu.cn [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China); You Hongjun, E-mail: hjyou@mail.xjtu.edu.cn [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China); Fang Jixiang; Ding Bingjun [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China)

    2012-07-15

    Porous Pt and Pt-Ag alloy mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesized using Ag mesoflowers as sacrificial template by galvanic reaction. The silver content in Pt-Ag alloys can be facilely controlled by nitric acid treatment. And the pure Pt MFs can be obtained by selective removal of silver element from Pt{sub 72}Ag{sub 28} MFs electrochemically. Both Pt{sub 45}Ag{sub 55}, Pt{sub 72}Ag{sub 28} and pure Pt show a high catalytic performance in methanol oxidation reaction (MOR). Especially, pure Pt MFs exhibited a 2 to 3 times current density enhancement in MOR compared with the commercial used Pt black, which can be attributed to their porous nanostructure with 3-dimentional nature and small crystal sizes. - Graphical Abstract: The CVs of MOR on Pt (red) and Pt black (green) catalysts in 0.1 M HClO{sub 4} and 0.5 M CH{sub 3}OH for specific mass current. The insert shows the SEM images of two porous Pt MFs. Platinum mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesised with Ag mesoflowers as sacrificial template by galvanic replacement. The porous Pt MFs exhibited a more than 3 times enhancement in electrocatalytic performance for methanol oxidation reaction compared the commercial used Pt black. Highlights: Black-Right-Pointing-Pointer Porous Pt and Pt-Ag mesoflowers (MFs) were synthesized using Ag MFs sacrifical template. Black-Right-Pointing-Pointer Pt MFs presents an improved catalytic activity in MOR compared with Pt black. Black-Right-Pointing-Pointer We provided a facile approach for the development of high performance Pt electrocatalysts for fuel cells.

  11. Imaging the reactions of molecular dications: a new probe of dicationic reaction dynamics and energetics

    International Nuclear Information System (INIS)

    Wan-Ping Hu, S.; Harper, S.M.; Price, S.D.

    2002-01-01

    Experiments which generated angularly resolved data to prove the dynamics of dication chemical reactions were performed using a position sensitive coincidence (PSCO) apparatus, to detect in coincidence both of the charged products from such reaction. It consists of a ion source, a hemispherical energy analyser, and a time-of-flight mass spectrometer. Initial experiments to test the apparatus performance were runned on the atomic electron transfer reaction: Ne 2+ + Ar → Ne + + Ar + . Angular distributions, translational and internal energies of the product ions were extracted, as well as the scattering diagram among other data. (nevyjel)

  12. Mass transfer model for two-layer TBP oxidation reactions

    International Nuclear Information System (INIS)

    Laurinat, J.E.

    1994-01-01

    To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments. Three cases were investigated: (1) transfer of water into the TBP layer with sparging of both the aqueous and TBP layers, (2) transfer of water into the TBP layer with sparging of just the TBP layer, and (3) transfer of butanol into the aqueous layer with sparging of both layers. The TBP layer was comprised of 99% pure TBP (spiked with butanol for the butanol transfer experiments), and the aqueous layer was comprised of either water or an aluminum nitrate solution. The liquid layers were air sparged to simulate the mixing due to the evolution of gases generated by oxidation reactions. A plastic tube and a glass frit sparger were used to provide different size bubbles. Rates of mass transfer were measured using infrared spectrophotometers provided by SRTC/Analytical Development

  13. Catalyzed oxidation reactions. IV. Picolinic acid catalysis of chromic acid oxidations

    International Nuclear Information System (INIS)

    Rocek, J.; Peng, T.Y.

    1977-01-01

    Picolinic acid and several closely related acids are effective catalysts in the chromic acid oxidation of primary and secondary alcohols; the oxidation of other substrates is accelerated only moderately. The reaction is first order in chromium-(VI), alcohol, and picolinic acid; it is second order in hydrogen ions at low acidity and approaches acidity independence at high perchloric acid concentrations. A primary deuterium kinetic isotope effect is observed at high but not at low acidities. At low acidity the reaction has a considerably lower activation energy and more negative activation entropy than at higher acidities. The reactive intermediate in the proposed mechanism is a negatively charged termolecular complex formed from chromic acid, picolinic acid, and alcohol. The rate-limiting step of the reaction changes with the acidity of the solution. At higher acidities the intermediate termolecular complex is formed reversibly and the overall reaction rate is determined by the rate of its decomposition into reaction products; at low acidities the formation of the complex is irreversible and hence rate limiting. Picolinic acids with a substituent in the 6 position show a greatly reduced catalytic activity. This observation is interpreted as suggesting a square pyramidal or octahedral structure for the reactive chromium (VI) intermediate. The temperature dependence of the deuterium isotope effect has been determined and the significance of the observed large values for E/sub a//sup D/ - E/sub a//sup H/ and A/sup D//A/sup H/ is discussed

  14. Activity of molybdenum-containing oxide catalysts in the reaction of ethane oxidation

    International Nuclear Information System (INIS)

    Konovalov, V.I.; Ehpova, T.I.; Shchukin, V.P.; Averbukh, A.Ya.

    1977-01-01

    Investigation results concerning the catalytic activity of molybdenum-containing catalysts in ethane oxidation reaction are presented. It has been found that the greatest activity in the temperature range from 450 to 600 deg C is exhibited by cobalt-molybdenum catalyst; at 600 deg C bismuth-molybdenum catalyst is the most active. Nickel-molybdenum catalyst is selective and active with respect to ethylene. Iron- and manganese-molybdenum catalysts do not show high ethane oxidation rates and their selectivity is insignificant

  15. Fractal sets generated by chemical reactions discrete chaotic dynamics

    International Nuclear Information System (INIS)

    Gontar, V.; Grechko, O.

    2007-01-01

    Fractal sets composed by the parameters values of difference equations derived from chemical reactions discrete chaotic dynamics (DCD) and corresponding to the sequences of symmetrical patterns were obtained in this work. Examples of fractal sets with the corresponding symmetrical patterns have been presented

  16. RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics

    KAUST Repository

    Suleimanov, Yu.V.

    2013-03-01

    We present RPMDrate, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett-Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH 4, OH+CH4 and H+C2H6 reactions. © 2012 Elsevier B.V. All rights reserved.

  17. RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics

    KAUST Repository

    Suleimanov, Yu.V.; Allen, J.W.; Green, W.H.

    2013-01-01

    We present RPMDrate, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett-Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH 4, OH+CH4 and H+C2H6 reactions. © 2012 Elsevier B.V. All rights reserved.

  18. Dynamics of anion-molecule reactions at low energy

    International Nuclear Information System (INIS)

    Mikosch, J.

    2007-11-01

    Anion-molecule reactions must find their way through deeply bound entrance and exit channel complexes separated by a central barrier. This results in low reaction rates and rich dynamics since direct pathways compete with the formation of transient intermediates. In this thesis we examine the probability of proton transfer to a small anion and transient lifetimes of a thermoneutral bimolecular nucleophilic substitution (S N 2) reaction at well defined variable temperature down to 8 Kelvin in a multipole trap. The observed strong inverse temperature dependence is attributed to the deficit of available quantum states in the entrance channel at decreasing temperature. Furthermore we investigate scattering dynamics of S N 2 reactions at defined relative energy between 0.4 and 10 eV by crossed beam slice imaging. A weakly exothermic reaction with high central barrier proceeds via an indirect, complex-mediated mechanism at low relative energies featuring high internal product excitation in excellent quantitative agreement with a statistical model. In contrast, direct backward scattering prevails for higher energies with product velocities close to the kinematical cutoff. For a strongly exothermic reaction, competing S N 2-, dihalide- and proton transfer-channels are explored which proceed by complex mediation for low energy and various rebound-, grazing- and collision induced bond rupture-mechanisms at higher energy. From our data and a collaboration with theory we identify a new indirect roundabout S N 2 mechanism involving CH 3 -rotation. (orig.)

  19. Dynamics of anion-molecule reactions at low energy

    Energy Technology Data Exchange (ETDEWEB)

    Mikosch, J.

    2007-11-15

    Anion-molecule reactions must find their way through deeply bound entrance and exit channel complexes separated by a central barrier. This results in low reaction rates and rich dynamics since direct pathways compete with the formation of transient intermediates. In this thesis we examine the probability of proton transfer to a small anion and transient lifetimes of a thermoneutral bimolecular nucleophilic substitution (S{sub N}2) reaction at well defined variable temperature down to 8 Kelvin in a multipole trap. The observed strong inverse temperature dependence is attributed to the deficit of available quantum states in the entrance channel at decreasing temperature. Furthermore we investigate scattering dynamics of S{sub N}2 reactions at defined relative energy between 0.4 and 10 eV by crossed beam slice imaging. A weakly exothermic reaction with high central barrier proceeds via an indirect, complex-mediated mechanism at low relative energies featuring high internal product excitation in excellent quantitative agreement with a statistical model. In contrast, direct backward scattering prevails for higher energies with product velocities close to the kinematical cutoff. For a strongly exothermic reaction, competing S{sub N}2-, dihalide- and proton transfer-channels are explored which proceed by complex mediation for low energy and various rebound-, grazing- and collision induced bond rupture-mechanisms at higher energy. From our data and a collaboration with theory we identify a new indirect roundabout S{sub N}2 mechanism involving CH{sub 3}-rotation. (orig.)

  20. Kinetics of reactions of chromium, molybdenum and tungsten hexacarbonyls with hydroxylamine and trimethylamine oxide

    International Nuclear Information System (INIS)

    Maksakov, V.A.; Ershova, V.A.

    1994-01-01

    Mechanism of M(CO) 6 (M = Cr, Mo, W) reaction with hydroxylamine was studied. On the basis of kinetic data it was ascertained that as a result of the reaction CO oxidation to CO 2 and intramolecular transfer of amine formed to the central atom of metal occur. Mechanisms of M(CO) 6 reactions with hydroxylamine and trimethylamine oxide are compared

  1. A novel tandem Betti/Ullmann oxidation reaction as an efficient route ...

    Indian Academy of Sciences (India)

    Betti reaction; cross-coupling reaction; oxidation; heterogeneous catalysis. Abstract. A novel tandem Betti/Ullmann/oxidation reaction was used for synthesis of new oxazepine derivatives containing kojic acid. This protocol ... This method provides a new and useful strategy for the construction of heterocycles. Also novel Betti ...

  2. Electrode Reaction Pathway in Oxide Anode for Solid Oxide Fuel Cells

    Science.gov (United States)

    Li, Wenyuan

    Oxide anodes for solid oxide fuel cells (SOFC) with the advantage of fuel flexibility, resistance to coarsening, small chemical expansion and etc. have been attracting increasing interest. Good performance has been reported with a few of perovskite structure anodes, such as (LaSr)(CrMn)O3. However, more improvements need to be made before meeting the application requirement. Understanding the oxidation mechanism is crucial for a directed optimization, but it is still on the early stage of investigation. In this study, reaction mechanism of oxide anodes is investigated on doped YCrO 3 with H2 fuel, in terms of the origin of electrochemical activity, rate-determining steps (RDS), extension of reactive zone, and the impact from overpotential under service condition to those properties. H2 oxidation on the YCs anodes is found to be limited by charge transfer and H surface diffusion. A model is presented to describe the elementary steps in H2 oxidation. From the reaction order results, it is suggested that any models without taking H into the charge transfer step are invalid. The nature of B site element determines the H2 oxidation kinetics primarily. Ni displays better adsorption ability than Co. However, H adsorption ability of such oxide anode is inferior to that of Ni metal anode. In addition, the charge transfer step is directly associated with the activity of electrons in the anode; therefore it can be significantly promoted by enhancement of the electron activity. It is found that A site Ca doping improves the polarization resistance about 10 times, by increasing the activity of electrons to promote the charge transfer process. For the active area in the oxide anode, besides the traditional three-phase boundary (3PB), the internal anode surface as two-phase boundary (2PB) is proven to be capable of catalytically oxidizing the H2 fuel also when the bulk lattice is activated depending on the B site elements. The contribution from each part is estimated by switching

  3. A dynamical theory of incomplete fusion reactions: The breakup-fusion reaction approach

    International Nuclear Information System (INIS)

    Udagawa, T.

    1984-01-01

    A dynamical theory of partial fusion reactions is presented, which may fill the gap between direct and compound nuclear reaction theories. With the new theory one can calculate partial fusion taking place in three-body (and many more) channels reached via direct reactions, e.g., breakup and knockout reactions. The authors present first the results for the cross section for such reactions, taking as an example breakup followed by fusion. They then discuss a physical picture which emerges from their theory, namely that the partial fusion reactions, particularly of the massive-transfer type, take place in a so-called deep peripheral region. It is also shown that the deep peripheral character of such processes diminishes as the mass of the fused system decreases, so that the reactions essentially evolve to the usual peripheral character. Finally, comparisons are made of results of numerical calculations with experimental data, taking as an example the /sup 159/Tb(/sup 14/N,α) reaction with E/sub lab/ = 95 MeV

  4. Oxidation Numbers, Oxidants, and Redox Reactions: Variants of the Electrophilic Bromination of Alkenes and Variants of the Application of Oxone

    Science.gov (United States)

    Eissen, Marco; Strudthoff, Merle; Backhaus, Solveig; Eismann, Carolin; Oetken, Gesa; Kaling, Soren; Lenoir, Dieter

    2011-01-01

    Oxidation-state and donor-acceptor concepts are important areas in the chemical education. Student worksheets containing problems that emphasize oxidation numbers, redox reactions of organic compounds, and stoichiometric reaction equations are presented. All of the examples are incorporated under one unifying topic: the production of vicinal…

  5. Graphite oxide and molybdenum disulfide composite for hydrogen evolution reaction

    Science.gov (United States)

    Niyitanga, Theophile; Jeong, Hae Kyung

    2017-10-01

    Graphite oxide and molybdenum disulfide (GO-MoS2) composite is prepared through a wet process by using hydrolysis of ammonium tetrathiomolybdate, and it exhibits excellent catalytic activity of the hydrogen evolution reaction (HER) with a low overpotential of -0.47 V, which is almost two and three times lower than those of precursor MoS2 and GO. The high performance of HER of the composite attributes to the reduced GO supporting MoS2, providing a conducting network for fast electron transport from MoS2 to electrodes. The composite also shows high stability after 500 cycles, demonstrating a synergistic effect of MoS2 and GO for efficient HER.

  6. Oxidation-reduction reactions. Overview and implications for repository studies

    International Nuclear Information System (INIS)

    Apted, Michael J.; Arthur, Randolph C.; Sasamoto, Hiroshi; Yui, Mikazu; Iwatsuki, Teruki

    2001-02-01

    The purpose of this report is to provide a survey and review on oxidation-reduction ('redox') reactions, with particular emphasis on implications for disposal of high-level waste (HLW) in deep geological formations. As an overview, the focus is on basic principles, problems, and proposed research related specifically to the assessment of redox for a HLW repository in Japan. For a more comprehensive treatment of redox and the myriad associated issues, the reader is directed to the cited textbooks used as primary references in this report. Low redox conditions in deep geological formations is a key assumption in the 'Second Progress Report on Research and Development for the Geological Disposal of HLW in Japan' (hereafter called H12'). The release behavior of multi-valent radioelements (e.g., Tc, Se, U, Pu, Np), as well as daughter radioelements of these radioelements, from a deep geological repository are sensitively related to redox conditions. Furthermore, the performance of certain barrier materials, such as overpack and buffer, may be impacted by redox conditions. Given this importance, this report summarizes some key topics for future technical studies supporting site characterization and repository performance as follows: To fully test the conceptual models for system Eh, it will be necessary to measure and evaluate trace element and isotopic information of both coexisting groundwater and reactive minerals of candidate rocks. Because of importance of volatile species (e.g., O 2 , H 2 etc.) in redox reactions, and given the high total pressure of a repository located 500 to 1000 meter deep, laboratory investigations of redox will necessarily require use of pressurized test devices that can fully simulate repository conditions. The stability (redox capacity) of the repository system with respect to potential changes in redox boundary condition induced by oxidizing waters intrusion should be established experimentally. An overall conceptual model that unifies

  7. Solar Thermochemical Hydrogen Production via Terbium Oxide Based Redox Reactions

    Directory of Open Access Journals (Sweden)

    Rahul Bhosale

    2016-01-01

    Full Text Available The computational thermodynamic modeling of the terbium oxide based two-step solar thermochemical water splitting (Tb-WS cycle is reported. The 1st step of the Tb-WS cycle involves thermal reduction of TbO2 into Tb and O2, whereas the 2nd step corresponds to the production of H2 through Tb oxidation by water splitting reaction. Equilibrium compositions associated with the thermal reduction and water splitting steps were determined via HSC simulations. Influence of oxygen partial pressure in the inert gas on thermal reduction of TbO2 and effect of water splitting temperature (TL on Gibbs free energy related to the H2 production step were examined in detail. The cycle (ηcycle and solar-to-fuel energy conversion (ηsolar-to-fuel efficiency of the Tb-WS cycle were determined by performing the second-law thermodynamic analysis. Results obtained indicate that ηcycle and ηsolar-to-fuel increase with the decrease in oxygen partial pressure in the inert flushing gas and thermal reduction temperature (TH. It was also realized that the recuperation of the heat released by the water splitting reactor and quench unit further enhances the solar reactor efficiency. At TH=2280 K, by applying 60% heat recuperation, maximum ηcycle of 39.0% and ηsolar-to-fuel of 47.1% for the Tb-WS cycle can be attained.

  8. Radiolytic oxidation of propane: Computer modeling of the reaction scheme

    Science.gov (United States)

    Gupta, Avinash K.; Hanrahan, Robert J.

    The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25°C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. Minor products include i-butyl alcohol, t-amyl alcohol, n-butyl alcohol, n-amyl alcohol, and i-amyl alcohol. Small yields of i-hexyl alcohol and n-hexyl alcohol were also observed. There was no apparent difference in the G-values at pressures of 50, 100 and 150 torr. When the oxygen concentration was decreased below 5%, the yields of acetone, i-propyl alcohol, and n-propyl alcohol increased, the propionaldehyde yield decreased, and the yields of other products remained constant. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases.

  9. Kinetics and Mechanism of the Reaction of Coherently Synchronized Oxidation and Dehydrogenation of Cyclohexane by Hydrogen Peroxide

    Directory of Open Access Journals (Sweden)

    Aghamammadova S.

    2016-01-01

    Based on this experimental researches, the complex reaction, consisting of parallel-sequential oxidation and dehydrogenation reactions, which are coherently synchronized, proceeds during the process of cyclohexane oxidation with biomimetic catalyst. Depending on the reaction parameters it is possible to deliberately adjust the direction of oxidation reaction and reaction rate.

  10. Surface oxidization-reduction reactions in Columbia Plateau basalts

    International Nuclear Information System (INIS)

    White, A.F.; Yee, A.

    1984-01-01

    Results are presented which define principal oxidation-reduction reactions expected between ground water and iron in the Umtanum and Cohassett basalt flows of south central Washington. Data include kinetics of aqueous iron speciation, rates of O 2 uptake and nature of oxyhydroxide precipitates. Such data are important in predicting behavior of radionuclides in basalt aquifers including determination of valence states, speciation, solubility, sorption, and coprecipitation on iron oxyhydroxide substrates and colloids. Analyses of the basalt by XPS indicates that ferrous iron is oxidized to ferric iron on the surface and that the total iron decreases as a function of pH during experimental weathering. Iron oxyhydroxide phases did not form surface coating on basalt surfaces but rather nucleated as separate plases in solution. No significant increases in Cs or Sr sorption were observed with increased weathering of the basalt. Concurrent increases in Fe(II) and decreases in Fe(III) in slightly to moderately acid solutions indicated continued oxidization of ferrous iron in the basalt. At neutral to basic pH, Fe(II) was strongly sorbed onto the basalt surface (Kd = 6.5 x 10 -3 1 x m 2 ) resulting in low dissolved concentrations even under anoxic conditions. The rate of O 2 uptake increased with decreasing pH. Diffusion rates (-- 10 -14 cm 2 x s -1 ), calculated using a one-dimensional analytical model, indicate grain boundary diffusion. Comparisons of Eh values calculated by Pt electrode, dissolved O 2 and Fe(II)/Fe(III) measurements showed considerable divergence, with the ferric-ferrous couple being the preferred method of estimating Eh

  11. Multiscale simulations of anisotropic particles combining molecular dynamics and Green's function reaction dynamics

    NARCIS (Netherlands)

    Vijaykumar, A.; Ouldridge, T.E.; ten Wolde, P.R.; Bolhuis, P.G.

    2017-01-01

    The modeling of complex reaction-diffusion processes in, for instance, cellular biochemical networks or self-assembling soft matter can be tremendously sped up by employing a multiscale algorithm which combines the mesoscopic Green's Function Reaction Dynamics (GFRD) method with explicit stochastic

  12. Electrochemical oxidation of quaternary ammonium electrolytes : Unexpected side reactions in organic electrochemistry

    NARCIS (Netherlands)

    Nouri Nigjeh, Eslam; de Vries, Marcel; Bruins, Andries P.; Bischoff, Rainer; Permentier, Hjalmar P.

    Quaternary ammonium salts are among the most widely used electrolytes in organic electrochemistry, but there is little known about their unwanted side oxidation reactions. We have, therefore, studied the constant potential oxidation products of quaternary ammonium electrolytes using mass

  13. Reaction dynamics of electronically excited alkali atoms with simpler molecules

    International Nuclear Information System (INIS)

    Weiss, P.S.; Mestdagh, J.M.; Schmidt, H.; Vernon, M.F.; Covinsky, M.H.; Balko, B.A.; Lee, Y.T.

    1985-05-01

    The reactions of electronically excited sodium atoms with simple molecules have been studied in crossed molecular beams experiments. Electronically excited Na(3 2 P/sub 3/2/, 4 2 D/sub 5/2/, and 5 2 S/sub 1/2/) were produced by optical pumping using single frequency dye lasers. The effects of the symmetry, and the orientation and alignment of the excited orbital on the chemical reactivity, and detailed information on the reaction dynamics were derived from measurements of the product angular and velocity distributions. 12 refs., 9 figs

  14. The GC/AED studies on the reactions of sulfur mustard with oxidants

    International Nuclear Information System (INIS)

    Popiel, StanisIaw; Witkiewicz, Zygfryd; Szewczuk, Aleksander

    2005-01-01

    A gas chromatograph coupled with an atomic emission detector was used to identify and to determine the products formed on oxidation of sulfur mustard. The oxidation rate and the resulting oxidates were studied in relation to oxidant type and reaction medium parameters. Hydrogen peroxide, sodium hypochlorite, sodium perborate, potassium monopercarbonate, ammonium peroxydisulfate, potassium peroxymonosulfate (oxone), and tert-butyl peroxide were used as oxidants. Oxidations were run in aqueous media or in solvents of varying polarities. The oxidation rate was found to be strongly related to oxidant type: potassium peroxymonosulfate (oxone) and sodium hypochlorite were fast-acting oxidants; sodium perborate, hydrogen peroxide, ammonium peroxydisulfate, and sodium monopercarbonate were moderate oxidants; tert-butyl peroxide was the slowest-acting oxidant. In non-aqueous solvents, the oxidation rate was strongly related to solvent polarity. The higher the solvent polarity, the faster the oxidation rate. In the acid and neutral media, the mustard oxidation rates were comparable. In the alkaline medium, oxidation was evidently slower. A suitable choice of the initial oxidant-to-mustard concentration ratio allowed to control the type of the resulting mustard oxidates. As the pH of the reaction medium was increased, the reaction of elimination of hydrogen chloride from mustard oxidates becomes more and more intensive

  15. Chemical reaction dynamics using the Advanced Light Source

    International Nuclear Information System (INIS)

    Yang, X.; Blank, D.A.; Heimann, P.A.; Lee, Y.T.; Suits, A.G.; Lin, J.; Wodtke, A.M.

    1995-01-01

    The recently commissioned Advanced Light Source (ALS) at Berkeley provides a high brightness, tunable VUV light source for chemical dynamics studies. A dedicated chemical dynamics beamline has been built at the ALS for studies of fundamental chemical processes. High flux (10(sup 16) photon/s with 2% bandwidth) VUV synchrotron radiation from 5 to 30 eV can be obtained from the beamline, whose source is the U8/10 undulator. Three endstations will be in operation for studies ranging from crossed beam reaction dynamics and photodissociation to high resolution photoionization dynamics and spectroscopy. A rotatable source crossed molecular beam apparatus (endstation one) has been established for unimolecular and bimolecular reactive scattering studies. Photodissociation of methylamine and ozone were carried out using VUV synchrotron radiation as the ionization detection technique at this endstation. Results show the advantages of the new endstation using VUV ionization as the detection scheme over similar machines using electron bombardment as the ionization source

  16. Chemical reaction dynamics using the Advanced Light Source

    International Nuclear Information System (INIS)

    Yang, X.; Blank, D.A.; Heimann, P.A.; Lee, Y.T.; Suits, A.G.; Lin, J.; Wodtke, A.M.

    1995-09-01

    The recently commissioned Advanced Light Source (ALS) at Berkeley provides a high brightness, tunable VUV light source for chemical dynamics studies. A dedicated chemical dynamics beamline has been built at the ALS for studies of fundamental chemical processes. High flux (10 16 photon/s with 2% bandwidth) VUV synchrotron radiation from 5 to 30 eV can be obtained from the beamline, whose source is the U8/10 undulator. Three endstations will be in operation for studies ranging from crossed beam reaction dynamics and photodissociation to high resolution photoionization dynamics and spectroscopy. A rotatable source crossed molecular beam apparatus (endstation one) has been established for unimolecular and bimolecular reactive scattering studies. Photodissociation of methylamine and ozone were carried out using VUV synchrotron radiation as the ionization detection technique at this endstation. Results show the advantages of the new endstation using VUV ionization as the detection scheme over similar machines using electron bombardment as the ionization source

  17. Internal Displacement Reactions in Multicomponent Oxides: Part I. Line Compounds with Narrow Homogeneity Range

    OpenAIRE

    Reddy, SNS; Leonard, DN; Wiggins, LB; Jacob, KT

    2005-01-01

    As a model of an internal displacement reaction involving a ternary oxide line compound, the following reaction was studied at 1273 K as a function of time, t: $Fe+NiTiO_3 = Ni + FeTiO_3$ Both polycrystalline and single-crystal materials were used as the starting $NiTiO_3$ oxide. During the reaction, the Ni in the oxide compound is displaced by Fe and it precipitates as a \\gamma -(Ni-Fe) alloy. The reaction preserves the starting ilmenite structure. The product oxide has a consta...

  18. Reaction kinetics of oxygen on single-phase alloys, oxidation of nickel and niobium alloys

    International Nuclear Information System (INIS)

    Lalauze, Rene

    1973-01-01

    This research thesis first addresses the reaction kinetics of oxygen on alloys. It presents some generalities on heterogeneous reactions (conventional theory, theory of jumps), discusses the core reaction (with the influence of pressure), discusses the influence of metal self-diffusion on metal oxidation kinetics (equilibrium conditions at the interface, hybrid diffusion regime), reports the application of the hybrid diffusion model to the study of selective oxidation of alloys (Wagner model, hybrid diffusion model) and the study of the oxidation kinetics of an alloy forming a solid solution of two oxides. The second part reports the investigation of the oxidation of single phase nickel and niobium alloys (phase α, β and γ)

  19. Mn(II) oxidation in Fenton and Fenton type systems : Identification of Reaction Efficiency and Reaction Products

    NARCIS (Netherlands)

    van Genuchten, C.M.; Peña, Jasquelin

    2017-01-01

    Efficient and low-cost methods of removing aqueous Mn(II) are required to improve the quality of impacted groundwater supplies. In this work, we show that Fe(0) electrocoagulation (EC) permits the oxidative removal of Mn(II) from solution by reaction with the reactive oxidant species produced

  20. Copper-catalyzed oxidative Heck reactions between alkyltrifluoroborates and vinyl arenes.

    Science.gov (United States)

    Liwosz, Timothy W; Chemler, Sherry R

    2013-06-21

    We report herein that potassium alkyltrifluoroborates can be utilized in oxidative Heck-type reactions with vinyl arenes. The reaction is catalyzed by a Cu(OTf)2/1,10-phenanthroline with MnO2 as the stoichiometric oxidant. In addition to the alkyl Heck, amination, esterification, and dimerization reactions of alkyltrifluoroborates are demonstrated under analogous reaction conditions. Evidence for an alkyl radical intermediate is presented.

  1. Chemical memory reactions induced bursting dynamics in gene expression.

    Science.gov (United States)

    Tian, Tianhai

    2013-01-01

    Memory is a ubiquitous phenomenon in biological systems in which the present system state is not entirely determined by the current conditions but also depends on the time evolutionary path of the system. Specifically, many memorial phenomena are characterized by chemical memory reactions that may fire under particular system conditions. These conditional chemical reactions contradict to the extant stochastic approaches for modeling chemical kinetics and have increasingly posed significant challenges to mathematical modeling and computer simulation. To tackle the challenge, I proposed a novel theory consisting of the memory chemical master equations and memory stochastic simulation algorithm. A stochastic model for single-gene expression was proposed to illustrate the key function of memory reactions in inducing bursting dynamics of gene expression that has been observed in experiments recently. The importance of memory reactions has been further validated by the stochastic model of the p53-MDM2 core module. Simulations showed that memory reactions is a major mechanism for realizing both sustained oscillations of p53 protein numbers in single cells and damped oscillations over a population of cells. These successful applications of the memory modeling framework suggested that this innovative theory is an effective and powerful tool to study memory process and conditional chemical reactions in a wide range of complex biological systems.

  2. The photodissociation and reaction dynamics of vibrationally excited molecules

    Energy Technology Data Exchange (ETDEWEB)

    Crim, F.F. [Univ. of Wisconsin, Madison (United States)

    1993-12-01

    This research determines the nature of highly vibrationally excited molecules, their unimolecular reactions, and their photodissociation dynamics. The goal is to characterize vibrationally excited molecules and to exploit that understanding to discover and control their chemical pathways. Most recently the author has used a combination of vibrational overtone excitation and laser induced fluorescence both to characterize vibrationally excited molecules and to study their photodissociation dynamics. The author has also begun laser induced grating spectroscopy experiments designed to obtain the electronic absorption spectra of highly vibrationally excited molecules.

  3. Switching dynamics in reaction networks induced by molecular discreteness

    International Nuclear Information System (INIS)

    Togashi, Yuichi; Kaneko, Kunihiko

    2007-01-01

    To study the fluctuations and dynamics in chemical reaction processes, stochastic differential equations based on the rate equation involving chemical concentrations are often adopted. When the number of molecules is very small, however, the discreteness in the number of molecules cannot be neglected since the number of molecules must be an integer. This discreteness can be important in biochemical reactions, where the total number of molecules is not significantly larger than the number of chemical species. To elucidate the effects of such discreteness, we study autocatalytic reaction systems comprising several chemical species through stochastic particle simulations. The generation of novel states is observed; it is caused by the extinction of some molecular species due to the discreteness in their number. We demonstrate that the reaction dynamics are switched by a single molecule, which leads to the reconstruction of the acting network structure. We also show the strong dependence of the chemical concentrations on the system size, which is caused by transitions to discreteness-induced novel states

  4. [Studies on the oxidation reaction of octanol-2 with nitric acid by infrared spectroscopy].

    Science.gov (United States)

    Zhang, G; Zhao, G; Wang, Y; Zhang, Q; Zhang, S; Lu, F

    1998-04-01

    In this paper, the reaction process of oxidation of octanol-2 with nitric acid has been studied by IR spectroscopy. It is found that the main components of non-sapoifiable matter are different in different oxidation degrees. The relation between oxidation products and the amount of nitric acid are investigated,the reaction mechanism has also been studied. Experimental results show that the oxidation process of octanol-2 is as follows: first, octanol-2 is oxidated to octanone-2, or to nitrate, nitrite and nitrile copmpounds, then these compounds are reoxidated to caproic acid in the meantime some by-products, such as valeric, enanthic acids are also found in oxidated products.

  5. Hydrogen Oxidation Reaction at the Ni/YSZ Anode of Solid Oxide Fuel Cells from First Principles

    Science.gov (United States)

    Cucinotta, Clotilde S.; Bernasconi, Marco; Parrinello, Michele

    2011-11-01

    By means of ab initio simulations we here provide a comprehensive scenario for hydrogen oxidation reactions at the Ni/zirconia anode of solid oxide fuel cells. The simulations have also revealed that in the presence of water chemisorbed at the oxide surface, the active region for H oxidation actually extends beyond the metal/zirconia interface unraveling the role of water partial pressure in the decrease of the polarization resistance observed experimentally.

  6. Direct single-molecule dynamic detection of chemical reactions.

    Science.gov (United States)

    Guan, Jianxin; Jia, Chuancheng; Li, Yanwei; Liu, Zitong; Wang, Jinying; Yang, Zhongyue; Gu, Chunhui; Su, Dingkai; Houk, Kendall N; Zhang, Deqing; Guo, Xuefeng

    2018-02-01

    Single-molecule detection can reveal time trajectories and reaction pathways of individual intermediates/transition states in chemical reactions and biological processes, which is of fundamental importance to elucidate their intrinsic mechanisms. We present a reliable, label-free single-molecule approach that allows us to directly explore the dynamic process of basic chemical reactions at the single-event level by using stable graphene-molecule single-molecule junctions. These junctions are constructed by covalently connecting a single molecule with a 9-fluorenone center to nanogapped graphene electrodes. For the first time, real-time single-molecule electrical measurements unambiguously show reproducible large-amplitude two-level fluctuations that are highly dependent on solvent environments in a nucleophilic addition reaction of hydroxylamine to a carbonyl group. Both theoretical simulations and ensemble experiments prove that this observation originates from the reversible transition between the reactant and a new intermediate state within a time scale of a few microseconds. These investigations open up a new route that is able to be immediately applied to probe fast single-molecule physics or biophysics with high time resolution, making an important contribution to broad fields beyond reaction chemistry.

  7. Microscopic study on dynamic barrier in fusion reactions

    International Nuclear Information System (INIS)

    Wu Xizhen; Tian Junlong; Zhao Kai; Li Zhuxia; Wang Ning

    2004-01-01

    The authors briefly review the fusion process of very heavy nuclear systems and some theoretical models. The authors propose a microscopic transport dynamic model, i.e. the Improved Quantum Molecular Dynamic model, for describing fusion reactions of heavy systems, in which the dynamical behavior of the fusion barrier in heavy fusion systems has been studied firstly. The authors find that with the incident energy decreasing the lowest dynamic barrier is obtained which approaches to the adiabatic static barrier and with increase of the incident energy the dynamic barrier goes up to the diabatic static barrier. The authors also indicate that how the dynamical fusion barrier is correlated with the development of the configuration of fusion partners along the fusion path. Associating the single-particle potentials obtained at different stages of fusion with the Two Center Shell Model, authors can study the time evolution of the single particle states of fusion system in configuration space of single particle orbits along the fusion path. (author)

  8. Multiscale simulations of anisotropic particles combining molecular dynamics and Green's function reaction dynamics

    Science.gov (United States)

    Vijaykumar, Adithya; Ouldridge, Thomas E.; ten Wolde, Pieter Rein; Bolhuis, Peter G.

    2017-03-01

    The modeling of complex reaction-diffusion processes in, for instance, cellular biochemical networks or self-assembling soft matter can be tremendously sped up by employing a multiscale algorithm which combines the mesoscopic Green's Function Reaction Dynamics (GFRD) method with explicit stochastic Brownian, Langevin, or deterministic molecular dynamics to treat reactants at the microscopic scale [A. Vijaykumar, P. G. Bolhuis, and P. R. ten Wolde, J. Chem. Phys. 143, 214102 (2015)]. Here we extend this multiscale MD-GFRD approach to include the orientational dynamics that is crucial to describe the anisotropic interactions often prevalent in biomolecular systems. We present the novel algorithm focusing on Brownian dynamics only, although the methodology is generic. We illustrate the novel algorithm using a simple patchy particle model. After validation of the algorithm, we discuss its performance. The rotational Brownian dynamics MD-GFRD multiscale method will open up the possibility for large scale simulations of protein signalling networks.

  9. Degradation of quinoline by wet oxidation - kinetic aspects and reaction mechanisms

    DEFF Research Database (Denmark)

    Thomsen, A.B.

    1998-01-01

    The high temperature, high pressure wet oxidation reaction of quinoline has been studied as a function of initial concentration, pH and temperature. At neutral to acidic pH, it is effective in the oxidation of quinoline at 240 degrees C and above, whereas under alkaline conditions the reaction...... is markedly slowed down. The results indicate that the reaction is an auto-catalysed, free radical chain reaction transforming 99% of quinoline to other substances. Of the quinoline. 30-50% was oxidised to CO2 and H2O depending on the initial concentration. Wet oxidation of deuterium-labelled quinoline...

  10. Multiscale simulations of patchy particle systems combining Molecular Dynamics, Path Sampling and Green's Function Reaction Dynamics

    Science.gov (United States)

    Bolhuis, Peter

    Important reaction-diffusion processes, such as biochemical networks in living cells, or self-assembling soft matter, span many orders in length and time scales. In these systems, the reactants' spatial dynamics at mesoscopic length and time scales of microns and seconds is coupled to the reactions between the molecules at microscopic length and time scales of nanometers and milliseconds. This wide range of length and time scales makes these systems notoriously difficult to simulate. While mean-field rate equations cannot describe such processes, the mesoscopic Green's Function Reaction Dynamics (GFRD) method enables efficient simulation at the particle level provided the microscopic dynamics can be integrated out. Yet, many processes exhibit non-trivial microscopic dynamics that can qualitatively change the macroscopic behavior, calling for an atomistic, microscopic description. The recently developed multiscale Molecular Dynamics Green's Function Reaction Dynamics (MD-GFRD) approach combines GFRD for simulating the system at the mesocopic scale where particles are far apart, with microscopic Molecular (or Brownian) Dynamics, for simulating the system at the microscopic scale where reactants are in close proximity. The association and dissociation of particles are treated with rare event path sampling techniques. I will illustrate the efficiency of this method for patchy particle systems. Replacing the microscopic regime with a Markov State Model avoids the microscopic regime completely. The MSM is then pre-computed using advanced path-sampling techniques such as multistate transition interface sampling. I illustrate this approach on patchy particle systems that show multiple modes of binding. MD-GFRD is generic, and can be used to efficiently simulate reaction-diffusion systems at the particle level, including the orientational dynamics, opening up the possibility for large-scale simulations of e.g. protein signaling networks.

  11. Cellular reprogramming dynamics follow a simple 1D reaction coordinate

    Science.gov (United States)

    Teja Pusuluri, Sai; Lang, Alex H.; Mehta, Pankaj; Castillo, Horacio E.

    2018-01-01

    Cellular reprogramming, the conversion of one cell type to another, induces global changes in gene expression involving thousands of genes, and understanding how cells globally alter their gene expression profile during reprogramming is an ongoing problem. Here we reanalyze time-course data on cellular reprogramming from differentiated cell types to induced pluripotent stem cells (iPSCs) and show that gene expression dynamics during reprogramming follow a simple 1D reaction coordinate. This reaction coordinate is independent of both the time it takes to reach the iPSC state as well as the details of the experimental protocol used. Using Monte-Carlo simulations, we show that such a reaction coordinate emerges from epigenetic landscape models where cellular reprogramming is viewed as a ‘barrier-crossing’ process between cell fates. Overall, our analysis and model suggest that gene expression dynamics during reprogramming follow a canonical trajectory consistent with the idea of an ‘optimal path’ in gene expression space for reprogramming.

  12. Consecutive dynamic resolutions of phosphine oxides

    NARCIS (Netherlands)

    Kortmann, Felix A.; Chang, Mu-Chieh; Otten, Edwin; Couzijn, Erik P. A.; Lutz, Martin; Minnaard, Adriaan J.

    2013-01-01

    A crystallization-induced asymmetric transformation (CIAT) involving a radical-mediated racemization provides access to enantiopure secondary phosphine oxides. A consecutive CIAT is used to prepare enantio-and diastereo-pure tert-butyl(hydroxyalkyl)phenylphosphine oxides.

  13. The dynamic of lipid oxidation in human myotubes

    DEFF Research Database (Denmark)

    Gaster, Michael

    2009-01-01

    Both endogenous and exogenous lipid levels may be regulators of total lipid oxidation in skeletal muscles. We studied the dynamics of lipid oxidation in human myotubes established from healthy, lean subjects exposed to acutely and chronically increased palmitate concentrations. The intramyocellular...... triacylglycerol content increased with chronic palmitate exposure. Both, ectopically increased intracellular and extracellular lipid levels were simultaneously oxidized and could partly suppress each other's oxidation. Overall, the highest acute palmitate treatments stimulated fatty acid oxidation whilst...... the highest chronic treatments decreased total lipid oxidation. Intracellular lipids showed a more complete oxidation than exogenous lipids. Endogenous lipids reduced insulin-mediated glucose oxidation. Thus, both endogenous and exogenous lipid concentrations regulated each other's oxidation and total lipid...

  14. Nuclear dynamics in heavy ion induced fusion-fission reactions

    International Nuclear Information System (INIS)

    Kapoor, S.S.

    1992-01-01

    Heavy ion induced fission and fission-like reactions evolve through a complex nuclear dynamics encountered in the medium energy nucleus-nucleus collisions. In the recent years, measurements of the fragment-neutron and fragment-charged particle angular correlations in heavy ion induced fusion-fission reactions, have provided new information on the dynamical times of nuclear deformations of the initial dinuclear complex to the fission saddle point and the scission point. From the studies of fragment angular distributions in heavy ion induced fission it has been possible to infer the relaxation times of the dinuclear complex in the K-degree of freedom and our recent measurements on the entrance channel dependence of fragment anisotropies have provided an experimental signature of the presence of fissions before K-equilibration. This paper reviews recent experimental and theoretical status of the above studies with particular regard to the questions relating to dynamical times, nuclear dissipation and the effect of nuclear dissipation on the K-distributions at the fission saddle in completely equilibrated compound nucleus. (author). 19 refs., 9 figs

  15. Nitric oxide and nitrous oxide turnover in natural and engineered microbial communities: biological pathways, chemical reactions, and novel technologies

    Science.gov (United States)

    Schreiber, Frank; Wunderlin, Pascal; Udert, Kai M.; Wells, George F.

    2012-01-01

    Nitrous oxide (N2O) is an environmentally important atmospheric trace gas because it is an effective greenhouse gas and it leads to ozone depletion through photo-chemical nitric oxide (NO) production in the stratosphere. Mitigating its steady increase in atmospheric concentration requires an understanding of the mechanisms that lead to its formation in natural and engineered microbial communities. N2O is formed biologically from the oxidation of hydroxylamine (NH2OH) or the reduction of nitrite (NO−2) to NO and further to N2O. Our review of the biological pathways for N2O production shows that apparently all organisms and pathways known to be involved in the catabolic branch of microbial N-cycle have the potential to catalyze the reduction of NO−2 to NO and the further reduction of NO to N2O, while N2O formation from NH2OH is only performed by ammonia oxidizing bacteria (AOB). In addition to biological pathways, we review important chemical reactions that can lead to NO and N2O formation due to the reactivity of NO−2, NH2OH, and nitroxyl (HNO). Moreover, biological N2O formation is highly dynamic in response to N-imbalance imposed on a system. Thus, understanding NO formation and capturing the dynamics of NO and N2O build-up are key to understand mechanisms of N2O release. Here, we discuss novel technologies that allow experiments on NO and N2O formation at high temporal resolution, namely NO and N2O microelectrodes and the dynamic analysis of the isotopic signature of N2O with quantum cascade laser absorption spectroscopy (QCLAS). In addition, we introduce other techniques that use the isotopic composition of N2O to distinguish production pathways and findings that were made with emerging molecular techniques in complex environments. Finally, we discuss how a combination of the presented tools might help to address important open questions on pathways and controls of nitrogen flow through complex microbial communities that eventually lead to N2O build

  16. Nitric oxide and nitrous oxide turnover in natural and engineered microbial communities: biological pathways, chemical reactions and novel technologies

    Directory of Open Access Journals (Sweden)

    Frank eSchreiber

    2012-10-01

    Full Text Available Nitrous oxide (N2O is an environmentally important atmospheric trace gas because it is an effective greenhouse gas and it leads to ozone depletion through photo-chemical nitric oxide (NO production in the stratosphere. Mitigating its steady increase in atmospheric concentration requires an understanding of the mechanisms that lead to its formation in natural and engineered microbial communities. N2O is formed biologically from the oxidation of hydroxylamine (NH2OH or the reduction of nitrite (NO2- to NO and further to N2O. Our review of the biological pathways for N2O production shows that apparently all organisms and pathways known to be involved in the catabolic branch of microbial N-cycle have the potential to catalyze the reduction of NO2- to NO and the further reduction of NO to N2O, while N2O formation from NH2OH is only performed by ammonia oxidizing bacteria. In addition to biological pathways, we review important chemical reactions that can lead to NO and N2O formation due to the reactivity of NO2-, NH2OH and nitroxyl (HNO. Moreover, biological N2O formation is highly dynamic in response to N-imbalance imposed on a system. Thus, understanding NO formation and capturing the dynamics of NO and N2O build-up are key to understand mechanisms of N2O release. Here, we discuss novel technologies that allow experiments on NO and N2O formation at high temporal resolution, namely NO and N2O microelectrodes and the dynamic analysis of the isotopic signature of N2O with quantum cascade laser based absorption spectroscopy. In addition, we introduce other techniques that use the isotopic composition of N2O to distinguish production pathways and findings that were made with emerging molecular techniques in complex environments. Finally, we discuss how a combination of the presented tools might help to address important open questions on pathways and controls of nitrogen flow through complex microbial communities that eventually lead to N2O build-up.

  17. Dynamical constraints and adiabatic invariants in chemical reactions.

    Science.gov (United States)

    Lorquet, J C

    2007-08-23

    For long-range electrostatic potentials and, more generally, when the topography of the potential energy surface is locally simple, the reaction path coordinate is adiabatically separable from the perpendicular degrees of freedom. For the ion-permanent dipole and ion-quadrupole interactions, the Poisson bracket of the adiabatic invariant decreases with the interfragment distance more rapidly than the electrostatic potential. The smaller the translational momentum, the moment of inertia of the neutral fragment, and the dipole or quadrupole moments are, the more reliable the adiabatic approximation is, as expected from the usual argumentation. Closed-form expressions for an effective one-dimensional potential in an adiabatic Hamiltonian are given. Connection with a model where the decoupling is exact is obtained in the limit of an infinitely heavy dipole. The dynamics is also constrained by adiabatic invariance for a harmonic valley about a curved reaction path, as shown by the reaction path Hamiltonian method. The maximum entropy method reveals that, as a result of the invariance properties of the entropy, constraints whose validity has been demonstrated locally only subsist in all parts of phase space. However, their form varies continuously, and they are not necessarily expressed in simple terms as they are in the asymptotic region. Therefore, although the influence of adiabatic invariance has been demonstrated at asymptotically large values of the reaction coordinate only, it persists in more interesting ranges.

  18. Electrocatalysis of the hydrogen evolution reaction by rhenium oxides electrodeposited by pulsed-current

    International Nuclear Information System (INIS)

    Vargas-Uscategui, Alejandro; Mosquera, Edgar; Chornik, Boris; Cifuentes, Luis

    2015-01-01

    Highlights: • Rhenium oxides were produced by means of pulsed current electrodeposition over ITO. • The electrocatalytic behavior of rhenium oxides electrodeposited over ITO was studied. • Electrodeposited rhenium oxides showed electrocatalytic behavior increasing the rate of the hydrogen evolution reaction. • The electrocatalysis behavior was explained considering the relative abundance of Re species on the surface of the electrodeposited material. - Abstract: Rhenium oxides are materials of interest for applications in the catalysis of reactions such as those occurring in fuel cells and photoelectrochemical cells. This research work was devoted to the production of rhenium oxide by means of pulsed current electrodeposition for the electrocatalysis of the hydrogen evolution reaction (HER). Rhenium oxides were electrodeposited over a transparent conductive oxide substrate (Indium Tin-doped Oxide – ITO) in an alkaline aqueous electrolyte. The electrodeposition process allowed the production of rhenium oxides islands (200–600 nm) with the presence of three oxidized rhenium species: Re"I"V associated to ReO_2, Re"V"I associated to ReO_3 and Re"V"I"I associated to H(ReO_4)H_2O. Electrodeposited rhenium oxides showed electrocatalytic behavior over the HER and an increase of one order of magnitude of the exchange current density was observed compared to the reaction taking place on the bare substrate. The electrocatalytic behavior varied with the morphology and relative abundance of oxidized rhenium species in the electrodeposits. Finally, two mechanisms of electrocatalysis were proposed to explain experimental results.

  19. Fission dynamics of superheavy nuclei formed in uranium induced reactions

    International Nuclear Information System (INIS)

    Gurjit Kaur; Sandhu, Kirandeep; Sharma, Manoj K.

    2017-01-01

    The compound nuclear system follows symmetric fission if the competing processes such as quasi-elastic, deep inelastic, quasi-fission etc are absent. The contribution of quasi fission events towards the fusion-fission mechanism depends on the entrance channel asymmetry of reaction partners, deformations and orientations of colliding nuclei beside the dependence on energy and angular momentum. Usually the 209 Bi and 208 Pb targets are opted for the production of superheavy nuclei with Z CN =104-113. The nuclei in same mass/charge range can also be synthesized using actinide targets + light projectiles (i.e. asymmetric reaction partners) via hot fusion interactions. These actinide targets are prolate deformed which prefer the compact configurations at above barrier energies, indicating the occurrence of symmetric fission events. Here an attempt is made to address the dynamics of light superheavy system (Z CN =104-106), formed via hot fusion interactions involving actinide targets

  20. Crossed-beam studies of the dynamics of radical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Liu, K. [Argonne National Laboratory, IL (United States)

    1993-12-01

    The objective of this program is to characterize the detailed dynamics of elementary radical reactions and to provide a better understanding of radical reactivity in general. The radical beam is typically generated by a laser photolysis method. After colliding with the reacting molecule in a crossed-beam apparatus, the reaction product state distribution is interrogated by laser spectroscopic techniques. Several radicals of combustion significance, such as O, CH, OH, CN and NCO have been successfully generated and their collisional behavior at the state-to-state integral cross section level of detail has been studied in this manner. During the past year, the detection system has been converted from LIF to REMPI schemes, and the emphasis of this program shifted to investigate the product angular distributions. Both inelastic and reactive processes have been studied.

  1. Dynamic phase transition in diffusion-limited reactions

    International Nuclear Information System (INIS)

    Tauber, U.C.

    2002-01-01

    Many non-equilibrium systems display dynamic phase transitions from active to absorbing states, where fluctuations cease entirely. Based on a field theory representation of the master equation, the critical behavior can be analyzed by means of the renormalization group. The resulting universality classes for single-species systems are reviewed here. Generically, the critical exponents are those of directed percolation (Reggeon field theory), with critical dimension d c = 4. Yet local particle number parity conservation in even-offspring branching and annihilating random walks implies an inactive phase (emerging below d c = 4/3) that is characterized by the power laws of the pair annihilation reaction, and leads to different critical exponents at the transition. For local processes without memory, the pair contact process with diffusion represents the only other non-trivial universality class. The consistent treatment of restricted site occupations and quenched random reaction rates are important open issues (Author)

  2. The quantum dynamics of electronically nonadiabatic chemical reactions

    Science.gov (United States)

    Truhlar, Donald G.

    1993-01-01

    Considerable progress was achieved on the quantum mechanical treatment of electronically nonadiabatic collisions involving energy transfer and chemical reaction in the collision of an electronically excited atom with a molecule. In the first step, a new diabatic representation for the coupled potential energy surfaces was created. A two-state diabatic representation was developed which was designed to realistically reproduce the two lowest adiabatic states of the valence bond model and also to have the following three desirable features: (1) it is more economical to evaluate; (2) it is more portable; and (3) all spline fits are replaced by analytic functions. The new representation consists of a set of two coupled diabatic potential energy surfaces plus a coupling surface. It is suitable for dynamics calculations on both the electronic quenching and reaction processes in collisions of Na(3p2p) with H2. The new two-state representation was obtained by a three-step process from a modified eight-state diatomics-in-molecules (DIM) representation of Blais. The second step required the development of new dynamical methods. A formalism was developed for treating reactions with very general basis functions including electronically excited states. Our formalism is based on the generalized Newton, scattered wave, and outgoing wave variational principles that were used previously for reactive collisions on a single potential energy surface, and it incorporates three new features: (1) the basis functions include electronic degrees of freedom, as required to treat reactions involving electronic excitation and two or more coupled potential energy surfaces; (2) the primitive electronic basis is assumed to be diabatic, and it is not assumed that it diagonalizes the electronic Hamiltonian even asymptotically; and (3) contracted basis functions for vibrational-rotational-orbital degrees of freedom are included in a very general way, similar to previous prescriptions for locally

  3. Ion-molecule reactions in the binary mixture of ethylene oxide and trioxane, 1

    International Nuclear Information System (INIS)

    Kumakura, Minoru; Sugiura, Toshio.

    1977-01-01

    The formation mechanism of protonated molecular ions by cross-reactions in ethylene oxide-trioxane mixtures has been studied with use of a modified time-of-flight mass spectrometer. The precursors of the product ions were determined by analysis of the fine structure of their ionization efficiency curves using deuterated ethylene oxide. Protonated ethylene oxide is formed by the hydrogen atom transfer reaction of ethylene oxide molecular ion with trioxane, and protonated trioxane by the proton transfer reaction of CHO + (from ethylene oxide) with trioxane. In the ion-molecule reactions of ethylene-d 4 oxide-trioxane mixtures, appreciable isotope effect was observed. The CHO + from ethylene oxide is an important reactant ion as compared with that from trioxane in the proton transfer reaction, and CHO + from ethylene oxide was suggested as a thermal reactive ion. The order of proton affinity could be estimated from the proton transfer reactions involving CHO + . It was found that the proton affinity of trioxane is smaller than that of ethylene oxide. (auth.)

  4. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

    Energy Technology Data Exchange (ETDEWEB)

    Bradforth, S.E.

    1992-11-01

    The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound [yields] bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN[sup [minus

  5. Dynamics of GeV light-ion-induced reactions

    International Nuclear Information System (INIS)

    Kwiatkowski, K.; Bracken, D.S.; Foxford, E.R.; Ginger, D.S.; Hsi, W.C.; Morley, K.B.; Viola, V.E.; Wang, G.; Korteling, R.G.; Legrain, R.

    1996-09-01

    Recent results from studies of the 1.8 - 4.8 GeV 3 He + nat Ag, 197 Au reactions at LNS with the ISiS detector array have shown evidence for a saturation in deposition energy and multifragmentation from a low-density source. The collision dynamics have been examined in the context of intranuclear cascade and BUU models, while breakup phenomena have been compared with EES and SMM models. Fragment-fragment correlations and isotope ratios are also investigated. (K.A.)

  6. Thermogravimetric study of the reaction of uranium oxides with fluorine

    International Nuclear Information System (INIS)

    Komura, Motohiro; Sato, Nobuaki; Kirishima, Akira; Tochiyama, Osamu

    2008-01-01

    Thermogravimetric study of the reaction of uranium oxides with fluorine was conducted by TG-DTA method using anti-corrosion type differential thermobalance. When UO 2 was heated from R.T. to 500 deg. C in 5% F 2 /He atmosphere, the weight increase appeared at ca. 250 deg. C with an exothermic peak. Then the weight decreased slightly with a small exothermic peak followed by the complete volatilization with a large exothermic peak at ca. 350 deg. C. At a flow rate of 15, 30, 60 ml min -1 , there seemed to be no significant change for the fluorination of UO 2 . With the different heating rates of 1, 2, 5 and 10 deg. C min -1 , the fluorination peak shifted to higher temperature with increasing heating rates. For the comparison with thermogravimetric results, phase analysis by XRD method was conducted for the products obtained at different temperatures. At 260 deg. C, the product was UO 2 with a small amount of the intermediate compound, UO 2 F. The amount of this compound increased with increasing temperature up to 320 deg. C. Then another phase of UO 2 F 2 appeared at 340 deg. C but it was immediately fluorinated to the volatile fluoride. When U 3 O 8 was used as a starting material, it was found that the steep weight decrease peak appeared at ca. 350 deg. C and the uranium volatilized completely. This result suggests that fluorination of U 3 O 8 occurs at this temperature forming UF 6 . Uranium trioxide showed the similar fluorination behavior to that of U 3 O 8

  7. Pattern dynamics of the reaction-diffusion immune system.

    Science.gov (United States)

    Zheng, Qianqian; Shen, Jianwei; Wang, Zhijie

    2018-01-01

    In this paper, we will investigate the effect of diffusion, which is ubiquitous in nature, on the immune system using a reaction-diffusion model in order to understand the dynamical behavior of complex patterns and control the dynamics of different patterns. Through control theory and linear stability analysis of local equilibrium, we obtain the optimal condition under which the system loses stability and a Turing pattern occurs. By combining mathematical analysis and numerical simulation, we show the possible patterns and how these patterns evolve. In addition, we establish a bridge between the complex patterns and the biological mechanism using the results from a previous study in Nature Cell Biology. The results in this paper can help us better understand the biological significance of the immune system.

  8. Dynamical isospin effects in nucleon-induced reactions

    International Nuclear Information System (INIS)

    Ou Li; Li Zhuxia; Wu Xizhen

    2008-01-01

    The isospin effects in proton-induced reactions on isotopes of 112-132 Sn and the corresponding β-stable isobars are studied by means of the improved quantum molecular dynamics model and some sensitive probes for the density dependence of the symmetry energy at subnormal densities are proposed. The beam energy range is chosen to be 100-300 MeV. Our study shows that the system size dependence of the reaction cross sections for p+ 112-132 Sn deviates from the Carlson's empirical expression obtained by fitting the reaction cross sections for proton on nuclei along the β-stability line and sensitively depends on the stiffness of the symmetry energy. We also find that the angular distribution of elastic scattering for p+ 132 Sn at large impact parameters is very sensitive to the density dependence of the symmetry energy, which is uniquely due to the effect of the symmetry potential with no mixture of the effect from the isospin dependence of the nucleon-nucleon cross sections. The isospin effects in neutron-induced reactions are also studied and it is found that the effects are just opposite to that in proton-induced reactions. We find that the difference between the peaks of the angular distributions of elastic scattering for p+ 132 Sn and n+ 132 Sn at E p,n =100 MeV and b=7.5 fm is positive for soft symmetry energy U sym sf and negative for super-stiff symmetry energy U sym nlin and close to zero for linear density dependent symmetry energy U sym lin , which seems very useful for constraining the density dependence of the symmetry energy at subnormal densities

  9. The influence of oscillations on product selectivity during the palladium-catalysed phenylacetylene oxidative carbonylation reaction.

    Science.gov (United States)

    Novakovic, Katarina; Grosjean, Christophe; Scott, Stephen K; Whiting, Andrew; Willis, Mark J; Wright, Allen R

    2008-02-07

    This paper reports on the influence of oscillations on product selectivity as well as the dynamics of product formation during the palladium-catalysed phenylacetylene oxidative carbonylation reaction in a catalytic system (PdI2, KI, Air, NaOAc in methanol). The occurrence of the pH oscillations is related to PdI2 granularity and the initial pH drop after phenylacetylene addition. To achieve pH and reaction exotherm oscillations regulation of the amount of PdI2 is required, ensuring that the initial pH does not fall significantly below 1 after phenylacetylene addition. Experiments in both oscillatory and non-oscillatory pH regimes were performed in an HEL SIMULAR reaction calorimeter with the concentration-time profiles measured using a GC-MS. It is demonstrated that when operating in an oscillatory pH regime product formation may be suppressed until oscillations occur after which there is a steep increase in the formation of Z-2-phenyl-but-2-enedioic acid dimethyl ester. When operating in non-oscillatory pH mode the products are formed steadily over time with the main products being Z-2-phenyl-but-2-enedioic acid dimethyl ester, 2-phenyl-acrylic acid methyl ester and E-3-phenyl-acrylic acid methyl ester.

  10. Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface.

    Science.gov (United States)

    den Boer, Duncan; Li, Min; Habets, Thomas; Iavicoli, Patrizia; Rowan, Alan E; Nolte, Roeland J M; Speller, Sylvia; Amabilino, David B; De Feyter, Steven; Elemans, Johannes A A W

    2013-07-01

    Manganese porphyrins have been extensively investigated as model systems for the natural enzyme cytochrome P450 and as synthetic oxidation catalysts. Here, we report single-molecule studies of the multistep reaction of manganese porphyrins with molecular oxygen at a solid/liquid interface, using a scanning tunnelling microscope (STM) under environmental control. The high lateral resolution of the STM, in combination with its sensitivity to subtle differences in the electronic properties of molecules, allowed the detection of at least four distinct reaction species. Real-space and real-time imaging of reaction dynamics enabled the observation of active sites, immobile on the experimental timescale. Conversions between the different species could be tuned by the composition of the atmosphere (argon, air or oxygen) and the surface bias voltage. By means of extensive comparison of the results to those obtained by analogous solution-based chemistry, we assigned the observed species to the starting compound, reaction intermediates and products.

  11. Relationship between measurements of blood oxidative metabolites and skin reaction in irradiated rats

    International Nuclear Information System (INIS)

    Kaneko, Takashi; Goto, Jun; Nomiya, Takuma; Nemoto, Kenji

    2011-01-01

    Recently, oxidative metabolites have been able to be measured by simple small device. It has been reported that the value of oxidative metabolites increases under several conditions such as hypertension, smoking, diabetes mellitus, etc. Radiation used in radiotherapy also causes free radicals and oxidative metabolites, and irradiation causes dermatitis and sometimes causes skin ulcer in the irradiated site. We analyzed the relationships between the value of oxidative metabolites and skin reactions. A certain doses of radiation were irradiated to the right thigh of rats, and oxidative metabolites of rat's blood from caudal vein were measured by d-reactive oxygen metabolites (ROMs) test using an exclusive device. Skin reactions were evaluated according to a skin-reaction grading system from the day before irradiation to day 38 after irradiation. As a results, a significant correlation was shown between irradiation dose and skin grade. And a significant correlation was also shown between the value of oxidative metabolites and irradiation dose. The increase in oxidative metabolites was seen in the Day 16 after irradiation, and that corresponded with the appearance of skin reaction. It was suggested that the value of oxidative metabolites seems to be useful for estimating degree of skin reaction and time to appear skin reaction after irradiation. (author)

  12. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

    Energy Technology Data Exchange (ETDEWEB)

    Bradforth, Stephen Edmund [Univ. of California, Berkeley, CA (United States)

    1992-11-01

    The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound {yields} bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN-, NCO- and NCS-. Transition state photoelectron spectra are presented for the following systems Br + HI, Cl + HI, F + HI, F + CH30H,F + C2H5OH,F + OH and F + H2. A time dependent framework for the simulation and interpretation of the bound → free transition state photoelectron spectra is subsequently developed and applied to the hydrogen transfer reactions Br + HI, F + OH → O(3P, 1D) + HF and F + H2. The theoretical approach for the simulations is a fully quantum-mechanical wave packet propagation on a collinear model reaction potential surface. The connection between the wavepacket time evolution and the photoelectron spectrum is given by the time autocorrelation function. For the benchmark F + H2 system, comparisons with three-dimensional quantum calculations are made.

  13. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

    International Nuclear Information System (INIS)

    Bradforth, S.E.

    1992-11-01

    The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound → bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN - , NCO - and NCS - . Transition state photoelectron spectra are presented for the following systems Br + HI, Cl + HI, F + HI, F + CH 3 0H,F + C 2 H 5 OH,F + OH and F + H 2 . A time dependent framework for the simulation and interpretation of the bound → free transition state photoelectron spectra is subsequently developed and applied to the hydrogen transfer reactions Br + HI, F + OH → O( 3 P, 1 D) + HF and F + H 2 . The theoretical approach for the simulations is a fully quantum-mechanical wave packet propagation on a collinear model reaction potential surface. The connection between the wavepacket time evolution and the photoelectron spectrum is given by the time autocorrelation function. For the benchmark F + H 2 system, comparisons with three-dimensional quantum calculations are made

  14. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

    2018-03-01

    In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

  15. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

    2018-06-01

    In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

  16. Limits and dynamics of methane oxidation in landfill cover soils

    Science.gov (United States)

    In order to understand the limits and dynamics of methane (CH4) oxidation in landfill cover soils, we investigated CH4 oxidation in daily, intermediate, and final cover soils from two California landfills as a function of temperature, soil moisture and CO2 concentration. The results indicate a signi...

  17. Consecutive dynamic resolutions of phosphine oxides

    NARCIS (Netherlands)

    Kortmann, Felix A.; Chang, Mu Chieh; Otten, Edwin; Couzijn, Erik P A; Lutz, Martin|info:eu-repo/dai/nl/304828971; Minnaard, Adriaan J.

    2014-01-01

    A crystallization-induced asymmetric transformation (CIAT) involving a radical-mediated racemization provides access to enantiopure secondary phosphine oxides. A consecutive CIAT is used to prepare enantio- and diastereo-pure tert-butyl(hydroxyalkyl)phenylphosphine oxides. © 2014 The Royal Society

  18. Combining molecular dynamics with mesoscopic Green’s function reaction dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Vijaykumar, Adithya, E-mail: vijaykumar@amolf.nl [FOM Institute AMOLF, Science Park 104, 1098 XG Amsterdam (Netherlands); van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, P.O. Box 94157, 1090 GD Amsterdam (Netherlands); Bolhuis, Peter G. [van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, P.O. Box 94157, 1090 GD Amsterdam (Netherlands); Rein ten Wolde, Pieter, E-mail: p.t.wolde@amolf.nl [FOM Institute AMOLF, Science Park 104, 1098 XG Amsterdam (Netherlands)

    2015-12-07

    In many reaction-diffusion processes, ranging from biochemical networks, catalysis, to complex self-assembly, the spatial distribution of the reactants and the stochastic character of their interactions are crucial for the macroscopic behavior. The recently developed mesoscopic Green’s Function Reaction Dynamics (GFRD) method enables efficient simulation at the particle level provided the microscopic dynamics can be integrated out. Yet, many processes exhibit non-trivial microscopic dynamics that can qualitatively change the macroscopic behavior, calling for an atomistic, microscopic description. We propose a novel approach that combines GFRD for simulating the system at the mesoscopic scale where particles are far apart, with a microscopic technique such as Langevin dynamics or Molecular Dynamics (MD), for simulating the system at the microscopic scale where reactants are in close proximity. This scheme defines the regions where the particles are close together and simulated with high microscopic resolution and those where they are far apart and simulated with lower mesoscopic resolution, adaptively on the fly. The new multi-scale scheme, called MD-GFRD, is generic and can be used to efficiently simulate reaction-diffusion systems at the particle level.

  19. Combining molecular dynamics with mesoscopic Green’s function reaction dynamics simulations

    International Nuclear Information System (INIS)

    Vijaykumar, Adithya; Bolhuis, Peter G.; Rein ten Wolde, Pieter

    2015-01-01

    In many reaction-diffusion processes, ranging from biochemical networks, catalysis, to complex self-assembly, the spatial distribution of the reactants and the stochastic character of their interactions are crucial for the macroscopic behavior. The recently developed mesoscopic Green’s Function Reaction Dynamics (GFRD) method enables efficient simulation at the particle level provided the microscopic dynamics can be integrated out. Yet, many processes exhibit non-trivial microscopic dynamics that can qualitatively change the macroscopic behavior, calling for an atomistic, microscopic description. We propose a novel approach that combines GFRD for simulating the system at the mesoscopic scale where particles are far apart, with a microscopic technique such as Langevin dynamics or Molecular Dynamics (MD), for simulating the system at the microscopic scale where reactants are in close proximity. This scheme defines the regions where the particles are close together and simulated with high microscopic resolution and those where they are far apart and simulated with lower mesoscopic resolution, adaptively on the fly. The new multi-scale scheme, called MD-GFRD, is generic and can be used to efficiently simulate reaction-diffusion systems at the particle level

  20. A short synthesis-stuttgart of (S)-pyrrolam A via domino oxidation-witting reaction

    Digital Repository Service at National Institute of Oceanography (India)

    Majik, M.S.; Shet, J.; Tilve, S.G.; Parameswaran, P.S.

    A short synthesis of (S)-pyrrolam A starting from readily available N-(benzyloxycarbonyl)-L prolinol is described that makes use of a domino primary alcohol oxidation-Witting reaction as the key step...

  1. Carbon-coated magnetic palladium: applications in partial oxidation of alcohols and coupling reactions.

    Science.gov (United States)

    Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; catalyst can be used for oxidation of alcohols, amination reaction and arylation of aryl halides (cross coupli...

  2. Oxidation kinetics of reaction products formed in uranium metal corrosion

    International Nuclear Information System (INIS)

    Totemeier, T. C.

    1998-01-01

    The oxidation behavior of uranium metal ZPPR fuel corrosion products in environments of Ar-4%O 2 and Ar-20%O 2 were studied using thermo-gravimetric analysis (TGA). These tests were performed to extend earlier work in this area specifically, to assess plate-to-plate variations in corrosion product properties and the effect of oxygen concentration on oxidation behavior. The corrosion products from two relatively severely corroded plates were similar, while the products from a relatively intact plate were not reactive. Oxygen concentration strongly affected the burning rate of reactive products, but had little effect on low-temperature oxidation rates

  3. Oxidation kinetics of reaction products formed in uranium metal corrosion.

    Energy Technology Data Exchange (ETDEWEB)

    Totemeier, T. C.

    1998-04-22

    The oxidation behavior of uranium metal ZPPR fuel corrosion products in environments of Ar-4%O{sub 2} and Ar-20%O{sub 2} were studied using thermo-gravimetric analysis (TGA). These tests were performed to extend earlier work in this area specifically, to assess plate-to-plate variations in corrosion product properties and the effect of oxygen concentration on oxidation behavior. The corrosion products from two relatively severely corroded plates were similar, while the products from a relatively intact plate were not reactive. Oxygen concentration strongly affected the burning rate of reactive products, but had little effect on low-temperature oxidation rates.

  4. Multiscale Reaction-Diffusion Algorithms: PDE-Assisted Brownian Dynamics

    KAUST Repository

    Franz, Benjamin

    2013-06-19

    Two algorithms that combine Brownian dynami cs (BD) simulations with mean-field partial differential equations (PDEs) are presented. This PDE-assisted Brownian dynamics (PBD) methodology provides exact particle tracking data in parts of the domain, whilst making use of a mean-field reaction-diffusion PDE description elsewhere. The first PBD algorithm couples BD simulations with PDEs by randomly creating new particles close to the interface, which partitions the domain, and by reincorporating particles into the continuum PDE-description when they cross the interface. The second PBD algorithm introduces an overlap region, where both descriptions exist in parallel. It is shown that the overlap region is required to accurately compute variances using PBD simulations. Advantages of both PBD approaches are discussed and illustrative numerical examples are presented. © 2013 Society for Industrial and Applied Mathematics.

  5. Laser-oxygen cutting of mild steel: the thermodynamics of the oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Powell, J; Kaplan, A F H [Department of Applied Physics and Mechanical Engineering, Luleaa University of Technology, SE-971 87 Luleaa (Sweden); Petring, D [Fraunhofer-Institute for Laser Technology (ILT), Steinbachstrasse 15, Aachen (Germany); Kumar, R V [Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB2 3QZ (United Kingdom); Al-Mashikhi, S O; Voisey, K T [Department of Mechanical, Materials and Manufacturing Engineering, Faculty of Engineering, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom)], E-mail: jpowell@laserexp.co.uk

    2009-01-07

    In a considerable proportion of the published work on the subject of laser-oxygen cutting of mild steel, the details of the oxidation reaction are overlooked or confused. For example, it is not uncommon for the oxidized material to be attributed with the physical characteristics of iron rather than iron oxide. Also, the fact that the oxidation reaction cannot take place above a certain temperature limit is usually overlooked. This paper presents, for the first time, an in-depth analysis of the Iron to FeO oxidation reaction in the context of laser-oxygen cutting of mild steel. The paper concludes by presenting a number of guidelines for future theoretical models.

  6. Laser-oxygen cutting of mild steel: the thermodynamics of the oxidation reaction

    International Nuclear Information System (INIS)

    Powell, J; Kaplan, A F H; Petring, D; Kumar, R V; Al-Mashikhi, S O; Voisey, K T

    2009-01-01

    In a considerable proportion of the published work on the subject of laser-oxygen cutting of mild steel, the details of the oxidation reaction are overlooked or confused. For example, it is not uncommon for the oxidized material to be attributed with the physical characteristics of iron rather than iron oxide. Also, the fact that the oxidation reaction cannot take place above a certain temperature limit is usually overlooked. This paper presents, for the first time, an in-depth analysis of the Iron to FeO oxidation reaction in the context of laser-oxygen cutting of mild steel. The paper concludes by presenting a number of guidelines for future theoretical models.

  7. Evidence concerning oxidation as a surface reaction in Baltic amber

    DEFF Research Database (Denmark)

    Shashoua, Yvonne

    2012-01-01

    , obtained from pressed amber powder, were subjected to accelerated thermal ageing. Cross-sections of the pellets were analyzed by infrared micro-spectroscopy, in order to identify and quantify changes in chemical properties. The experimental results showed strong oxidation exclusively at the exterior part...... of cross-sections from samples subjected to long-term thermal ageing, confirming that oxidation of Baltic amber starts from the surface....

  8. Dynamical calculations of nuclear fission and heavy-ion reactions

    International Nuclear Information System (INIS)

    Nix, J.R.; Sierk, A.J.

    1984-01-01

    With the goal of determining the magnitude and mechanism of nuclear dissipation from comparisons of predictions with experimental data, we describe recent calculations in a unified macroscopic-microscopic approach to large-amplitude collective nuclear motion such as occurs in fission and heavy-ion reactions. We describe the time dependence of the distribution function in phase space of collective coordinates and momenta by a generalized Fokker-Planck equation. The nuclear potential energy of deformation is calculated as the sum of repulsive Coulomb and centrifugal energies and an attractive Yukawa-plus-exponential potential, the inertia tensor is calculated for a superposition of rigid-body rotation and incompressible, nearly irrotational flow by use of the Werner-Wheeler method, and the dissipation ensor that describes the conversion of collective energy into single-particle excitation energy is calculated for two prototype mechanisms that represent opposite extremes of large and small dissipation. We solve the generalized Hamilton equations of motion for the first moments of the distribution function to obtain the mean translational fission-fragment kinetic energy and mass of a third fragment that sometimes forms between the two end fragments, as well as dynamical thresholds, capture cross sections, and ternary events in heavy-ion reactions. 33 references

  9. New Insights into the Diels-Alder Reaction of Graphene Oxide.

    Science.gov (United States)

    Brisebois, Patrick P; Kuss, Christian; Schougaard, Steen B; Izquierdo, Ricardo; Siaj, Mohamed

    2016-04-18

    Graphene oxide is regarded as a major precursor for graphene-based materials. The development of graphene oxide based derivatives with new functionalities requires a thorough understanding of its chemical reactivity, especially for canonical synthetic methods such as the Diels-Alder cycloaddition. The Diels-Alder reaction has been successfully extended with graphene oxide as a source of diene by using maleic anhydride as a dienophile, thereby outlining the presence of the cis diene present in the graphene oxide framework. This reaction provides fundamental information for understanding the exact structure and chemical nature of graphene oxide. On the basis of high-resolution (13) C-SS NMR spectra, we show evidence for the formation of new sp(3) carbon centers covalently bonded to graphene oxide following hydrolysis of the reaction product. DFT calculations are also used to show that the presence of a cis dihydroxyl and C vacancy on the surface of graphene oxide are promoting the reaction with significant negative reaction enthalpies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. CO2 as an Oxidant for High Temperature Reactions

    Directory of Open Access Journals (Sweden)

    Sibudjing eKawi

    2015-03-01

    Full Text Available This paper presents a review on the developments in catalyst technology for the reactions utilizing CO2 for high temperature applications. These include dehydrogenation of alkanes to olefins, the dehydrogenation of ethylbenzene to styrene and finally CO2 reforming of hydrocarbon feedstock (i.e. methane and alcohols. Aspects on the various reaction pathways are also highlighted. The literature on the role of promoters and catalyst development is critically evaluated. Most of the reactions discussed in this review are exploited in industries and related to on-going processes, thus providing extensive data from literature. However some reactions, such as CO2 reforming of ethanol and glycerol which have not reached industrial scale are also reviewed owing to their great potential in terms of sustainability which are essential as energy for the future. This review further illustrates the building-up of knowledge which shows the role of support and catalysts for each reaction and the underlying linkage between certain catalysts which can be adapted for the multiple CO2-related reactions.

  11. Stereoselectivity in catalytic reactions: CO oxidation on Pd(100) by rotationally aligned O2 molecules

    Science.gov (United States)

    Vattuone, L.; Gerbi, A.; Savio, L.; Cappelletti, D.; Pirani, F.; Rocca, M.

    2010-05-01

    We report on stereodynamical effects in heterogeneous catalytic reactions as measured by molecular beam-surface experiments. Specifically for CO oxidation on Pd(100) we find that the rotational alignment of the incoming O2 at low (Θ = 0.04 ML) and at intermediate (ΘCO = 0.17 ML) CO pre-coverage, causes a higher reactivity of molecules in high and in low helicity states, respectively (corresponding to helicoptering and cartwheeling motion of O2). In first approximation, at low CO pre-coverage the difference in reactivity is determined by the different location of the O atoms generated in the dissociation process by the different parent molecules, while at intermediate CO pre-coverage the reactivity is influenced also by the different ability of cartwheeling and helicoptering O2 to penetrate through the CO adlayer. In accord with this the total amount of CO2 produced is always largest for helicopters which generate supersurface O atoms at least in the low CO pre-coverage limit. A deeper inspection of the data indicates, however, that the dynamics is more complex, two different pathways being present for the reaction with O generated by helicopters and one for O generated by cartwheels. Moreover, cartwheels generated oxygen influences the reactivity of subsequently arriving helicopters.

  12. Effect of surface functionalisation on the interaction of iron oxide nanoparticles with polymerase chain reaction.

    Science.gov (United States)

    Aysan, Ayse Beyza; Knejzlík, Zdeněk; Ulbrich, Pavel; Šoltys, Marek; Zadražil, Aleš; Štěpánek, František

    2017-05-01

    The combination of nanoparticles with the polymerase chain reaction (PCR) can have benefits such as easier sample handling or higher sensitivity, but also drawbacks such as loss of colloidal stability or inhibition of the PCR. The present work systematically investigates the interaction of magnetic iron oxide nanoparticles (MIONs) with the PCR in terms of colloidal stability and potential PCR inhibition due to interaction between the PCR components and the nanoparticle surface. Several types of MIONs with and without surface functionalisation by sodium citrate, dextran and 3-aminopropyl-triethoxysilane (APTES) were prepared and characterised by Transmission Electron Microscopy (TEM), dynamic light scattering (DLS) and Fourier Transform Infrared (FT-IR) spectroscopy. Colloidal stability in the presence of the PCR components was investigated both at room temperature and under PCR thermo-cycling. Dextran-stabilized MIONs show the best colloidal stability in the PCR mix at both room and elevated temperatures. Citrate- and APTES-stabilised as well as uncoated MIONs show a comparable PCR inhibition near the concentration 0.1mgml -1 while the inhibition of dextran stabilized MIONs became apparent near 0.5mgml -1 . It was demonstrated that the PCR could be effectively carried out even in the presence of elevated concentration of MIONs up to 2mgml -1 by choosing the right coating approach and supplementing the reaction mix by critical components, Taq DNA polymerase and Mg 2+ ions. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Optimization of reaction parameters for the electrochemical oxidation of lidocaine with a Design of Experiments approach

    NARCIS (Netherlands)

    Gul, Turan; Bischoff, Rainer; Permentier, Hjalmar

    2015-01-01

    Identification of potentially toxic oxidative drug metabolites is a crucial step in the development of new drugs. Electrochemical methods are useful to study oxidative drug metabolism, but are not widely used to synthesize metabolites for follow-up studies. Careful optimization of reaction

  14. Concentrated Aqueous Sodium Tosylate as Green Medium for Alkene Oxidation and Nucleophilic Substitution Reactions.

    Science.gov (United States)

    Sela, Tal; Lin, Xiaoxi; Vigalok, Arkadi

    2017-11-03

    A hydrotropic solution of highly concentrated sodium tosylate (NaOTs) can be used as a recyclable medium for the environmentally benign oxidation of conjugated alkenes with H 2 O 2 . Both uncatalyzed and metal-catalyzed reactions provided the corresponding oxidation products in higher yields than in pure water or many common organic solvents.

  15. Process for the reduction of competitive oxidant consuming reactions in the solution mining of a mineral

    International Nuclear Information System (INIS)

    Stover, D.E.

    1980-01-01

    The present invention relates to an improved method for the solution mining of a mineral from a subterranean formation. More specifically, the invention relates to an improved method which enhances significantly the recovery of the mineral from a subterranean formation via solution mining by reducing the oxidant consuming reactions which compete with the mineral for the oxidant injected therein

  16. Chemiluminescence from the reaction of Ba 3D with nitric oxide

    International Nuclear Information System (INIS)

    Johnson, S.A.; Solarz, R.W.; Dubrin, J.W.; Brotzmann, R.

    1977-01-01

    The reaction of laser excited Ba*( 3 D) states with nitric oxide is presented. BaO product is not detected, although the channel is thermodynamically open, and instead chemiluminescence is observed. Experiments which suggest that radiative recombination, Ba + NO → BaNO* → BaNO, is the observed reaction channel will also be presented

  17. Development of a redox-free Mitsunobu reaction exploiting phosphine oxides as precursors to dioxyphosphoranes.

    Science.gov (United States)

    Tang, Xiaoping; Chapman, Charlotte; Whiting, Matthew; Denton, Ross

    2014-07-14

    The development of the first redox-free protocol for the Mitsunobu reaction is described. This has been achieved by exploiting triphenylphosphine oxide--the unwanted by-product in the conventional Mitsunobu reaction--as the precursor to the active P(V) coupling reagent. Multinuclear NMR studies are consistent with hydroxyl activation via an alkoxyphosphonium salt.

  18. Effect of thermal treatment conditions on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid

    International Nuclear Information System (INIS)

    Gorshkova, T.P.; Tarasova, D.V.; Olen'kova, I.P.; Andrushkevich, T.V.; Nikoro, T.A.

    1984-01-01

    The effect of thermal treatment conditions (temperature and gas medium) on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid is investigated. It is shown that active and selective catalysts are formed in the course of thermal decomposition of the drying product of ammonium metavanadate and paramolybdate under the conditions ensuring the vanadium ion reduction up to tetravalent state with conservation of molybdenum oxidation degree equal to 6. It is possible to realize it either by treatment of the catalyst calcinated in the air flow at 300 deg by the reaction mixture at the activation stage or by gas-reducer flow treatment at 280 deg. Thermal treatment in the reducing medium of the oxidized catalyst does not lead to complete regeneration of its properties

  19. Dynamics of Oxidation of Aluminum Nanoclusters using Variable Charge Molecular-Dynamics Simulations on Parallel Computers

    Science.gov (United States)

    Campbell, Timothy; Kalia, Rajiv K.; Nakano, Aiichiro; Vashishta, Priya; Ogata, Shuji; Rodgers, Stephen

    1999-06-01

    Oxidation of aluminum nanoclusters is investigated with a parallel molecular-dynamics approach based on dynamic charge transfer among atoms. Structural and dynamic correlations reveal that significant charge transfer gives rise to large negative pressure in the oxide which dominates the positive pressure due to steric forces. As a result, aluminum moves outward and oxygen moves towards the interior of the cluster with the aluminum diffusivity 60% higher than that of oxygen. A stable 40 Å thick amorphous oxide is formed; this is in excellent agreement with experiments.

  20. Reaction path of the oxidative coupling of methane over a lithium-doped magnesium oxide catalyst : Factors affecting the Rate of Total Oxidation of Ethane and Ethylene

    NARCIS (Netherlands)

    Roos, J.A.; Korf, S.J.; Veehof, R.H.J.; van Ommen, J.G.; Ross, J.R.H.

    1989-01-01

    Experiments using gas mixtures of O2, C2H6 or C2H4 and CH4 or He have been carried out with a Li/MgO catalyst using a well-mixed reaction system which show that the total oxidation products, CO and CO2, are formed predominantly from ethylene, formed in the oxidative coupling of methane. It is

  1. The Atmospheric Oxidation of Volatile Organic Compounds Through Hydrogen Shift Reactions

    DEFF Research Database (Denmark)

    Knap, Hasse Christian

    a radical is denoted as a H-shift reaction. Quantum chemical calculations were carried out to investigate the potential energy surface of the H-shift reactions and the subsequent decomposition pathways. The transition state theory including the Eckart quantum tunneling correction have been used to calculate...... the reaction rate constants of the H-shift reactions. The autoxidation of volatile organic compounds is an important oxidation mechanism that produces secondary organic aerosols (SOA) and recycles hydroxyl (OH) radicals. The autoxidation cycle produces a second generation peroxy radical (OOQOOH) through...... a series of H-shift reactions and O2 attachments. I have investigated the H-shift reactions in two OOQOOH radicals (hydroperoxy peroxy radicals and hydroperoxy acyl peroxy radicals). The H-shift reaction rate constants have been compared with the bimolecular reaction rate constants of the peroxy radicals...

  2. Supercritical carbon dioxide as an innovative reaction medium for selective oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Loeker, F.; Leitner, W. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

    1998-12-31

    Although the catalytic efficiency of all catalytic oxidation processes studied in scCO{sub 2} up to now is far from being satisfactory, the principle possibility to carry out such reactions in this medium is clearly evident. Future research in our group will be directed towards the development of homogeneous and heterogeneous catalysts that are adopted to the special requirements of both the oxidation process and the supercritical reaction medium. Preliminary results from these studies regarding the epoxidation of olefins with molecular oxygen as oxidant will be presented on the conference poster. (orig.)

  3. Microreactor as Efficient Tool for Light Induced Oxidation Reactions

    Czech Academy of Sciences Publication Activity Database

    Hejda, S.; Drhová, Magdalena; Křišťál, Jiří; Buzek, D.; Krystyník, Pavel; Klusoň, Petr

    2014-01-01

    Roč. 255, NOV 1 (2014), s. 178-184 ISSN 1385-8947 Grant - others:GA MŠMT(CZ) MŠk:CZ.1.07/2.2.00/28.0205 Institutional support: RVO:67985858 Keywords : photo microreactor * phthalocyanine * chlorophenol oxidation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 4.321, year: 2014

  4. Thermodynamic analysis of reduction reactions of niobium oxides

    International Nuclear Information System (INIS)

    Takano, C.

    1981-01-01

    Reduction processes of niobium oxides by hydrogen, carbon and aluminium are analysed thermodinamically. It is shown that reduction by hydrogen is not technically feasible. High purity of raw materials is required. In the carbothermic process impurities which react to form high stability carbides should be avoided. (Author) [pt

  5. Things fall apart: Fragmentation reactions in the oxidative aging of organic species

    Science.gov (United States)

    Kroll, J. H.; Isaacman-VanWertz, G. A.; Wilson, K. R.; Daumit, K. E.; Kessler, S. H.; Lim, C. Y.; Worsnop, D. R.

    2016-12-01

    The atmospheric oxidation of organic compounds involves a wide array of chemical transformations, including functionalization reactions (addition of polar functional groups to the carbon skeleton), fragmentation reactions (formation of lower carbon-number products via C-C bond scission), and accretion reactions (increases in molecular weight by the combination of two chemical species). Each of these reaction classes can lead to large changes in volatility, and hence can have major implications for atmospheric organic aerosol (OA). For example, the formation of OA is predominantly driven by functionalization and accretion reactions, which generally lead to decreases in volatility. Here we describe a series of laboratory studies of the subsequent organic "aging", the multiday oxidation processes that occur after the initial OA formation and growth. In these studies, the multigenerational oxidation of organic compounds in various phases (the gas phase, the condensed OA phase, and the aqueous phase) is carried out within either an environmental chamber or a flow reactor, and monitored using various high-resolution mass spectrometric techniques. In all cases it is found that fragmentation reactions play a major role in the observed aging chemistry, dominated by the formation of small, volatile oxidation products. These results suggest that multi-day oxidative aging processes do not lead to sustained aerosol growth, but rather may serve as a chemical sink for atmospheric OA.

  6. Hysteresis in the solid oxide fuel cell cathode reaction

    DEFF Research Database (Denmark)

    Jacobsen, Torben; Zachau-Christiansen, Birgit; Bay, Lasse

    2001-01-01

    The oxygen electrode reaction at the Pt/yttria-stabilised zirconia (YSZ) interface is investigated at 1000degreesC on Pt point electrodes on YSZ and YSZ point contacts on Pt. Linear potential sweeps show a pronounced non-linear current-voltage relation and inductive hysteresis, in particular at l...

  7. Aqueous Oxidative Heck Reaction as a Protein-Labeling Strategy

    NARCIS (Netherlands)

    Ourailidou, Marilena; van der Meer, Jan-Ytzen; Baas, Bert-Jan; Jeronimus-Stratingh, Catherine; Gottumukkala, Aditya L.; Poelarends, Gerrit J.; Minnaard, Adriaan J.; Dekker, Frans

    2014-01-01

    An increasing number of chemical reactions are being employed for bio-orthogonal ligation of detection labels to protein-bound functional groups. Several of these strategies, however, are limited in their application to pure proteins and are ineffective in complex biological samples such as cell

  8. Epoxidation and oxidation reactions using 1,4-butanediol ...

    Indian Academy of Sciences (India)

    Unknown

    and aryl halides to hydroxy compounds through a .... Epoxidation of olefins using 1,4-BDDMA-crosslinked polystyrene supported t- butyl hydroperoxide. Reaction. Isolated. Olefina timeb (h). Productc yield (%). Cinnamic acid. 39 ... aCinnamic acid; bcyclohexene; csubstrate to resin 1 : 2; solvent, dioxan, temperature, 70°C.

  9. Oxide Interfaces: emergent structure and dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Clarke, Roy [Univ. of Michigan, Ann Arbor, MI (United States)

    2016-08-16

    This Final Report describes the scientific accomplishments that have been achieved with support from grant DE-FG02-06ER46273 during the period 6/1/2012– 5/31/2016. The overall goals of this program were focused on the behavior of epitaxial oxide heterostructures at atomic length scales (Ångstroms), and correspondingly short time-scales (fs -ns). The results contributed fundamentally to one of the currently most active frontiers in condensed matter physics research, namely to better understand the intricate relationship between charge, lattice, orbital and spin degrees of freedom that are exhibited by complex oxide heterostructures. The findings also contributed towards an important technological goal which was to achieve a better basic understanding of structural and electronic correlations so that the unusual properties of complex oxides can be exploited for energy-critical applications. Specific research directions included: probing the microscopic behavior of epitaxial interfaces and buried layers; novel materials structures that emerge from ionic and electronic reconfiguration at epitaxial interfaces; ultrahigh-resolution mapping of the atomic structure of heterointerfaces using synchrotron-based x-ray surface scattering, including direct methods of phase retrieval; using ultrafast lasers to study the effects of transient strain on coherent manipulation of multi-ferroic order parameters; and investigating structural ordering and relaxation processes in real-time.

  10. Controlled nitric oxide production via O(1D) + N2O reactions for use in oxidation flow reactor studies

    Science.gov (United States)

    Lambe, Andrew; Massoli, Paola; Zhang, Xuan; Canagaratna, Manjula; Nowak, John; Daube, Conner; Yan, Chao; Nie, Wei; Onasch, Timothy; Jayne, John; Kolb, Charles; Davidovits, Paul; Worsnop, Douglas; Brune, William

    2017-06-01

    Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O3) is photolyzed at 254 nm to produce O(1D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NOx (NO + NO2) to nitric acid (HNO3), making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2) radicals as a sink for organic peroxy (RO2) radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(1D) + N2O → 2NO, followed by the reaction NO + O3 → NO2 + O2. Laboratory measurements coupled with photochemical model simulations suggest that O(1D) + N2O reactions can be used to systematically vary the relative branching ratio of RO2 + NO reactions relative to RO2 + HO2 and/or RO2 + RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO3-) reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.

  11. Exploiting Fission Chain Reaction Dynamics to Image Fissile Materials

    Science.gov (United States)

    Chapman, Peter Henry

    Radiation imaging is one potential method to verify nuclear weapons dismantlement. The neutron coded aperture imager (NCAI), jointly developed by Oak Ridge National Laboratory (ORNL) and Sandia National Laboratories (SNL), is capable of imaging sources of fast (e.g., fission spectrum) neutrons using an array of organic scintillators. This work presents a method developed to discriminate between non-multiplying (i.e., non-fissile) neutron sources and multiplying (i.e., fissile) neutron sources using the NCAI. This method exploits the dynamics of fission chain-reactions; it applies time-correlated pulse-height (TCPH) analysis to identify neutrons in fission chain reactions. TCPH analyzes the neutron energy deposited in the organic scintillator vs. the apparent neutron time-of-flight. Energy deposition is estimated from light output, and time-of-flight is estimated from the time between the neutron interaction and the immediately preceding gamma interaction. Neutrons that deposit more energy than can be accounted for by their apparent time-of-flight are identified as fission chain-reaction neutrons, and the image is reconstructed using only these neutron detection events. This analysis was applied to measurements of weapons-grade plutonium (WGPu) metal and 252Cf performed at the Nevada National Security Site (NNSS) Device Assembly Facility (DAF) in July 2015. The results demonstrate it is possible to eliminate the non-fissile 252Cf source from the image while preserving the fissileWGPu source. TCPH analysis was also applied to additional scenes in which theWGPu and 252Cf sources were measured individually. The results of these separate measurements further demonstrate the ability to remove the non-fissile 252Cf source and retain the fissileWGPu source. Simulations performed using MCNPX-PoliMi indicate that in a one hour measurement, solid spheres ofWGPu are retained at a 1sigma level for neutron multiplications M -˜ 3.0 and above, while hollowWGPu spheres are

  12. Criegee Intermediates: What Direct Production and Detection Can Teach Us About Reactions of Carbonyl Oxides

    Science.gov (United States)

    Taatjes, Craig A.

    2017-05-01

    The carbonyl oxide intermediates in the ozonolysis of alkenes, often known as Criegee intermediates, are potentially important reactants in Earth's atmosphere. For decades, careful analysis of ozonolysis systems was employed to derive an understanding of the formation and reactions of these species. Recently it has proved possible to synthesize at least some of these intermediates separately from ozonolysis, and hence to measure their reaction kinetics directly. Direct measurements have allowed new or more detailed understanding of each type of gas-phase reaction that carbonyl oxides undergo, often acting as a complement to highly detailed ozonolysis experiments. Moreover, the use of direct characterization methods to validate increasingly accurate theoretical investigations can enhance their impact well beyond the set of specific reactions that have been measured. Reactions that initiate particles or fuel their growth could be a new frontier for direct measurements of Criegee intermediate chemistry.

  13. Effects of (n, γ) reaction on chromium oxides (VI)

    International Nuclear Information System (INIS)

    Di Risio, Cecilia; Marques, Roberto

    1988-01-01

    A study of the behaviour of the recoil atom in irradiated CrO 3 has been performed. Irradiations were made in a nuclear reactor; post-irradiation analysis was performed using low voltage paper electrophoresis; an isothermal step annealing study was also conducted. Obtained values for rate constants and the activation energy for the annealing reaction are presented. A comparison with the behaviour reported for different chromates was performed. (Author) [es

  14. Dynamics of nuclear fission and heavy-ion reactions

    International Nuclear Information System (INIS)

    Nix, J.R.; Sierk, A.J.

    1979-01-01

    Large-amplitude collective motion in fission and heavy-ion reactions is studied by solving classical equations of motion for the time evolution of the nuclear shape. In the nuclear potential energy of deformation, the generalized surface energy was calculated by means of a double volume integral of a Yukawa-plus-exponential function, which was obtained by requiring that two semi-infinite slabs of constant-density nuclear matter have minimum energy at zero separation. The collective kinetic energy is calculated for nuclear flow that is a superposition of incompressible, nearly irrotational collective-shape motion and rigid-body rotation. Nuclear dissipation is included by means of the Rayleigh dissipation function, which depends upon the physical mechanism that converts collective energy into internal energy. For both ordinary two-body viscosity and a combined wall and window one-body dissipation, fission-fragment kinetic energies are calculated for the fission of nuclei throughout the periodic table and compare with experimental results. Finally, the one-body dynamics of nucleons inside a cylinder colliding with a moving piston is explicitly studied by solving exactly the collisionless Boltzmann equation for the distribution function. By examining the relative phases of the pressure at the piston and the piston's velocity, a dissipative force and an elastic restoring force can be separately identified. 9 references

  15. Analysis of reaction products formed in the gas phase reaction of E,E-2,4-hexadienal with atmospheric oxidants: Reaction mechanisms and atmospheric implications

    Science.gov (United States)

    Colmenar, I.; Martin, P.; Cabañas, B.; Salgado, S.; Martinez, E.

    2018-03-01

    An analysis of reaction products for the reaction of E,E-2,4-hexadienal with chlorine atoms (Cl) and OH and NO3 radicals has been carried out at the first time with the aim of obtaining a better understanding of the tropospheric reactivity of α,β-unsaturated carbonyl compounds. Fourier Transform Infrared (FTIR) spectroscopy and Gas Chromatography-Mass Spectrometry with a Time of Flight detector (GC-TOFMS) were used to carry out the qualitative and/or quantitative analyses. Reaction products in gas and particulate phase were observed from the reactions of E,E-2,4- hexadienal with all oxidants. E/Z-Butenedial and maleic anhydride were the main products identified in gas phase. E-butenedial calculated molar yield ranging from 4 to 10%. A significant amount of multifunctional compounds (chloro and hydroxy carbonyls) was identified. These compounds could be formed in particulate phase explaining the ∼90% of unaccounted carbon in gas phase. The reaction with Cl atoms in the presence of NOx with a long reaction time gave Peroxy Acetyl Nitrate (PAN) as an additional product, which is known for being an important specie in the generation of the photochemical smog. Nitrated compounds were the major organic products from the reaction with the NO3 radical. Based on the identified products, the reaction mechanisms have been proposed. In these mechanisms a double bond addition of the atmospheric oxidant at C4/C5 of E,E-2,4-hexadienal is the first step for tropospheric degradation.

  16. Reaction mechanism for the free-edge oxidation of soot by O 2

    KAUST Repository

    Raj, Abhijeet; da Silva, Gabriel; Chung, Suk-Ho

    2012-01-01

    The reaction pathways for the oxidation by O 2 of polycyclic aromatic hydrocarbons present in soot particles are investigated using density functional theory at B3LYP/6-311++G(d,p) level of theory. For this, pyrene radical (4-pyrenyl) is chosen as the model molecule, as most soot models present in the literature employ the reactions involving the conversion of 4-pyrenyl to 4-phenanthryl by O 2 and OH to account for soot oxidation. Several routes for the formation of CO and CO 2 are proposed. The addition of O 2 on a radical site to form a peroxyl radical is found to be barrierless and exothermic with reaction energy of 188kJ/mol. For the oxidation reaction to proceed further, three pathways are suggested, each of which involve the activation energies of 104, 167 and 115kJ/mol relative to the peroxyl radical. The effect of the presence of H atom on a carbon atom neighboring the radical site on the energetics of carbon oxidation is assessed. Those intermediate species formed during oxidation with seven-membered rings or with a phenolic group are found to be highly stable. The rate constants evaluated using transition state theory in the temperature range of 300-3000K for the reactions involved in the mechanism are provided. © 2012 The Combustion Institute.

  17. Reaction mechanism for the free-edge oxidation of soot by O 2

    KAUST Repository

    Raj, Abhijeet

    2012-11-01

    The reaction pathways for the oxidation by O 2 of polycyclic aromatic hydrocarbons present in soot particles are investigated using density functional theory at B3LYP/6-311++G(d,p) level of theory. For this, pyrene radical (4-pyrenyl) is chosen as the model molecule, as most soot models present in the literature employ the reactions involving the conversion of 4-pyrenyl to 4-phenanthryl by O 2 and OH to account for soot oxidation. Several routes for the formation of CO and CO 2 are proposed. The addition of O 2 on a radical site to form a peroxyl radical is found to be barrierless and exothermic with reaction energy of 188kJ/mol. For the oxidation reaction to proceed further, three pathways are suggested, each of which involve the activation energies of 104, 167 and 115kJ/mol relative to the peroxyl radical. The effect of the presence of H atom on a carbon atom neighboring the radical site on the energetics of carbon oxidation is assessed. Those intermediate species formed during oxidation with seven-membered rings or with a phenolic group are found to be highly stable. The rate constants evaluated using transition state theory in the temperature range of 300-3000K for the reactions involved in the mechanism are provided. © 2012 The Combustion Institute.

  18. Cellular and molecular dynamics in the foreign body reaction

    NARCIS (Netherlands)

    Luttikhuizen, Daniel T.; Harmsen, Martin C.; Van Luyn, Marja J. A.

    Intracorporally implanted materials, such as medical devices, will provoke the body to initiate an inflammatory reaction. This inflammatory reaction to implanted materials is known as the foreign body reaction (FBR) and is characterized by 3 distinct phases: onset, progression, and resolution. The

  19. Extensive Bone Reaction From Catastrophic Oxidized Zirconium Wear.

    Science.gov (United States)

    Cassar-Gheiti, Adrian J; Collins, Dennis; McCarthy, Tom

    2016-01-01

    The use of alternative bearing surfaces for total hip arthroplasty has become popular to minimize wear and increase longevity, especially in young patients. Oxidized zirconium (Oxinium; Smith & Nephew, Memphis, Tennessee) femoral heads were introduced in the past decade for use in total hip arthroplasty. The advantages of oxidized zirconium include less risk of fracture compared with traditional ceramic heads. This case report describes a patient with a history of bilateral avascular necrosis of the femoral head after chemotherapy for acute lymphoblastic leukemia. Nonoperative management of avascular necrosis failed, and the patient was treated with bilateral total hip arthroplasty. The patient was followed at regular intervals and had slow eccentric polyethylene wear during a 10-year period. After 10 years, the patient had accelerated wear, with femoral and acetabular bone changes as a result of Oxinium and ultrahigh-molecular-weight polyethylene wear during a 6-month period. This article highlights the unusual accelerated bone changes that occurred as a result of Oxinium wear particles. Copyright 2016, SLACK Incorporated.

  20. Oxidation of ligand-protected aluminum clusters: An ab initio molecular dynamics study

    International Nuclear Information System (INIS)

    Alnemrat, Sufian; Hooper, Joseph P.

    2014-01-01

    We report Car-Parrinello molecular dynamics simulations of the oxidation of ligand-protected aluminum clusters that form a prototypical cluster-assembled material. These clusters contain a small aluminum core surrounded by a monolayer of organic ligand. The aromatic cyclopentadienyl ligands form a strong bond with surface Al atoms, giving rise to an organometallic cluster that crystallizes into a low-symmetry solid and is briefly stable in air before oxidizing. Our calculations of isolated aluminum/cyclopentadienyl clusters reacting with oxygen show minimal reaction between the ligand and O 2 molecules at simulation temperatures of 500 and 1000 K. In all cases, the reaction pathway involves O 2 diffusing through the ligand barrier, splitting into atomic oxygen upon contact with the aluminum, and forming an oxide cluster with aluminum/ligand bonds still largely intact. Loss of individual aluminum-ligand units, as expected from unimolecular decomposition calculations, is not observed except following significant oxidation. These calculations highlight the role of the ligand in providing a steric barrier against oxidizers and in maintaining the large aluminum surface area of the solid-state cluster material

  1. Vanadium oxide V2O5 reaction with calcium metavanadate

    International Nuclear Information System (INIS)

    Krasnenko, T.I.; Slobodin, B.V.; Zhilyaev, V.A.

    1983-01-01

    Complex physicochemical studies on the V 2 O 5 Ca(VO 3 ) 2 mixtures, annealed under different conditions, were conducted. It was established that the V 2 O 5 -Ca(VO 3 ) 2 system is characterized by the following features: defective structure of initial components, which are in equilibrium state; irreversible structural transformation without changes in the macrosymmetry (530 deg C) of calcium metavanadate, deficient in calcium and oxygen; melting of eutectic mixture of components which are in equilibrium at 616+-3 deg C; Ca(VO 3 ) 2 melting with decomposition at 775+-3 deg C. Besides this, the formation of oxide vanadium bronze of β-type calcium is possible under some conditions (narrow temperature range, certain partial oxygen pressure, etc)

  2. Palladium-based electrocatalysts for ethanol oxidation reaction in DEFC

    International Nuclear Information System (INIS)

    Moraes, L.P.R. de; Elsheikh, A.; Silva, E. L. da; Radtke, C.; Amico, S.C.; Malfatti, C.F.

    2014-01-01

    Direct ethanol fuel cells require the use of electrocatalysts to promote bond cleavage of the ethanol molecule in an efficient way. Currently, most electrocatalysts contain platinum, which enables improved catalytic activity and stability in acidic media. However platinum presents high cost and low availability. Based on that, novel catalysts have been developed, such as those based on palladium and its alloys, which have attained excellent results in the oxidation of ethanol in alkaline media. In this work, Pd, PdSn and PdNiSn catalysts supported on Vulcan XC72R carbon were synthesized via impregnation/reduction. The electrocatalysts were characterized by RBS, XRD and cyclic voltammetry. The X-ray diffraction results showed the formation of an alloy and not the deposition of isolated elements. The synthesized catalysts displayed good catalytic activity, as observed by cyclic voltammetry, being the best electrochemical performance achieved by the ternary alloy. (author)

  3. Measuring the complex behavior of the SO2 oxidation reaction

    Directory of Open Access Journals (Sweden)

    Muhammad Shahzad

    2015-09-01

    Full Text Available The two step reversible chemical reaction involving five chemical species is investigated. The quasi equilibrium manifold (QEM and spectral quasi equilibrium manifold (SQEM are used for initial approximation to simplify the mechanisms, which we want to utilize in order to investigate the behavior of the desired species. They show a meaningful picture, but for maximum clarity, the investigation method of invariant grid (MIG is employed. These methods simplify the complex chemical kinetics and deduce low dimensional manifold (LDM from the high dimensional mechanism. The coverage of the species near equilibrium point is investigated and then we shall discuss moving along the equilibrium of ODEs. The steady state behavior is observed and the Lyapunov function is utilized to study the stability of ODEs. Graphical results are used to describe the physical aspects of measurements.

  4. Selection of Suitable Microorganism for Biocatalytic Oxidation Reaction of Racemic Propranolol

    Directory of Open Access Journals (Sweden)

    Rahime SONGÜR

    2017-12-01

    Full Text Available Propranolol is one of the β-blockers which are pharmaceutically important, especially used for treatment of cardiovasculer disease. In this study, the production of enantiomerically pure propranolol was aimed via biocatalytic deracemization including tandem oxidation-reduction reactions of racemic propranolol. Within this content, firstly suitable microorganism for the oxidation of racemic propranolol was investigated. Alcohol dehydrogenase (ADH enzyme for oxidation of propranolol and NADH oxidase enzyme for cofactor regeneration were necessary for the oxidation reactions. For this reason, ADH and NADH oxidase enzymes activities of different microorganisms were measured to select the microorganism for using as enzyme source. These microorganisms are Lactobacillus kefir NRRL B-1839, Rhodotorula glutunis DSM 70398, Rhizopus oryzae CBS 111718, Rhizopus arhizus. The highest ADH and NADH oxidase activities were obtained for L. kefir.

  5. Neutron Reflectivity Measurement for Polymer Dynamics near Graphene Oxide Monolayers

    Science.gov (United States)

    Koo, Jaseung

    We investigated the diffusion dynamics of polymer chains confined between graphene oxide layers using neutron reflectivity (NR). The bilayers of polymethylmetacrylate (PMMA)/ deuterated PMMA (d-PMMA) films and polystyrene (PS)/d-PS films with various film thickness sandwiched between Langmuir-Blodgett (LB) monolayers of graphene oxide (GO) were prepared. From the NR results, we found that PMMA diffusion dynamics was reduced near the GO surface while the PS diffusion was not significantly changed. This is due to the different strength of GO-polymer interaction. In this talk, these diffusion results will be compared with dewetting dynamics of polymer thin films on the GO monolayers. This has given us the basis for development of graphene-based nanoelectronics with high efficiency, such as heterojunction devices for polymer photovoltaic (OPV) applications.

  6. Morphological impact on the reaction kinetics of size-selected cobalt oxide nanoparticles

    International Nuclear Information System (INIS)

    Bartling, Stephan; Meiwes-Broer, Karl-Heinz; Barke, Ingo; Pohl, Marga-Martina

    2015-01-01

    Apart from large surface areas, low activation energies are essential for efficient reactions, particularly in heterogeneous catalysis. Here, we show that not only the size of nanoparticles but also their detailed morphology can crucially affect reaction kinetics, as demonstrated for mass-selected, soft-landed, and oxidized cobalt clusters in a 6 nm to 18 nm size range. The method of reflection high-energy electron diffraction is extended to the quantitative determination of particle activation energies which is applied for repeated oxidation and reduction cycles at the same particles. We find unexpectedly small activation barriers for the reduction reaction of the largest particles studied, despite generally increasing barriers for growing sizes. We attribute these observations to the interplay of reaction-specific material transport with a size-dependent inner particle morphology

  7. Redox regulation and pro-oxidant reactions in the physiology of circadian systems.

    Science.gov (United States)

    Méndez, Isabel; Vázquez-Martínez, Olivia; Hernández-Muñoz, Rolando; Valente-Godínez, Héctor; Díaz-Muñoz, Mauricio

    2016-05-01

    Rhythms of approximately 24 h are pervasive in most organisms and are known as circadian. There is a molecular circadian clock in each cell sustained by a feedback system of interconnected "clock" genes and transcription factors. In mammals, the timing system is formed by a central pacemaker, the suprachiasmatic nucleus, in coordination with a collection of peripheral oscillators. Recently, an extensive interconnection has been recognized between the molecular circadian clock and the set of biochemical pathways that underlie the bioenergetics of the cell. A principle regulator of metabolic networks is the flow of electrons between electron donors and acceptors. The concomitant reduction and oxidation (redox) reactions directly influence the balance between anabolic and catabolic processes. This review summarizes and discusses recent findings concerning the mutual and dynamic interactions between the molecular circadian clock, redox reactions, and redox signaling. The scope includes the regulatory role played by redox coenzymes (NAD(P)+/NAD(P)H, GSH/GSSG), reactive oxygen species (superoxide anion, hydrogen peroxide), antioxidants (melatonin), and physiological events that modulate the redox state (feeding condition, circadian rhythms) in determining the timing capacity of the molecular circadian clock. In addition, we discuss a purely metabolic circadian clock, which is based on the redox enzymes known as peroxiredoxins and is present in mammalian red blood cells and in other biological systems. Both the timing system and the metabolic network are key to a better understanding of widespread pathological conditions such as the metabolic syndrome, obesity, and diabetes. Copyright © 2015 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.

  8. Enhancement of nitrite on heme-induced oxidative reactions: A potential toxicological implication.

    Science.gov (United States)

    Lu, Naihao; Chen, Wei; Zhu, Jingjie; Peng, Yi-Yuan

    2012-02-01

    Evidence to support the role of heme as major inducers of oxidative damage is increasingly present. Nitrite (NO(2)(-)) is one of the major end products of NO metabolism. Although the biological significance of heme/NO(2)(-)-mediated protein tyrosine nitration is a subject of great interest, the important roles of NO(2)(-) on heme-dependent redox reaction have been greatly underestimated. In this study, we investigated the influence of NO(2)(-) on heme -dependent oxidative reactions. It was found that NO(2)(-) had the capacity to act as a reducing agent to remove high oxidation states of heme iron. In the reduction of ferryl heme to ferric heme, NO(2)(-) was oxidized to a nitrating agent NO(2), and subsequently, tyrosine residues in bovine serum albumin (BSA) were nitrated. However, the presence of NO(2)(-) surprisingly exerted pro-oxidant effect on heme-H(2)O(2)-induced formation of BSA carbonyls at lower concentrations and enhanced the loss of HepG2 cell viability dose-dependently, which was probably due to the ability of this inorganic compound to efficiently enhance the peroxidase activity and oxidative degradation of heme. These data provide novel evidence that the dietary intake and experimental use of NO(2)(-) in vivo and in vitro would possess the pro-oxidant activity through interfering in heme-dependent oxidative reactions. Besides the classic role in protein tyrosine nitration, the deleterious effects on heme redox reactions may provide new insights into the toxicological implications of NO(2)(-) with cellular heme proteins. Copyright © 2011 Elsevier Ltd. All rights reserved.

  9. Structural and surface changes of cobalt modified manganese oxide during activation and ethanol steam reforming reaction

    Science.gov (United States)

    Gac, Wojciech; Greluk, Magdalena; Słowik, Grzegorz; Turczyniak-Surdacka, Sylwia

    2018-05-01

    Surface and structural changes of unmodified manganese and cobalt-manganese oxide during activation and ethanol steam reforming reaction conditions (ESR) were studied by means of X-ray diffraction, X-ray photoelectron spectroscopy, temperature-programmed reduction/oxidation (TPR/TPO) and transmission electron microscopy. It was shown that synthesis of cobalt manganese oxide by the redox precipitation method led to the formation of strongly dispersed cobalt ionic species within cryptomelane-based manganese oxide structure. Development of large cube-like MnO nanoparticles with spherical cobalt metallic crystallites decorated by manganese oxide on the high oxidation state and potassium species was observed during reduction. Cobalt manganese catalyst showed high initial activity and selectivity to H2 and CO2 in ethanol stem reforming reaction in the range of 390-480 °C. The drop of ethanol conversion and changes of selectivity with the time-on-stream were observed. An increase of reaction temperature led to intensification of deactivation phenomena. TEM studies evidenced coexistence of Co and CoOx nanoparticles formed under ethanol steam reforming conditions, partially covered by filamentous and encapsulating carbonaceous deposits.

  10. Langevin dynamics of A+A reactions in one dimension

    International Nuclear Information System (INIS)

    Sancho, J M; Romero, A H; Lacasta, A M; Lindenberg, Katja

    2007-01-01

    We propose a set of Langevin equations of motion together with a reaction rule for the study of binary reactions. Our scheme is designed to address this problem for arbitrary friction γ and temperature T. It easily accommodates the inclusion of a substrate potential, and it lends itself to straightforward numerical integration. We test this approach on diffusion-limited (γ → ∞) as well as ballistic (γ = 0) A+A → P reactions for which there are extensive exact and approximate theoretical results as well as extensive Monte Carlo results. We reproduce the known results using our integration scheme, and also present new results for the ballistic reactions

  11. Development of a quantum chemical molecular dynamics tribochemical simulator and its application to tribochemical reaction dynamics of lubricant additives

    International Nuclear Information System (INIS)

    Onodera, T; Tsuboi, H; Hatakeyama, N; Endou, A; Miyamoto, A; Miura, R; Takaba, H; Suzuki, A; Kubo, M

    2010-01-01

    Tribology at the atomistic and molecular levels has been theoretically studied by a classical molecular dynamics (MD) method. However, this method inherently cannot simulate the tribochemical reaction dynamics because it does not consider the electrons in nature. Although the first-principles based MD method has recently been used for understanding the chemical reaction dynamics of several molecules in the tribology field, the method cannot simulate the tribochemical reaction dynamics of a large complex system including solid surfaces and interfaces due to its huge computation costs. On the other hand, we have developed a quantum chemical MD tribochemical simulator on the basis of a hybrid tight-binding quantum chemical/classical MD method. In the simulator, the central part of the chemical reaction dynamics is calculated by the tight-binding quantum chemical MD method, and the remaining part is calculated by the classical MD method. Therefore, the developed tribochemical simulator realizes the study on tribochemical reaction dynamics of a large complex system, which cannot be treated by using the conventional classical MD or the first-principles MD methods. In this paper, we review our developed quantum chemical MD tribochemical simulator and its application to the tribochemical reaction dynamics of a few lubricant additives

  12. Physical Chemistry of Reaction Dynamics in Ionic Liquid

    Energy Technology Data Exchange (ETDEWEB)

    Maroncelli, Mark [Pennsylvania State Univ., University Park, PA (United States)

    2016-10-02

    Work completed over the past year mainly involves finishing studies related to solvation dynamics in ionic liquids, amplifying and extending our initial PFG-NMR work on solute diffusion, and learning how to probe rotational dynamics in ionic liquids.

  13. A combinatorial chemistry approach to the investigation of cerium oxide and plutonium oxide reactions with small molecules

    Science.gov (United States)

    Brady, John T.; Warner, Benjamin P.; Bridgewater, Jon S.; Havrilla, George J.; Morris, David E.; Buscher, C. Thomas

    2000-07-01

    We are currently investigating the potential chemistry of the 3013 Standard waste storage containers. These containers are filled with waste that is a mixture of inorganic salts and plutonium oxide that has been calcined to remove water and other volatiles. There has been concern about possible pressure buildup due to the formation of hydrogen or other gases. We are utilizing a combinatorial chemistry approach to investigate a range of possible reactions that may occur in the containers with various concentrations of metal oxides and inorganic salts.

  14. Ferrocyanide Safety Project Dynamic X-Ray Diffraction studies of sodium nickel ferrocyanide reactions with equimolar nitrate/nitrite salts

    International Nuclear Information System (INIS)

    Dodds, J.N.; UNOCAL, Brea, CA

    1994-07-01

    Dynamic X-ray Diffraction (DXRD) has been to used to identify and quantify the solid state reactions that take place between sodium nickel ferrocyanide, Na 2 NiFe(CN) 6 , and equimolar concentrations of sodium nitrate/nitrite, reactions of interest to the continued environmental safety of several large underground waste storage tanks at the Hanford site in eastern Washington. The results are supportive of previous work, which indicated that endothermic dehydration and melting of the nitrates take place before the occurrence of exothermic reactions that being about 300 degrees C. The DXRD results show that a major reaction set at these temperatures is the occurrence of a series reaction that produces sodium cyanate, NaCNO, as an intermediate in a mildly exothermic first step. In the presence of gaseous oxygen, NaCNO subsequently reacts exothermally and at a faster rate to form metal oxides. Measurements of the rate of this reaction are used to estimate the heat release. Comparisons of this estimated heat release rate with heat transfer rates from a hypothetical ''hot spot'' show that, even in a worst-case scenario, the heat transfer rates are approximately eight times higher than the rate of energy release from the exothermic reactions

  15. Laccase-Functionalized Graphene Oxide Assemblies as Efficient Nanobiocatalysts for Oxidation Reactions

    NARCIS (Netherlands)

    Patila, Michaela; Kouloumpis, Antonios; Gournis, Dimitrios; Rudolf, Petra; Stamatis, Haralambos

    Multi-layer graphene oxide-enzyme nanoassemblies were prepared through the multi-point covalent immobilization of laccase from Trametes versicolor (TvL) on functionalized graphene oxide (fGO). The catalytic properties of the fGO-TvL nanoassemblies were found to depend on the number of the graphene

  16. Catalytic activity of metall-like carbides in carbon oxide oxidation reaction

    International Nuclear Information System (INIS)

    Kharlamov, A.I.; Kosolapova, T.Ya.; Rafal, A.N.; Kirillova, N.V.

    1980-01-01

    Kinetics of carbon oxide oxidation upon carbides of hafnium, niobium, tantalum, molybdenum, zirconium and chromium is studied. Probable mechanism of the catalysts action is suggested. The established character of the change of the carbide catalytic activity is explained by the change of d-electron contribution to the metal-metal interaction

  17. Sulphation reactions of oxidic dust particles in waste heat boiler environment. Literature review

    Energy Technology Data Exchange (ETDEWEB)

    Ranki, T.

    1999-09-01

    Sulphation of metal oxides has an important role in many industrial processes. In different applications sulphation reactions have different aims and characteristics. In the flash smelting process sulphation of oxidic flue dust is a spontaneous and inevitable phenomena, which takes place in the waste heat boiler (WHB) when cooling down hot dust laden off-gases from sulphide smelters. Oxidic dust particles (size 0 - 50 {mu}m) react with O{sub 2} and SO{sub 2} or SO{sub 3} in a certain temperature range (500 - 800 deg C). Sulphation reactions are highly exothermic releasing large amount of heat, which affects the gas cooling and thermal performance of the boiler. Thermodynamics and kinetics of the system have to be known to improve the process and WHB operation. The rate of sulphation is affected by the prevailing conditions (temperature, gas composition) and particle size and microstructure (porosity, surface area). Some metal oxides (CuO) can react readily with SO{sub 2} and O{sub 2} and act as self-catalysts, but others (NiO) require the presence of an external catalyst to enhance the SO{sub 3} formation and sulphation to proceed. Some oxides (NiO) sulphate directly, some (CuO) may form first intermediate phases (basic sulphates) depending on the reaction conditions. Thus, the reaction mechanisms are very complex. The aim of this report was to search information about the factors affecting the dust sulphation reactions and suggested reaction mechanisms and kinetics. Many investigators have studied sulphation thermodynamics and reaction kinetics and mechanisms of macroscopical metal oxide pieces, but only few articles have been published about sulphation of microscopical particles, like dust. All the found microscale studies dealt with sulphation reactions of calcium oxide, which is not present in the flash smelting process, but used as an SO{sub 2} absorbent in the combustion processes. However, also these investigations may give some hints about the sulphation

  18. An Alternative Reaction Pathway for Iridium Catalyzed Water Oxidation Driven by CAN

    KAUST Repository

    Bucci, Alberto

    2016-06-10

    The generation of solar fuels by means of a photosynthetic apparatus strongly relies on the development of an efficient water oxidation catalyst (WOC). Cerium ammonium nitrate (CAN) is the most commonly used sacrificial oxidant to explore the potentiality of WOCs. It is usually assumed that CAN has the unique role to oxidatively energize WOCs, making them capable to offer a low energy reaction pathway to transform H2O to O2. Herein we show that CAN might have a much more relevant and direct role in WO, mainly related to the capture and liberation of O–O containing molecular moieties.

  19. An Alternative Reaction Pathway for Iridium Catalyzed Water Oxidation Driven by CAN

    KAUST Repository

    Bucci, Alberto; Menendez Rodriguez, Gabriel; Bellachioma, Gianfranco; Zuccaccia, Cristiano; Poater, Albert; Cavallo, Luigi; Macchioni, Alceo

    2016-01-01

    The generation of solar fuels by means of a photosynthetic apparatus strongly relies on the development of an efficient water oxidation catalyst (WOC). Cerium ammonium nitrate (CAN) is the most commonly used sacrificial oxidant to explore the potentiality of WOCs. It is usually assumed that CAN has the unique role to oxidatively energize WOCs, making them capable to offer a low energy reaction pathway to transform H2O to O2. Herein we show that CAN might have a much more relevant and direct role in WO, mainly related to the capture and liberation of O–O containing molecular moieties.

  20. RuO4-mediated oxidation of secondary amines 2. imines as main reaction intermediates

    Directory of Open Access Journals (Sweden)

    Florea Cristina A.

    2017-01-01

    Full Text Available Oxidation by RuO4 (generated in situ from RuO2 and NaIO4 of secondary amines such as Bn–NH–CH2R (1; R=H, Me gave complex reaction mixtures, but mainly amides. In the presence of cyanide, the leading products were α-aminonitriles. Comparison of the oxidation products of 1 with those from the corresponding imines PhCH=N–CH2R and Bn–N=CH–R showed that formation of the indicated imines is the first main step in the oxidation of 1. A detailed mechanism is proposed.

  1. Factors responsible for activity of catalysts of different chemical types in the reaction of hydrogen oxidation

    International Nuclear Information System (INIS)

    Il'chenko, N.I.; Dolgikh, L.Yu.

    1985-01-01

    Reasons of differences in the kinetics and mechanism of the H 2 oxidation on optimum metallic (Pt), carbide (WC) and oxide (Co 3 O 4 ) catalysts are discussed. These differences lead to unequal specific activity. It is shown that the catalytic activity of the catalysts in question increases with respect to reactions of isotopic exchange and hydrogen oxidation with an increasing electron-donating ability of anat of the transition metal M on which H 2 is adsorbed. The possibility is considered of increasing the transition metal activity by introduction of additions to increase the electron-donating ability of M

  2. The Dynamics of Chemical Reactions: Atomistic Visualizations of Organic Reactions, and Homage to van 't Hoff.

    Science.gov (United States)

    Yang, Zhongyue; Houk, K N

    2018-03-15

    Jacobus Henricus van 't Hoff was the first Nobel Laureate in Chemistry. He pioneered in the study of chemical dynamics, which referred at that time to chemical kinetics and thermodynamics. The term has evolved in modern times to refer to the exploration of chemical transformations in a time-resolved fashion. Chemical dynamics has been driven by the development of molecular dynamics trajectory simulations, which provide atomic visualization of chemical processes and illuminate how dynamic effects influence chemical reactivity and selectivity. In homage to the legend of van 't Hoff, we review the development of the chemical dynamics of organic reactions, our area of research. We then discuss our trajectory simulations of pericyclic reactions, and our development of dynamic criteria for concerted and stepwise reaction mechanisms. We also describe a method that we call environment-perturbed transition state sampling, which enables trajectory simulations in condensed-media using quantum mechanics and molecular mechanics (QM/MM). We apply the method to reactions in solvent and in enzyme. Jacobus Henricus van 't Hoff (1852, Rotterdam-1911, Berlin) received the Nobel Prize for Chemistry in 1901 "in recognition of the extraordinary services he has rendered by the discovery of the laws of chemical dynamics and osmotic pressure in solutions". van 't Hoff was born the Netherlands, and earned his doctorate in Utrecht in 1874. In 1896 he moved to Berlin, where he was offered a position with more research and less teaching. van 't Hoff is considered one of the founders of physical chemistry. A key step in establishing this new field was the start of Zeitschrift für Physikalische Chemie in 1887. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Reaction dynamics of small molecules at metal surfaces

    International Nuclear Information System (INIS)

    Samson, P.A.

    1999-09-01

    The dissociation-desorption dynamics of D 2 upon the Sn/Pt(111) surface alloy are dependent on the surface concentration of Sn. The p(2 x 2) Sn/Pt(111) alloy surface (Θ Sn = 0.25 ML), is initially ∼30 times less reactive towards D 2 adsorption than clean Pt(111). On the (√3 x √3) R30 deg Sn/Pt(111) alloy surface (Θ Sn = 0.33 ML), increased inhibition of D 2 adsorption is reported, with S o ∼ 10 -5 at low energy, coinciding with the loss of stable Pt 3 hollow sites and a significant reduction in the D atom binding energy. Sticking on the √3 alloy is activated with an increased energy threshold of ∼280 meV, with no evidence that vibration enhances dissociation. The barrier to dissociation remains in the entrance channel before the D 2 bond begins to stretch. Vibrational excitation is, however, observed in nitrogen desorption from the catalytic reaction of NO + H 2 over Pd(110). For a surface at 600 K, N 2 vibrational state population ratios of P(v=1/v=0) = 0.50 ± 0.05 and P(v=2/v=0) = 0.60 ± 0.20 are reported. Desorption occurs via the N(ad) + N(ad) recombination channel with little energy released into translation and rotation. The translational energy release observed is dependent on the N 2 vibrational state, with translational temperatures of 425 K, 315 K and 180 K reported for the v=0, 1 and 2 states respectively. Sub-thermal energy releases and normally directed angular distributions suggest the influence of a trapping mechanism, recombining molecules scattering through a molecularly adsorbed state, with a transition state of large d NN responsible for the product vibrational excitation. Although N 2 dissociation on Fe(100) forms a simple overlayer structure, on Fe(110), molecular chemisorption does not occur at or above room temperature and the sticking is extremely small (∼10 -6 to 10 -7 ). Activated nitrogen bombardment can be used to prepare a 'surface nitride' with a structure related to the geometry of bulk Fe 4 N. Scanning tunnelling

  4. Literature information applicable to the reaction of uranium oxides with chlorine to prepare uranium tetrachloride

    Energy Technology Data Exchange (ETDEWEB)

    Haas, P.A.

    1992-02-01

    The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl{sub 4}) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbon monoxide (CO) to give CO or carbon dioxide (CO{sub 2}) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl{sub 4}-UO{sub 2} shows a reaction to form uranium oxychloride (UOCl{sub 2}) that has a good solubility in molten UCl{sub 4}. This appears more favorable to good rates of reaction than reaction of solids and gases. There is limited information on U-O-Cl salt properties. Information on the preparation of titanium, zirconium, silicon, and thorium tetrachlorides (TiCl{sub 4}, ZrCl{sub 4}, SiCl{sub 4}, ThCl{sub 4}) by reaction of oxides with chlorine (Cl{sub 2}) and carbon has application to the preparation of UCl{sub 4}.

  5. Literature information applicable to the reaction of uranium oxides with chlorine to prepare uranium tetrachloride

    International Nuclear Information System (INIS)

    Haas, P.A.

    1992-02-01

    The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl 4 ) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbon monoxide (CO) to give CO or carbon dioxide (CO 2 ) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl 4 -UO 2 shows a reaction to form uranium oxychloride (UOCl 2 ) that has a good solubility in molten UCl 4 . This appears more favorable to good rates of reaction than reaction of solids and gases. There is limited information on U-O-Cl salt properties. Information on the preparation of titanium, zirconium, silicon, and thorium tetrachlorides (TiCl 4 , ZrCl 4 , SiCl 4 , ThCl 4 ) by reaction of oxides with chlorine (Cl 2 ) and carbon has application to the preparation of UCl 4

  6. Stochastic modeling and simulation of reaction-diffusion system with Hill function dynamics.

    Science.gov (United States)

    Chen, Minghan; Li, Fei; Wang, Shuo; Cao, Young

    2017-03-14

    Stochastic simulation of reaction-diffusion systems presents great challenges for spatiotemporal biological modeling and simulation. One widely used framework for stochastic simulation of reaction-diffusion systems is reaction diffusion master equation (RDME). Previous studies have discovered that for the RDME, when discretization size approaches zero, reaction time for bimolecular reactions in high dimensional domains tends to infinity. In this paper, we demonstrate that in the 1D domain, highly nonlinear reaction dynamics given by Hill function may also have dramatic change when discretization size is smaller than a critical value. Moreover, we discuss methods to avoid this problem: smoothing over space, fixed length smoothing over space and a hybrid method. Our analysis reveals that the switch-like Hill dynamics reduces to a linear function of discretization size when the discretization size is small enough. The three proposed methods could correctly (under certain precision) simulate Hill function dynamics in the microscopic RDME system.

  7. Studies in the reaction dynamics of beam-gas chemiluminescent reactions

    International Nuclear Information System (INIS)

    Prisant, M.G.

    1984-01-01

    This thesis develops techniques for the analysis and interpretation of data obtained from beam-gas chemiluminescence experiments. These techniques are applied to experimental studies of atom transfer reactions of the type A + BC → AB + C. A procedure is developed for determining the product rotational alignment in the center-of-mass frame from polarization measurements of chemiluminescent atom-diatom exchange reactions under beam-gas conditions. Knowledge of a vector property of a reaction, such as product alignment, provides information on the disposition of angular momentum by a chemical reaction. Fluorescence polarization and hence product alignment are measured for two prototype reactions. The reaction of metastable calcium atoms with hydrogen-chloride gas yields highly aligned calcium-chloride product which exhibits little variation of alignment with vibrational state. The reaction of ground-state calcium with fluorine gas yields moderately aligned product which shows strong variation of alignment with vibration. A multi-surface direct-interaction model is developed to interpret product alignment and population data. The predictions of this model for the reaction of calcium with fluorine show reasonable agreement with experiment

  8. Propan-1-ol Oxidation Reaction on Au/TiO2 Catalysts

    African Journals Online (AJOL)

    MBI

    2014-11-27

    Nov 27, 2014 ... a decomposition pathway, producing CO2 and H2O. However, the presence of gold ... complete oxidation reaction of propan-1-ol on the catalysts. Keywords: Gold Catalysis ... flowed at a rate of 30 mL min-1. Propan- o-l was.

  9. The family of berberine bridge enzyme-like enzymes: A treasure-trove of oxidative reactions.

    Science.gov (United States)

    Daniel, Bastian; Konrad, Barbara; Toplak, Marina; Lahham, Majd; Messenlehner, Julia; Winkler, Andreas; Macheroux, Peter

    2017-10-15

    Biological oxidations form the basis of life on earth by utilizing organic compounds as electron donors to drive the generation of metabolic energy carriers, such as ATP. Oxidative reactions are also important for the biosynthesis of complex compounds, i.e. natural products such as alkaloids that provide vital benefits for organisms in all kingdoms of life. The vitamin B 2 -derived cofactors flavin mononucleotide (FMN) and flavin adenine dinucleotide (FAD) enable an astonishingly diverse array of oxidative reactions that is based on the versatility of the redox-active isoalloxazine ring. The family of FAD-linked oxidases can be divided into subgroups depending on specific sequence features in an otherwise very similar structural context. The sub-family of berberine bridge enzyme (BBE)-like enzymes has recently attracted a lot of attention due to the challenging chemistry catalyzed by its members and the unique and unusual bi-covalent attachment of the FAD cofactor. This family is the focus of the present review highlighting recent advancements into the structural and functional aspects of members from bacteria, fungi and plants. In view of the unprecedented reaction catalyzed by the family's namesake, BBE from the California poppy, recent studies have provided further insights into nature's treasure chest of oxidative reactions. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

  10. Ion-molecule reactions in the binary mixture of ethylene oxide and trioxane, 2

    International Nuclear Information System (INIS)

    Kumakura, Minoru; Arakawa, Kazuo; Sugiura, Toshio.

    1978-01-01

    The ion-molecule reactions in the binary mixture of ethylene oxide and trioxane have been studied with use of a modified time-of-flight mass spectrometer. As cross-reaction product ions, C 3 H 5 O 2 + , C 3 H 6 O 2 +sup(, and C**3**H**7**O**2**)+sup( were observed under the conditions of long delay times and elevated pressure. It was found that these ions are formed by the dissociation of unstable intermediate-complex resulting from the reaction of ethylene oxide molecular ion with trioxane. It was proposed that the complex is of cyclic structure in which positive charge is delocalized. From the consideration of isotopic distribution of the product ions in ethylene-d**4** oxide-trioxane mixtures, the skeletal structures of the product ions were investigated. The rate constants of the formation reactions of C**3**H**5**O**2**)+sup(, C**3**H**6**O**2**)+sup(, and C**3**H**7**O**2**)+sup( in ethylene oxide-trioxane mixtures were found to be 2.20 x 10)-10sup(, 2.61 x 10)-10sup(, and 1.74 x 10)-10sup( cm)3sup( molecule)-1sup(s)-1 , respectively. (auth.)

  11. Learning the Fundamentals of Kinetics and Reaction Engineering with the Catalytic Oxidation of Methane

    Science.gov (United States)

    Cybulskis, Viktor J.; Smeltz, Andrew D.; Zvinevich, Yury; Gounder, Rajamani; Delgass, W. Nicholas; Ribeiro, Fabio H.

    2016-01-01

    Understanding catalytic chemistry, collecting and interpreting kinetic data, and operating chemical reactors are critical skills for chemical engineers. This laboratory experiment provides students with a hands-on supplement to a course in chemical kinetics and reaction engineering. The oxidation of methane with a palladium catalyst supported on…

  12. Atomic platinum layer coated titanium copper nitride supported on carbon nanotubes for the methanol oxidation reaction

    CSIR Research Space (South Africa)

    Zheng, Y

    2017-09-01

    Full Text Available measurements. The results confirm the core-shell structure of the prepared TiN@Pt/CNTs catalyst. More importantly, the catalyst exhibits superb mass activity and durability for the methanol oxidation reaction (MOR) than that of the commercial JM Pt/C catalyst...

  13. Iron(III) porphyrin-catalysed oxidation reactions by m-chloro ...

    Indian Academy of Sciences (India)

    Unknown

    The notable feature in this study is that none of the kinetic traces are expo- nential. A representative plot is given in figure 1 and the quantitative spectrum of TTBP• radical in dichloromethane is given in figure 2 (bold line). In this oxidation reaction under all the conditions, non-exponential kinetic traces were always obser-.

  14. Sulfur Poisoning of the Water Gas Shift Reaction on Anode Supported Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Hagen, Anke

    2013-01-01

    resistance increased both in the high and low frequency region, which indicates a strong poisoning of the water gas shift reaction and thus a lack of hydrogen fuel in addition to the poisoning of the electrochemical hydrogen oxidation. All poisoning effects are reversible under the applied operating...

  15. Methanol electrocatalytic oxidation on Pt nanoparticles on nitrogen doped graphene prepared by the hydrothermal reaction of graphene oxide with urea

    International Nuclear Information System (INIS)

    Xu, Xiao; Zhou, Yingke; Yuan, Tao; Li, Yawei

    2013-01-01

    A facile hydrothermal reaction of graphene oxide with urea was used to produce nitrogen doped graphene, and Pt nanoparticles were deposited on the obtained nitrogen doped graphene by the NaBH 4 reduction route. The morphology and microstructure of the synthesized catalysts were characterized by transmission electron microscopy, X-ray powder diffraction and X-ray photoelectron spectroscopy, while the functional groups on the surface of the catalysts were investigated by the Fourier transform infrared spectroscopy and ultraviolet-visible absorption spectra. Cyclic voltammetry, chronoamperometry and electrochemical impedance techniques were carried out to evaluate the methanol electrocatalytic oxidation activity and durability of Pt catalysts supported on the nitrogen doped graphene. The results showed that nitrogen doping and reduction of GO were achieved simultaneously by the facile hydrothermal reaction, which had beneficial effects for the deposition process and electrocatalytic activity of Pt nanoparticles. The Pt catalysts supported on the nitrogen doped graphene substrate presented excellent activity and durability of methanol oxidation reaction, which might be promising for application in direct methanol fuel cells

  16. Ab initio molecular dynamics simulation of aqueous solution of nitric oxide in different formal oxidation states

    Science.gov (United States)

    Venâncio, Mateus F.; Rocha, Willian R.

    2015-10-01

    Ab initio molecular dynamics simulations were used to investigate the early chemical events involved in the dynamics of nitric oxide (NOrad), nitrosonium cation (NO+) and nitroxide anion (NO-) in aqueous solution. The NO+ ion is very reactive in aqueous solution having a lifetime of ∼4 × 10-13 s, which is shorter than the value of 3 × 10-10 s predicted experimentally. The NO+ reacts generating the nitrous acid as an intermediate and the NO2- ion as the final product. The dynamics of NOrad revealed the reversibly formation of a transient anion radical species HONOrad -.

  17. Storage stability of cauliflower soup powder: The effect of lipid oxidation and protein degradation reactions.

    Science.gov (United States)

    Raitio, Riikka; Orlien, Vibeke; Skibsted, Leif H

    2011-09-15

    Soups based on cauliflower soup powders, prepared by dry mixing of ingredients and rapeseed oil, showed a decrease in quality, as evaluated by a sensory panel, during the storage of the soup powder in the dark for up to 12weeks under mildly accelerated conditions of 40°C and 75% relative humidity. Antioxidant, shown to be effective in protecting the rapeseed bulk oil, used for the powder preparation, had no effect on storage stability of the soup powder. The freshly prepared soup powder had a relatively high concentration of free radicals, as measured by electron spin resonance spectroscopy, which decreased during storage, and most remarkably during the first two weeks of storage, with only marginal increase in lipid hydroperoxides as primary lipid oxidation products, and without any increase in secondary lipid oxidation products. Analyses of volatiles by SPME-GC-MS revealed a significant increase in concentrations of 2-methyl- and 3-methyl butanals, related to Maillard reactions, together with an increase in 2-acetylpyrrole concentration. The soup powders became more brown during storage, as indicated by a decreasing Hunter L-value, in accord with non-enzymatic browning reactions. A significant increase in the concentrations of dimethyl disulfide in soup powder headspace indicated free radical-initiated protein oxidation. Protein degradation, including Maillard reactions and protein oxidation, is concluded to be more important than lipid oxidation in determining the shelf-life of dry cauliflower soup powder. Copyright © 2011 Elsevier Ltd. All rights reserved.

  18. Redox regulation of mitochondrial function with emphasis on cysteine oxidation reactions.

    Science.gov (United States)

    Mailloux, Ryan J; Jin, Xiaolei; Willmore, William G

    2014-01-01

    Mitochondria have a myriad of essential functions including metabolism and apoptosis. These chief functions are reliant on electron transfer reactions and the production of ATP and reactive oxygen species (ROS). The production of ATP and ROS are intimately linked to the electron transport chain (ETC). Electrons from nutrients are passed through the ETC via a series of acceptor and donor molecules to the terminal electron acceptor molecular oxygen (O2) which ultimately drives the synthesis of ATP. Electron transfer through the respiratory chain and nutrient oxidation also produces ROS. At high enough concentrations ROS can activate mitochondrial apoptotic machinery which ultimately leads to cell death. However, if maintained at low enough concentrations ROS can serve as important signaling molecules. Various regulatory mechanisms converge upon mitochondria to modulate ATP synthesis and ROS production. Given that mitochondrial function depends on redox reactions, it is important to consider how redox signals modulate mitochondrial processes. Here, we provide the first comprehensive review on how redox signals mediated through cysteine oxidation, namely S-oxidation (sulfenylation, sulfinylation), S-glutathionylation, and S-nitrosylation, regulate key mitochondrial functions including nutrient oxidation, oxidative phosphorylation, ROS production, mitochondrial permeability transition (MPT), apoptosis, and mitochondrial fission and fusion. We also consider the chemistry behind these reactions and how they are modulated in mitochondria. In addition, we also discuss emerging knowledge on disorders and disease states that are associated with deregulated redox signaling in mitochondria and how mitochondria-targeted medicines can be utilized to restore mitochondrial redox signaling.

  19. Interfacial Redox Reactions Associated Ionic Transport in Oxide-Based Memories.

    Science.gov (United States)

    Younis, Adnan; Chu, Dewei; Shah, Abdul Hadi; Du, Haiwei; Li, Sean

    2017-01-18

    As an alternative to transistor-based flash memories, redox reactions mediated resistive switches are considered as the most promising next-generation nonvolatile memories that combine the advantages of a simple metal/solid electrolyte (insulator)/metal structure, high scalability, low power consumption, and fast processing. For cation-based memories, the unavailability of in-built mobile cations in many solid electrolytes/insulators (e.g., Ta 2 O 5 , SiO 2 , etc.) instigates the essential role of absorbed water in films to keep electroneutrality for redox reactions at counter electrodes. Herein, we demonstrate electrochemical characteristics (oxidation/reduction reactions) of active electrodes (Ag and Cu) at the electrode/electrolyte interface and their subsequent ions transportation in Fe 3 O 4 film by means of cyclic voltammetry measurements. By posing positive potentials on Ag/Cu active electrodes, Ag preferentially oxidized to Ag + , while Cu prefers to oxidize into Cu 2+ first, followed by Cu/Cu + oxidation. By sweeping the reverse potential, the oxidized ions can be subsequently reduced at the counter electrode. The results presented here provide a detailed understanding of the resistive switching phenomenon in Fe 3 O 4 -based memory cells. The results were further discussed on the basis of electrochemically assisted cations diffusions in the presence of absorbed surface water molecules in the film.

  20. Iron(III Fluorinated Porphyrins: Greener Chemistry from Synthesis to Oxidative Catalysis Reactions

    Directory of Open Access Journals (Sweden)

    Susana L. H. Rebelo

    2016-04-01

    Full Text Available Iron(III fluorinated porphyrins play a central role in the biomimetics of heme enzymes and enable cleaner routes to the oxidation of organic compounds. The present work reports significant improvements in the eco-compatibility of the synthesis of 5,10,15,20-tetrakis-pentafluorophenylporphyrin (H2TPFPP and the corresponding iron complex [Fe(TPFPPCl], and the use of [Fe(TPFPPCl] as an oxidation catalyst in green conditions. The preparations of H2TPFPP and [Fe(TPFPPCl] typically use toxic solvents and can be made significantly greener and simpler using microwave heating and optimization of the reaction conditions. In the optimized procedure it was possible to eliminate nitrobenzene from the porphyrin synthesis and replace DMF by acetonitrile in the metalation reaction, concomitant with a significant reduction of reaction time and simplification of the purification procedure. The Fe(IIIporphyrin is then tested as catalyst in the selective oxidation of aromatics at room temperature using a green oxidant (hydrogen peroxide and green solvent (ethanol. Efficient epoxidation of indene and selective oxidation of 3,5-dimethylphenol and naphthalene to the corresponding quinones is observed.

  1. Iron(III) Fluorinated Porphyrins: Greener Chemistry from Synthesis to Oxidative Catalysis Reactions.

    Science.gov (United States)

    Rebelo, Susana L H; Silva, André M N; Medforth, Craig J; Freire, Cristina

    2016-04-12

    Iron(III) fluorinated porphyrins play a central role in the biomimetics of heme enzymes and enable cleaner routes to the oxidation of organic compounds. The present work reports significant improvements in the eco-compatibility of the synthesis of 5,10,15,20-tetrakis-pentafluorophenylporphyrin (H₂TPFPP) and the corresponding iron complex [Fe(TPFPP)Cl], and the use of [Fe(TPFPP)Cl] as an oxidation catalyst in green conditions. The preparations of H₂TPFPP and [Fe(TPFPP)Cl] typically use toxic solvents and can be made significantly greener and simpler using microwave heating and optimization of the reaction conditions. In the optimized procedure it was possible to eliminate nitrobenzene from the porphyrin synthesis and replace DMF by acetonitrile in the metalation reaction, concomitant with a significant reduction of reaction time and simplification of the purification procedure. The Fe(III)porphyrin is then tested as catalyst in the selective oxidation of aromatics at room temperature using a green oxidant (hydrogen peroxide) and green solvent (ethanol). Efficient epoxidation of indene and selective oxidation of 3,5-dimethylphenol and naphthalene to the corresponding quinones is observed.

  2. A Generalizable Top-Down Nanostructuring Method of Bulk Oxides: Sequential Oxygen-Nitrogen Exchange Reaction.

    Science.gov (United States)

    Lee, Lanlee; Kang, Byungwuk; Han, Suyoung; Kim, Hee-Eun; Lee, Moo Dong; Bang, Jin Ho

    2018-05-27

    A thermal reaction route that induces grain fracture instead of grain growth is devised and developed as a top-down approach to prepare nanostructured oxides from bulk solids. This novel synthesis approach, referred to as the sequential oxygen-nitrogen exchange (SONE) reaction, exploits the reversible anion exchange between oxygen and nitrogen in oxides that is driven by a simple two-step thermal treatment in ammonia and air. Internal stress developed by significant structural rearrangement via the formation of (oxy)nitride and the creation of oxygen vacancies and their subsequent combination into nanopores transforms bulk solid oxides into nanostructured oxides. The SONE reaction can be applicable to most transition metal oxides, and when utilized in a lithium-ion battery, the produced nanostructured materials are superior to their bulk counterparts and even comparable to those produced by conventional bottom-up approaches. Given its simplicity and scalability, this synthesis method could open a new avenue to the development of high-performance nanostructured electrode materials that can meet the industrial demand of cost-effectiveness for mass production. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. A hydrogen-bonding network is important for oxidation and isomerization in the reaction catalyzed by cholesterol oxidase

    International Nuclear Information System (INIS)

    Lyubimov, Artem Y.; Chen, Lin; Sampson, Nicole S.; Vrielink, Alice

    2009-01-01

    The importance of active-site electrostatics for oxidative and reductive half-reactions in a redox flavoenzyme (cholesterol oxidase) have been investigated by a combination of biochemistry and atomic resolution crystallography. A detailed examination of active-site dynamics demonstrates that the oxidation of substrate and the re-oxidation of the flavin cofactor by molecular oxygen are linked by a single active-site asparagine. Cholesterol oxidase is a flavoenzyme that catalyzes the oxidation and isomerization of 3β-hydroxysteroids. Structural and mutagenesis studies have shown that Asn485 plays a key role in substrate oxidation. The side chain makes an NH⋯π interaction with the reduced form of the flavin cofactor. A N485D mutant was constructed to further test the role of the amide group in catalysis. The mutation resulted in a 1800-fold drop in the overall k cat . Atomic resolution structures were determined for both the N485L and N485D mutants. The structure of the N485D mutant enzyme (at 1.0 Å resolution) reveals significant perturbations in the active site. As predicted, Asp485 is oriented away from the flavin moiety, such that any stabilizing interaction with the reduced flavin is abolished. Met122 and Glu361 form unusual hydrogen bonds to the functional group of Asp485 and are displaced from the positions they occupy in the wild-type active site. The overall effect is to disrupt the stabilization of the reduced FAD cofactor during catalysis. Furthermore, a narrow transient channel that is shown to form when the wild-type Asn485 forms the NH⋯π interaction with FAD and that has been proposed to function as an access route of molecular oxygen, is not observed in either of the mutant structures, suggesting that the dynamics of the active site are altered

  4. Structural parameter identifiability analysis for dynamic reaction networks

    DEFF Research Database (Denmark)

    Davidescu, Florin Paul; Jørgensen, Sten Bay

    2008-01-01

    method based on Lie derivatives. The proposed systematic two phase methodology is illustrated on a mass action based model for an enzymatically catalyzed reaction pathway network where only a limited set of variables is measured. The methodology clearly pinpoints the structurally identifiable parameters...... where for a given set of measured variables it is desirable to investigate which parameters may be estimated prior to spending computational effort on the actual estimation. This contribution addresses the structural parameter identifiability problem for the typical case of reaction network models....... The proposed analysis is performed in two phases. The first phase determines the structurally identifiable reaction rates based on reaction network stoichiometry. The second phase assesses the structural parameter identifiability of the specific kinetic rate expressions using a generating series expansion...

  5. Chemical reaction at ferromagnet/oxide interface and its influence on anomalous Hall effect

    International Nuclear Information System (INIS)

    Liu, Yi-Wei; Teng, Jiao; Zhang, Jing-Yan; Liu, Yang; Chen, Xi; Li, Xu-Jing; Feng, Chun; Wang, Hai-Cheng; Li, Ming-Hua; Yu, Guang-Hua; Wu, Zheng-Long

    2014-01-01

    Chemical reactions at the ferromagnet/oxide interface in [Pt/Fe] 3 /MgO and [Pt/Fe] 3 /SiO 2 multilayers before and after annealing were investigated by X-ray photoelectron spectroscopy. The results show that Fe atoms at the Fe/MgO interface were completely oxidized in the as-grown state and significantly deoxidized after vacuum annealing. However, only some of the Fe atoms at the Fe/SiO 2 interface were oxidized and rarely deoxidized after annealing. The anomalous Hall effect was modified by this interfacial chemical reaction. The saturation anomalous Hall resistance (R xy ) was greatly increased in the [Pt/Fe] 3 /MgO multilayers after annealing and was 350% higher than that in the as-deposited film, while R xy of the [Pt/Fe] 3 /SiO 2 multilayer only increased 10% after annealing.

  6. QSARs for phenols and phenolates: oxidation potential as a predictor of reaction rate constants with photochemically produced oxidants.

    Science.gov (United States)

    Arnold, William A; Oueis, Yan; O'Connor, Meghan; Rinaman, Johanna E; Taggart, Miranda G; McCarthy, Rachel E; Foster, Kimberley A; Latch, Douglas E

    2017-03-22

    Quantitative structure-activity relationships (QSARs) for prediction of the reaction rate constants of phenols and phenolates with three photochemically produced oxidants, singlet oxygen, carbonate radical, and triplet excited state sensitizers/organic matter, are developed. The predictive variable is the one-electron oxidation potential (E 1 ), which is calculated for each species using density functional theory. The reaction rate constants are obtained from the literature, and for singlet oxygen, are augmented with new experimental data. Calculated E 1 values have a mean unsigned error compared to literature values of 0.04-0.06 V. For singlet oxygen, a single linear QSAR that includes both phenols and phenolates is developed that predicts experimental rate constants, on average, to within a factor of three. Predictions for only 6 out of 87 compounds are off by more than a factor of 10. A more limited data set for carbonate radical reactions with phenols and phenolates also gives a single linear QSAR with prediction of rate constant being accurate to within a factor of three. The data for the reactions of phenols with triplet state sensitizers demonstrate that two sensitizers, 2-acetonaphthone and methylene blue, most closely predict the reactivity trend of triplet excited state organic matter with phenols. Using sensitizers with stronger reduction potentials could lead to overestimation of rate constants and thus underestimation of phenolic pollutant persistence.

  7. Synthesis of propylene carbonate from urea and propylene glycol over zinc oxide: A homogeneous reaction

    Directory of Open Access Journals (Sweden)

    Dengfeng Wang

    2014-11-01

    Full Text Available In this work, several metal oxides and zinc salts were used to catalyze propylene carbonate (PC synthesis from urea and propylene glycol (PG. According to the results of catalytic test and characterization, the catalytic pattern of ZnO was different from that of other metal oxides such as CaO, MgO and La2O3, but similar to that of zinc salts. In fact, the leaching of Zn species took place during reaction for ZnO. And ZnO was found to be the precursor of homogenous catalyst for reaction of urea and PG. Thus, the relationship between the amount of dissolved zinc species and the catalytic performance of employed ZnO was revealed. In addition, a possible reaction mechanism over ZnO was discussed based on the catalytic runs and the characterization of XRD, FTIR, and element analysis.

  8. Magnetically Separable Iron Oxide Nanoparticles: An Efficient and Reusable Catalyst for Imino Diels-Alder Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Basavegowda, Nagaraj; Mishra, Kanchan; Lee, Yong Rok; Joh, Young-Gull [Yeungnam University, Gyeongsan (Korea, Republic of)

    2016-02-15

    Iron oxide nanoparticles were synthesized using Saururus chinensis (S. chinensis) leaf extract as a reducing and stabilizing agent via ultrasonication. The size, morphology, crystallinity, elemental composition, weight loss, surface chemical state, and magnetic properties of the synthesized nanoparticles were investigated. The synthe-sized nanoparticles were used as an efficient and recyclable catalyst for the synthesis of a variety of 2-methyl-4-substituted-1,2,3,4-tetrahydroquinoline derivatives by the imino Diels-Alder reaction. After the reaction, the catalyst was recovered by an external magnetic field. The recovered catalyst was then reused in a subsequent reaction under identical conditions. The recycled iron oxide nanoparticles (IONPs) were reused five times with-out any significant loss of catalytic activity.

  9. Magnetically Separable Iron Oxide Nanoparticles: An Efficient and Reusable Catalyst for Imino Diels-Alder Reaction

    International Nuclear Information System (INIS)

    Basavegowda, Nagaraj; Mishra, Kanchan; Lee, Yong Rok; Joh, Young-Gull

    2016-01-01

    Iron oxide nanoparticles were synthesized using Saururus chinensis (S. chinensis) leaf extract as a reducing and stabilizing agent via ultrasonication. The size, morphology, crystallinity, elemental composition, weight loss, surface chemical state, and magnetic properties of the synthesized nanoparticles were investigated. The synthe-sized nanoparticles were used as an efficient and recyclable catalyst for the synthesis of a variety of 2-methyl-4-substituted-1,2,3,4-tetrahydroquinoline derivatives by the imino Diels-Alder reaction. After the reaction, the catalyst was recovered by an external magnetic field. The recovered catalyst was then reused in a subsequent reaction under identical conditions. The recycled iron oxide nanoparticles (IONPs) were reused five times with-out any significant loss of catalytic activity.

  10. Electronic interactions decreasing the activation barrier for the hydrogen electro-oxidation reaction

    International Nuclear Information System (INIS)

    Santos, Elizabeth; Schmickler, Wolfgang

    2008-01-01

    A unified model for electrochemical electron transfer reactions which explicitly accounts for the electronic structure of the electrode recently proposed by us is applied to the hydrogen oxidation reaction at different metal electrocatalysts. We focus on the changes produced in the transition state (saddle point) as a consequence of the interactions with d-bands. We discuss different empirical correlations between properties of the metal and catalytic activity proposed in the past. We show which role is played by the band structure of the different metals and its interaction with the molecule for decreasing the activation barrier. Finally, we demonstrate why some metals are better electrocatalysts for the hydrogen electro-oxidation reaction than others

  11. Effect of magnetic field on the zero valent iron induced oxidation reaction

    International Nuclear Information System (INIS)

    Kim, Dong-hyo; Kim, Jungwon; Choi, Wonyong

    2011-01-01

    Highlights: → We investigate the zero valent iron induced oxidation in the presence of magnetic field. → The oxidative degradation of 4-chlorophenol is enhanced by the magnetic field. → ESR measurement confirms that more OH radicals are generated in the presence of magnetic field. → The magnetic field affects the mass transfer of O 2 and the recombination of radicals. - Abstract: The magnetic field (MF) effect on the zero valent iron (ZVI) induced oxidative reaction was investigated for the first time. The degradation of 4-chlorophenol (4-CP) in the ZVI system was employed as the test oxidative reaction. MF markedly enhanced the degradation of 4-CP with the concurrent production of chlorides. The consumption of dissolved O 2 by ZVI reaction was also enhanced in the presence of MF whereas the competing reaction of H 2 production from proton reduction was retarded. Since the ZVI-induced oxidation is mainly driven by the in situ generated hydroxyl radicals, the production of OH radicals was monitored by the spin trap method using electron spin resonance (ESR) spectroscopy. It was confirmed that the concentration of trapped OH radicals was enhanced in the presence of MF. Since both O 2 and Fe 0 are paramagnetic, the diffusion of O 2 onto the iron surface might be accelerated under MF. The magnetized iron can attract oxygen on itself, which makes the mass transfer process faster. As a result, the surface electrochemical reaction between Fe 0 and O 2 can be accelerated with the enhanced production of OH radicals. MF might retard the recombination of OH radicals as well.

  12. Investigating Atmospheric Oxidation with Molecular Dynamics Imaging and Spectroscopy

    Science.gov (United States)

    Merrill, W. G.; Case, A. S.; Keutsch, F. N.

    2013-06-01

    Volatile organic compounds (VOCs) in the Earth's atmosphere constitute trace gas species emitted primarily from the biosphere, and are the subject of inquiry for a variety of air quality and climate studies. Reactions intiated (primarily) by the hydroxyl radical (OH) lead to a myriad of oxygenated species (OVOCs), which in turn are prone to further oxidation. Investigations of the role that VOC oxidation plays in tropospheric chemistry have brought to light two troubling scenarios: (1) VOCs are responsible in part for the production of two EPA-regulated pollutants---tropospheric ozone and organic aerosol---and (2) the mechanistic details of VOC oxidation remain convoluted and poorly understood. The latter issue hampers the implementation of near-explicit atmospheric simulations, and large discrepancies in OH reactivity exist between measurements and models at present. Such discrepancies underscore the need for a more thorough description of VOC oxidation. Time-of-flight measurements and ion-imaging techniques are viable options for resolving some of the mechanistic and energetic details of VOC oxidation. Molecular beam studies have the advantage of foregoing unwanted bimolecular reactions, allowing for the characterization of specific processes which must typically compete with the complex manifold of VOC oxidation pathways. The focus of this work is on the unimolecular channels of organic peroxy radical intermediates, which are necessarily generated during VOC oxidation. Such intermediates may isomerize and decompose into distinct chemical channels, enabling the unambiguous detection of each pathway. For instance, a (1 + 1') resonance enhanced multiphoton ionization (REMPI) scheme may be employed to detect carbon monoxide generated from a particular unimolecular process. A number of more subtle mechanistic details may be explored as well. By varying the mean free path of the peroxy radicals in a flow tube, the role of collisional quenching in these unimolecular

  13. Mass transfer model for two-layer TBP oxidation reactions: Revision 1

    International Nuclear Information System (INIS)

    Laurinat, J.E.

    1994-01-01

    To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the Canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. Bubbles containing reaction products enhance the rate of transfer of water from the aqueous layer to the organic layer. These bubbles are generated by the oxidation of TBP and its reaction products in the organic layer and by the oxidation of butanol in the aqueous layer. Butanol is formed by the hydrolysis of TBP in the organic layer. For aqueous-layer bubbling to occur, butanol must transfer into the aqueous layer. Consequently, the rate of oxidation and bubble generation in the aqueous layer strongly depends on the rate of transfer of butanol from the organic to the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments

  14. Strategies for catalyst development: possibilities of the ``rational approach`` illustrated with partial oxidation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, W.; Schedel-Niedrig, T.; Schloegl, R. [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany). Abt. Oberflaechenphysik

    1998-12-31

    The paper discusses two petrochemical selective oxidation reactions namely the practised formation of styrene (STY) and the desired oxidative functionalisation of propane. The present knowledge about the mode of operation of oxide catalysts is critically considered. The dehydrogenation of ethylbenzene (EB) should be described by an oxidehydration with water acting as oxidant. The potential role of the coke formed during catalytic reaction as co-catalyst will be discussed. Selective oxidation is connected with the participation of lattice oxygen mechanism which transforms unselective gas phase oxygen into selective oxygen. The atomistic description of this process is still quite unclear as well as the electron structural properties of the activated oxygen atom. The Role of solid state acidity as compared to the role of lattice oxygen is much less well investigated modern multiphase-multielement oxide (MMO) catalysts. The rationale is that the significant efforts made to improve current MMO systems by chemical modifications can be very much more fruitful when in a first step the mode of action of a catalyst is clarified on the basis of suitable experiments. Such time-consuming experiments at the beginning of a campaign for catalyst improvement pay back their investment in later stages of the project when strategies of chemical development can be derived on grounds of understanding. (orig.)

  15. Investigation of oxidative degradation and non‐enzymatic browning reactions in krill and fish oils

    DEFF Research Database (Denmark)

    Thomsen, Birgitte Raagaard; Haugsgjerd, Bjørn Ole; Griinari, Mikko

    2013-01-01

    conditions using the Oxipres™ at 90°C. The results from analysis of PV, AV, TBARS, conjugated dienes and trienes, and the antioxidant content suggested that krill oil was more oxidatively stable than fish oil. However, the color or other constituents of the krill oil might affect the result......The aim of this research was to investigate the oxidation progress and pathways of krill and fish oil during 21 days of incubation at 40°C. The oxidative stability of the oils was investigated through: (i) classical methods such as peroxide value (PV), anisidine value (AV), thiobarbituric reactive...... substance (TBARS), conjugated dienes and trienes, and antioxidant content, and (ii) advanced methods such as determination of volatiles content by dynamic headspace (DHS)‐GC/MS, lipid classes, and pyrrole content. In addition, the oxidative stability of the oils was evaluated under accelerated oxidation...

  16. Microbial Fe(II) oxidation at circumneutral pH: Reaction kinetics, mineral products, and distribution of neutrophilic iron oxidizers in wetland soils

    NARCIS (Netherlands)

    Vollrath, S.

    2012-01-01

    Multiple studies have shown that neutrophilic Fe(II) oxidizers can conserve energy from Fe(II) oxidation, however, it is still unclear how they can compete against the fast abiotic reaction at neutral pH, or to which extent these bacteria increase the overall Fe(II) oxidation rate. Similar to

  17. Dynamic simulations on the mitochondrial fatty acid Beta-oxidation network

    Directory of Open Access Journals (Sweden)

    Weinberger Klaus M

    2009-01-01

    Full Text Available Abstract Background The oxidation of fatty acids in mitochondria plays an important role in energy metabolism and genetic disorders of this pathway may cause metabolic diseases. Enzyme deficiencies can block the metabolism at defined reactions in the mitochondrion and lead to accumulation of specific substrates causing severe clinical manifestations. Ten of the disorders directly affecting mitochondrial fatty acid oxidation have been well-defined, implicating episodic hypoketotic hypoglycemia provoked by catabolic stress, multiple organ failure, muscle weakness, or hypertrophic cardiomyopathy. Additionally, syndromes of severe maternal illness (HELLP syndrome and AFLP have been associated with pregnancies carrying a fetus affected by fatty acid oxidation deficiencies. However, little is known about fatty acids kinetics, especially during fasting or exercise when the demand for fatty acid oxidation is increased (catabolic stress. Results A computational kinetic network of 64 reactions with 91 compounds and 301 parameters was constructed to study dynamic properties of mitochondrial fatty acid β-oxidation. Various deficiencies of acyl-CoA dehydrogenase were simulated and verified with measured concentrations of indicative metabolites of screened newborns in Middle Europe and South Australia. The simulated accumulation of specific acyl-CoAs according to the investigated enzyme deficiencies are in agreement with experimental data and findings in literature. Investigation of the dynamic properties of the fatty acid β-oxidation reveals that the formation of acetyl-CoA – substrate for energy production – is highly impaired within the first hours of fasting corresponding to the rapid progress to coma within 1–2 hours. LCAD deficiency exhibits the highest accumulation of fatty acids along with marked increase of these substrates during catabolic stress and the lowest production rate of acetyl-CoA. These findings might confirm gestational loss to

  18. Chemical dynamics simulations of X- + CH3Y → XCH3 + Y- gas-phase S(N)2 nucleophilic substitution reactions. Nonstatistical dynamics and nontraditional reaction mechanisms.

    Science.gov (United States)

    Manikandan, Paranjothy; Zhang, Jiaxu; Hase, William L

    2012-03-29

    Extensive classical chemical dynamics simulations of gas-phase X(-) + CH(3)Y → XCH(3) + Y(-) S(N)2 nucleophilic substitution reactions are reviewed and discussed and compared with experimental measurements and predictions of theoretical models. The primary emphasis is on reactions for which X and Y are halogen atoms. Both reactions with the traditional potential energy surface (PES), which include pre- and postreaction potential energy minima and a central barrier, and reactions with nontraditional PESs are considered. These S(N)2 reactions exhibit important nonstatistical atomic-level dynamics. The X(-) + CH(3)Y → X(-)---CH(3)Y association rate constant is less than the capture model as a result of inefficient energy transfer from X(-)+ CH(3)Y relative translation to CH(3)Y rotation and vibration. There is weak coupling between the low-frequency intermolecular modes of the X(-)---CH(3)Y complex and higher frequency CH(3)Y intramolecular modes, resulting in non-RRKM kinetics for X(-)---CH(3)Y unimolecular decomposition. Recrossings of the [X--CH(3)--Y](-) central barrier is important. As a result of the above dynamics, the relative translational energy and temperature dependencies of the S(N)2 rate constants are not accurately given by statistical theory. The nonstatistical dynamics results in nonstatistical partitioning of the available energy to XCH(3) +Y(-) reaction products. Besides the indirect, complex forming atomic-level mechanism for the S(N)2 reaction, direct mechanisms promoted by X(-) + CH(3)Y relative translational or CH(3)Y vibrational excitation are possible, e.g., the roundabout mechanism.

  19. Characterization of Titanium Oxide Nanoparticles Obtained by Hydrolysis Reaction of Ethylene Glycol Solution of Alkoxide

    International Nuclear Information System (INIS)

    Uekawa, N.; Endo, N.; Ishii, K.; Kojima, T.; Kakegawa, K.

    2012-01-01

    Transparent and stable sols of titanium oxide nanoparticles were obtained by heating a mixture of ethylene glycol solution of titanium tetraisopropoxide (TIP) and a NH 3 aqueous solution at 368 K for 24 h. The concentration of NH 3 aqueous solution affected the structure of the obtained titanium oxide nanoparticles. For NH 3 aqueous solution concentrations higher than 0.2 mol/L, a mixture of anatase TiO 2 nanoparticles and layered titanic acid nanoparticles was obtained. The obtained sol was very stable without formation of aggregated precipitates and gels. Coordination of ethylene glycol to Ti4+ ions inhibited the rapid hydrolysis reaction and aggregation of the obtained nanoparticles. The obtained titanium oxide nanoparticles had a large specific surface area: larger than 350 m2/g. The obtained titanium oxide nanoparticles showed an enhanced adsorption towards the cationic dye molecules. The selective adsorption corresponded to presence of layered titanic acid on the obtained anatase TiO 2 nanoparticles.

  20. Analysis of the nucleon-nucleus reactions by the quantum molecular dynamics

    International Nuclear Information System (INIS)

    Chiba, Satoshi; Niita, Koji; Maruyama, Toshiki; Fukahori, Tokio; Takada, Hiroshi; Iwamoto, Akira

    1995-01-01

    The quantum molecular dynamics + statistical decay model has been applied to analyze the nucleon-induced nuclear reactions in the energy range from 50 to 3 GeV in order to verify its applicability to light-ion induced nuclear reactions. It was found that the present approach could give a quantitative description of various cross sections such as (p,p'), (p,n), (n,p) reactions from a wide range of targets and also target-like isotope production cross sections from p+Fe reaction, showing its basic ability as a tool for the study of intermediate energy nuclear reactions and nuclear data evaluation. (author)

  1. Chemistry in interstellar space. [environment characteristics influencing reaction dynamics

    Science.gov (United States)

    Donn, B.

    1973-01-01

    The particular characteristics of chemistry in interstellar space are determined by the unique environmental conditions involved. Interstellar matter is present at extremely low densities. Large deviations from thermodynamic equilibrium are, therefore, to be expected. A relatively intense ultraviolet radiation is present in many regions. The temperatures are in the range from 5 to 200 K. Data concerning the inhibiting effect of small activation energies in interstellar clouds are presented in a table. A summary of measured activation energies or barrier heights for exothermic exchange reactions is also provided. Problems of molecule formation are discussed, taking into account gas phase reactions and surface catalyzed processes.

  2. Isotope yield ratios as a probe of the reaction dynamics

    International Nuclear Information System (INIS)

    Trautmann, W.; Hildenbrand, K.D.; Lynen, U.; Mueller, W.F.J.; Rabe, H.J.; Sann, H.; Stelzer, H.; Trockel, R.; Wada, R.; Brummund, N.; Glasow, R.; Kampert, K.H.; Santo, R.; Eckert, E.M.; Pochodzalla, J.; Bock, I.; Pelte, D.

    1987-04-01

    Isotopically resolved yields of particles and complex fragments from 12 C and 18 O induced reactions on 53 Ni, 54 Ni, Ag, and 197 Au in the intermediate range of bombarding energies 30 MeV ≤ E/A ≤ 84 MeV were measured. The systematic variation of the deduced isotope yield ratios with projectile and target is used to determine the degree of N/Z equilibration achieved and to establish time scales for the reaction process. A quantum statistical model is employed in order to derive entropies of the emitting systems from the measured isotope yield ratios. (orig.)

  3. Dynamics of ion–molecule reactions from beam experiments: A historical survey

    Czech Academy of Sciences Publication Activity Database

    Herman, Zdeněk; Futrell, J. H.

    2015-01-01

    Roč. 377, FEB 2015 (2015), s. 84-92 ISSN 1387-3806 Institutional support: RVO:61388955 Keywords : Ion–molecule reactions * Dynamics * Beam scattering Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.183, year: 2015

  4. Variable Lysozyme Transport Dynamics on Oxidatively Functionalized Polystyrene Films.

    Science.gov (United States)

    Moringo, Nicholas A; Shen, Hao; Tauzin, Lawrence J; Wang, Wenxiao; Bishop, Logan D C; Landes, Christy F

    2017-10-17

    Tuning protein adsorption dynamics at polymeric interfaces is of great interest to many biomedical and material applications. Functionalization of polymer surfaces is a common method to introduce application-specific surface chemistries to a polymer interface. In this work, single-molecule fluorescence microscopy is utilized to determine the adsorption dynamics of lysozyme, a well-studied antibacterial protein, at the interface of polystyrene oxidized via UV exposure and oxygen plasma and functionalized by ligand grafting to produce varying degrees of surface hydrophilicity, surface roughness, and induced oxygen content. Single-molecule tracking indicates lysozyme loading capacities, and surface mobility at the polymer interface is hindered as a result of all functionalization techniques. Adsorption dynamics of lysozyme depend on the extent and the specificity of the oxygen functionalities introduced to the polystyrene surface. Hindered adsorption and mobility are dominated by hydrophobic effects attributed to water hydration layer formation at the functionalized polystyrene surfaces.

  5. The effect of interfaces on solid-state reactions between oxides

    International Nuclear Information System (INIS)

    Johnson, M.T.; Carter, C.B.

    1998-01-01

    A thin-film geometry has been used to study fundamental solid-state reaction processes occurring at interfaces in two spinel-forming oxide systems. In the first system, NiO/Al 2 O 3 , epitactic NiO films were deposited on various orientations of single-crystal α-Al 2 O 3 . In this case, the reaction kinetics were studied and correlated with the interfacial structure (or substrate orientation). In the second, In 2 O 3 /MgO, solid-state reactions were studied under the influence of an electric field. The electric field provides a driving force for mass transport that affects both the reaction process and the morphological stability of an interface

  6. Single-Site Palladium(II) Catalyst for Oxidative Heck Reaction: Catalytic Performance and Kinetic Investigations

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Hui; Li, Mengyang; Zhang, Guanghui; Gallagher, James R.; Huang, Zhiliang; Sun, Yu; Luo, Zhong; Chen, Hongzhong; Miller, Jeffrey T.; Zou, Ruqiang; Lei, Aiwen; Zhao, Yanli

    2015-01-01

    ABSTRACT: The development of organometallic single-site catalysts (SSCs) has inspired the designs of new heterogeneous catalysts with high efficiency. Nevertheless, the application of SSCs in certain modern organic reactions, such as C-C bond formation reactions, has still been less investigated. In this study, a single-site Pd(II) catalyst was developed, where 2,2'-bipyridine-grafted periodic mesoporous organosilica (PMO) was employed as the support of a Pd(II) complex. The overall performance of the single-site Pd(II) catalyst in the oxidative Heck reaction was then investigated. The investigation results show that the catalyst displays over 99% selectivity for the product formation with high reaction yield. Kinetic profiles further confirm its high catalytic efficiency, showing that the rate constant is nearly 40 times higher than that for the free Pd(II) salt. X-ray absorption spectroscopy reveals that the catalyst has remarkable lifetime and recyclability.

  7. Photoactivity of N-doped ZnO nanoparticles in oxidative and reductive reactions

    Science.gov (United States)

    Oliveira, Jéssica A.; Nogueira, André E.; Gonçalves, Maria C. P.; Paris, Elaine C.; Ribeiro, Caue; Poirier, Gael Y.; Giraldi, Tania R.

    2018-03-01

    N-doped ZnO is a prospective material for photocatalytic reactions. However, only oxidative paths are well investigated in the literature. This paper describes a comparative study about ZnO and ZnO:N potential for oxidative and reductive reactions, probed by rhodamine B dye photodegradation and CO2 photoreduction. The materials were prepared by the polymeric precursor method, using urea as a nitrogen source, and different heat treatments were used to observe their effects on surface decontamination, crystallinity, particle sizes and shapes, and photocatalytic performance. ZnO and ZnO:N presented a wurtzite crystalline structure and nanometric-scale particles. Samples submitted to higher temperatures showed lower specific surface areas, but higher crystallinity and lower contents of species adsorbed on their surfaces. On the other hand, the photocatalysts annealed in shorter times presented smaller crystallite sizes and lower crystallinity. These factors influenced the photoactivity in both conditions, i.e., oxidation and reduction reactions, under the ultraviolet and visible light, indicating that structural factors influenced the adequate charge separation and consequent photocatalytic activity since the as-synthesized samples were versatile photocatalysts in both redox reactions.

  8. Heterogeneous reactions of carbonyl sulfide on mineral oxides: mechanism and kinetics study

    Directory of Open Access Journals (Sweden)

    Y. Liu

    2010-11-01

    Full Text Available The heterogeneous reactions of carbonyl sulfide (OCS on the typical mineral oxides in the mineral dust particles were investigated using a Knudsen cell flow reactor and a diffuse reflectance UV-vis spectroscopy. The reaction pathway for OCS on mineral dust was identified based on the gaseous products and surface species. The hydrolysis of OCS and succeeding oxidation of intermediate products readily took place on α-Al2O3, MgO, and CaO. Reversible and irreversible adsorption of OCS were observed on α-Fe2O3 and ZnO, respectively, whereas no apparent uptake of OCS by SiO2 and TiO2 was observed. The reactivity of OCS on these oxides depends on both the basicity of oxides and the decomposition reactivity of oxides for H2S. Based on the individual uptake coefficients and chemical composition of authentic mineral dust, the uptake coefficient (γBET of mineral dust was estimated to be in the range of 3.84×10−7–2.86×10−8. The global flux of OCS due to heterogeneous reactions and adsorption on mineral dust was estimated at 0.13–0.29 Tg yr−1, which is comparable to the annual flux of OCS for its reaction with ·OH.

  9. Reaction Mechanism for m- Xylene Oxidation in the Claus Process by Sulfur Dioxide

    KAUST Repository

    Sinha, Sourab

    2015-09-24

    In the Claus process, the presence of aromatic contaminants such benzene, toluene, and xylenes (BTX), in the H2S feed stream has a detrimental effect on catalytic reactors, where BTX form soot particles and clog and deactivate the catalysts. Among BTX, xylenes are proven to be most damaging contaminant for catalysts. BTX oxidation in the Claus furnace, before they enter catalyst beds, provides a solution to this problem. A reaction kinetics study on m-xylene oxidation by SO2, an oxidant present in Claus furnace, is presented. The density functional theory is used to study the formation of m-xylene radicals (3-methylbenzyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl) through H-abstraction and their oxidation by SO2. The mechanism begins with SO2 addition on the radicals through an O-atom rather than the S-atom with the release of 180.0-183.1 kJ/mol of reaction energies. This exothermic reaction involves energy barriers in the range 3.9-5.2 kJ/mol for several m-xylene radicals. Thereafter, O-S bond scission takes place to release SO, and the O-atom remaining on aromatics leads to CO formation. Among four m-xylene radicals, the resonantly stabilized 3-methylbenzyl exhibited the lowest SO2 addition and SO elimination rates. The reaction rate constants are provided to facilitate Claus process simulations to find conditions suitable for BTX oxidation. © 2015 American Chemical Society.

  10. Reaction Mechanism for m- Xylene Oxidation in the Claus Process by Sulfur Dioxide

    KAUST Repository

    Sinha, Sourab; Raj, Abhijeet; Al Shoaibi, Ahmed S.; Chung, Suk-Ho

    2015-01-01

    In the Claus process, the presence of aromatic contaminants such benzene, toluene, and xylenes (BTX), in the H2S feed stream has a detrimental effect on catalytic reactors, where BTX form soot particles and clog and deactivate the catalysts. Among BTX, xylenes are proven to be most damaging contaminant for catalysts. BTX oxidation in the Claus furnace, before they enter catalyst beds, provides a solution to this problem. A reaction kinetics study on m-xylene oxidation by SO2, an oxidant present in Claus furnace, is presented. The density functional theory is used to study the formation of m-xylene radicals (3-methylbenzyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl) through H-abstraction and their oxidation by SO2. The mechanism begins with SO2 addition on the radicals through an O-atom rather than the S-atom with the release of 180.0-183.1 kJ/mol of reaction energies. This exothermic reaction involves energy barriers in the range 3.9-5.2 kJ/mol for several m-xylene radicals. Thereafter, O-S bond scission takes place to release SO, and the O-atom remaining on aromatics leads to CO formation. Among four m-xylene radicals, the resonantly stabilized 3-methylbenzyl exhibited the lowest SO2 addition and SO elimination rates. The reaction rate constants are provided to facilitate Claus process simulations to find conditions suitable for BTX oxidation. © 2015 American Chemical Society.

  11. One-electron oxidation reactions of purine and pyrimidine bases in cellular DNA.

    Science.gov (United States)

    Cadet, Jean; Wagner, J Richard; Shafirovich, Vladimir; Geacintov, Nicholas E

    2014-06-01

    The aim of this survey is to critically review the available information on one-electron oxidation reactions of nucleobases in cellular DNA with emphasis on damage induced through the transient generation of purine and pyrimidine radical cations. Since the indirect effect of ionizing radiation mediated by hydroxyl radical is predominant in cells, efforts have been made to selectively ionize bases using suitable one-electron oxidants that consist among others of high intensity UVC laser pulses. Thus, the main oxidation product in cellular DNA was found to be 8-oxo-7,8-dihydroguanine as a result of direct bi-photonic ionization of guanine bases and indirect formation of guanine radical cations through hole transfer reactions from other base radical cations. The formation of 8-oxo-7,8-dihydroguanine and other purine and pyrimidine degradation products was rationalized in terms of the initial generation of related radical cations followed by either hydration or deprotonation reactions in agreement with mechanistic pathways inferred from detailed mechanistic studies. The guanine radical cation has been shown to be implicated in three other nucleophilic additions that give rise to DNA-protein and DNA-DNA cross-links in model systems. Evidence was recently provided for the occurrence of these three reactions in cellular DNA. There is growing evidence that one-electron oxidation reactions of nucleobases whose mechanisms have been characterized in model studies involving aqueous solutions take place in a similar way in cells. It may also be pointed out that the above cross-linked lesions are only produced from the guanine radical cation and may be considered as diagnostic products of the direct effect of ionizing radiation.

  12. Triangular Diagrams Teach Steady and Dynamic Behaviour of Catalytic Reactions.

    Science.gov (United States)

    Klusacek, K.; And Others

    1989-01-01

    Illustrates how triangular diagrams can aid in presenting some of the rather complex transient interactions that occur among gas and surface species during heterogeneous catalytic reactions. The basic equations and numerical examples are described. Classroom use of the triangular diagram is discussed. Several diagrams and graphs are provided. (YP)

  13. Reaction Mechanism for the Formation of Nitrogen Oxides (NO x ) During Coke Oxidation in Fluidized Catalytic Cracking Units

    KAUST Repository

    Chaparala, Sree Vidya

    2015-06-11

    Fluidized catalytic cracking (FCC) units in refineries process heavy feedstock obtained from crude oil distillation. While cracking feed, catalysts get deactivated due to coke deposition. During catalyst regeneration by burning coke in air, nitrogen oxides (NOx) are formed. The increase in nitrogen content in feed over time has resulted in increased NOx emissions. To predict NOx concentration in flue gas, a reliable model for FCC regenerators is needed that requires comprehensive understanding and accurate kinetics for NOx formation. Based on the nitrogen-containing functional groups on coke, model molecules are selected to study reactions between coke-bound nitrogen and O2 to form NO and NO2 using density functional theory. The reaction kinetics for the proposed pathways are evaluated using transition state theory. It is observed that the addition of O2 on coke is favored only when the free radical is present on the carbon atom instead of nitrogen atom. Thus, NOx formation during coke oxidation does not result from the direct attack by O2 on N atoms of coke, but from the transfer of an O atom to N from a neighboring site. The low activation energies required for NO formation indicate that it is more likely to form than NO2 during coke oxidation. The favorable pathways for NOx formation that can be used in FCC models are identified. Copyright © 2015 Taylor & Francis Group, LLC.

  14. Highly efficient oxidation of amines to imines by singlet oxygen and its application in Ugi-type reactions.

    Science.gov (United States)

    Jiang, Gaoxi; Chen, Jian; Huang, Jie-Sheng; Che, Chi-Ming

    2009-10-15

    A variety of secondary benzylic amines were oxidized to imines in 90% to >99% yields by singlet oxygen generated from oxygen and a porphyrin photosensitizer. On the basis of these reactions, a protocol was developed for oxidative Ugi-type reactions with singlet oxygen as the oxidant. This protocol has been used to synthesize C1- and N-functionalized benzylic amines in up to 96% yields.

  15. Dynamic Modelling and Identification of Precipitation Reactions in Full-Scale WWTP

    DEFF Research Database (Denmark)

    Mbamba, Christian Kazadi; Tait, Stephan; Flores-Alsina, Xavier

    , this paper evaluates plant-wide modelling of precipitation reactions using a generic approach integrated within activated sludge and anaerobic models. Preliminary results of anaerobic digester sludge in batch system suggest that the model is able to simulate the dynamics of precipitation reactions. Kinetic...

  16. Computerized infrared spectroscopic study of surface reactions on selected lanthanide oxides

    International Nuclear Information System (INIS)

    Dellisante, G.N.

    1982-01-01

    The natures of adsorption sites on La 2 O 3 , Nd 2 O 3 , and selected praseodymium oxides were investigated by examining surface reactions of probe molecules using computerized transmission ir spectroscopy on unsupported samples. Additionally, the rehydration/dehydration behavior and crystallographic phase transitions of these oxides were examined in pretreatment temperature experiments involving rehydration of the sesquioxides to hydroxides by water exposure. Following rehydration of La 2 O 3 to La(OH) 3 , the effect of increasing vacuum pretreatment temperature (350 to 1000 0 C) is to gradually remove surface hydroxyl and carbonate entities (up to 650 0 C), and increase the degree of A-type crystallinity. Increasing crystallinity causes a concomitant decrease in surface oxide basicity. The removal of hydroxyl and carbonate species, as well as increases in oxide basicity, strongly correlated to increases in certain catalytic activities. The adsorption of NH 3 , CO 2 , mixtures of NH 3 and CO 2 , formic acid, acetic acid, acetaldehyde, and ethanol on the oxides was determined to weakly coordinate in Ln 3 + sites, and the surface reactions are discussed. Heating was found to desorb the adsorbed compounds and/or causes changes of the originally adsorbed form into other compounds. The effects of temperature on both adsorption and desorption are reported

  17. Reaction dynamics of inflammation proteins and T lymphocytes during radon balneotherapy

    International Nuclear Information System (INIS)

    Peter, A.; Vulpe, B.

    1989-01-01

    During a three-week radon treatment with daily administration of baths a periodical course of reaction with antidromic dynamics of inflammation proteins and T lymphocytes could be shown. A conspicuous reaction of the organism (moment of the treatment reaction) is to be observed one week after the beginning of the treatment. At the end of the cure a decrease of the activity of inflammation as well as of individual acute-phase proteins and immunoglobulins it to be proved. (author)

  18. Free radical reaction characteristics of coal low-temperature oxidation and its inhibition method.

    Science.gov (United States)

    Li, Zenghua; Kong, Biao; Wei, Aizhu; Yang, Yongliang; Zhou, Yinbo; Zhang, Lanzhun

    2016-12-01

    Study on the mechanism of coal spontaneous combustion is significant for controlling fire disasters due to coal spontaneous combustion. The free radical reactions can explain the chemical process of coal at low-temperature oxidation. Electron spin resonance (ESR) spectroscopy was used to measure the change rules of the different sorts and different granularity of coal directly; ESR spectroscopy chart of free radicals following the changes of temperatures was compared by the coal samples applying air and blowing nitrogen, original coal samples, dry coal samples, and demineralized coal samples. The fragmentation process was the key factor of producing and initiating free radical reactions. Oxygen, moisture, and mineral accelerated the free radical reactions. Combination of the free radical reaction mechanism, the mechanical fragmentation leaded to the elevated CO concentration, fracturing of coal pillar was more prone to spontaneous combustion, and spontaneous combustion in goaf accounted for a large proportion of the fire in the mine were explained. The method of added diphenylamine can inhibit the self-oxidation of coal effectively, the action mechanism of diphenylamine was analyzed by free radical chain reaction, and this research can offer new method for the development of new flame retardant.

  19. Direct gas-phase epoxidation of propylene to propylene oxide through radical reactions: A theoretical study

    Science.gov (United States)

    Kizilkaya, Ali Can; Fellah, Mehmet Ferdi; Onal, Isik

    2010-03-01

    The gas-phase radical chain reactions which utilize O 2 as the oxidant to produce propylene oxide (PO) are investigated through theoretical calculations. The transition states and energy profiles were obtained for each path. The rate constants were also calculated. The energetics for the competing pathways indicate that PO can be formed selectively due to its relatively low activation barrier (9.3 kcal/mol) which is in a good agreement with the experimental value (11 kcal/mol) of gas-phase propylene epoxidation. The formation of the acrolein and combustion products have relatively high activation barriers and are not favored. These results also support the recent experimental findings.

  20. Reaction of Antimony-Uranium Composite Oxide in the Chlorination Treatment of Waste Catalyst - 13521

    International Nuclear Information System (INIS)

    Sawada, Kayo; Hirabayashi, Daisuke; Enokida, Youichi

    2013-01-01

    The effect of oxygen gas concentration on the chlorination treatment of antimony-uranium composite oxide catalyst waste was investigated by adding different concentrations of oxygen at 0-6 vol% to its chlorination agent of 0.6 or 6 vol% hydrogen chloride gas at 1173 K. The addition of oxygen tended to prevent the chlorination of antimony in the oxide. When 6 vol% hydrogen chloride gas was used, the addition of oxygen up to 0.1 vol% could convert the uranium contained in the catalyst to U 3 O 8 without any significant decrease in the reaction rate compared to that of the treatment without oxygen. (authors)

  1. Density-functional molecular-dynamics study of the redox reactions of two anionic, aqueous transition-metal complexes

    International Nuclear Information System (INIS)

    Tateyama, Yoshitaka; Blumberger, Jochen; Sprik, Michiel; Tavernelli, Ivano

    2005-01-01

    The thermochemistry of the RuO 4 2- +MnO 4 - →RuO 4 - +MnO 4 2- redox reaction in aqueous solution is studied by separate density-functional-based ab initio molecular-dynamics simulations of the component half reactions RuO 4 2- →RuO 4 - +e - and MnO 4 2- →MnO 4 - +e - . We compare the results of a recently developed grand-canonical method for the computation of oxidation free energies to the predictions by the energy-gap relations of the Marcus theory that can be assumed to apply to these reactions. The calculated redox potentials are in good agreement. The subtraction of the half-reaction free energies gives an estimate of the free energy of the full reaction. The result obtained from the grand-canonical method is -0.4 eV, while the application of the Marcus theory gives -0.3 eV. These should be compared to the experimental value of 0.0 eV. Size effects, in response to increasing the number of water molecules in the periodic model system from 30 to 48, are found to be small (≅0.1 eV). The link to the Marcus theory also has enabled us to compute reorganization free energies for oxidation. For both the MnO 4 2- and RuO 4 2- redox reactions we find the same reorganization free energy of 0.8 eV (1.0 eV in the larger system). The results for the free energies and further analysis of solvation and electronic structure confirm that these two tetrahedral oxoanions show very similar behavior in solution in spite of the central transition-metal atoms occupying a different row and column in the periodic table

  2. Hantzsch Reaction Starting Directly from Alcohols through a Tandem Oxidation Process

    Directory of Open Access Journals (Sweden)

    Xiaobing Liu

    2017-01-01

    Full Text Available A Brønsted acidic ionic liquid, 3-(N,N-dimethyldodecylammonium propanesulfonic acid hydrogen sulphate ([DDPA][HSO4], has been successfully applied to catalyze sequential oxidation of aromatic alcohols with NaNO3 followed by their condensation with dicarbonyl compound and ammonium acetate. The corresponding pyridine analogues of Hantzsch 1,4-dihydropyridines could be obtained as a major product with high yields by the multicomponent reaction. The present work utilizing alcohols instead of aldehyde in Hantzsch reaction is a valid and green alternative to the classical synthesis of the corresponding pyridine analogues of Hantzsch 1,4-dihydropyridines.

  3. Multiscale Informatics for Low-Temperature Propane Oxidation: Further Complexities in Studies of Complex Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Burke, Michael P.; Goldsmith, C. Franklin; Klippenstein, Stephen J.; Welz, Oliver; Huang, Haifeng; Antonov, Ivan O.; Savee, John D.; Osborn, David L.; Zádor, Judit; Taatjes, Craig A.; Sheps, Leonid

    2015-07-16

    We have developed a multi-scale approach (Burke, M. P.; Klippenstein, S. J.; Harding, L. B. Proc. Combust. Inst. 2013, 34, 547–555.) to kinetic model formulation that directly incorporates elementary kinetic theories as a means to provide reliable, physics-based extrapolation to unexplored conditions. Here, we extend and generalize the multi-scale modeling strategy to treat systems of considerable complexity – involving multi-well reactions, potentially missing reactions, non-statistical product branching ratios, and non-Boltzmann (i.e. non-thermal) reactant distributions. The methodology is demonstrated here for a subsystem of low-temperature propane oxidation, as a representative system for low-temperature fuel oxidation. A multi-scale model is assembled and informed by a wide variety of targets that include ab initio calculations of molecular properties, rate constant measurements of isolated reactions, and complex systems measurements. Active model parameters are chosen to accommodate both “parametric” and “structural” uncertainties. Theoretical parameters (e.g. barrier heights) are included as active model parameters to account for parametric uncertainties in the theoretical treatment; experimental parameters (e.g. initial temperatures) are included to account for parametric uncertainties in the physical models of the experiments. RMG software is used to assess potential structural uncertainties due to missing reactions. Additionally, branching ratios among product channels are included as active model parameters to account for structural uncertainties related to difficulties in modeling sequences of multiple chemically activated steps. The approach is demonstrated here for interpreting time-resolved measurements of OH, HO2, n-propyl, i-propyl, propene, oxetane, and methyloxirane from photolysis-initiated low-temperature oxidation of propane at pressures from 4 to 60 Torr and temperatures from 300 to 700 K. In particular, the multi-scale informed

  4. Kinetic isotope effects in reaction of ferment oxidation of tritium-labelled D-galactosamine

    International Nuclear Information System (INIS)

    Akulov, G.P.; Korsakova, N.A.

    1992-01-01

    Primary, secondary and intramolecular kinetic isotopic effects in reaction of ferment oxidation of D-galactosamine labelled by tritium in position 6, were measured. When comparing values of the effects with previously obtained results for similar reaction D-[6- 3 H]galactose, it was ascertained that the presence of aminogroup in galactopyranosyl mainly affects kinetics of substrate-ferment complex formation stage. The possibility to use kinetic isotope effects for increase in molar activity of D-galactosamine, labelled by tritium in position 6, is shown

  5. Reaction dynamics of molecular hydrogen on silicon surfaces

    DEFF Research Database (Denmark)

    Bratu, P.; Brenig, W.; Gross, A.

    1996-01-01

    of the preexponential factor by about one order of magnitude per lateral degree of freedom. Molecular vibrations have practically no effect on the adsorption/desorption dynamics itself, but lead to vibrational heating in desorption with a strong isotope effect. Ab initio calculations for the H-2 interaction...... between the two surfaces. These results indicate that tunneling, molecular vibrations, and the structural details of the surface play only a minor role for the adsorption dynamics. Instead, they appear to be governed by the localized H-Si bonding and Si-Si lattice vibrations. Theoretically, an effective......Experimental and theoretical results on the dynamics of dissociative adsorption and recombinative desorption of hydrogen on silicon are presented. Using optical second-harmonic generation, extremely small sticking probabilities in the range 10(-9)-10(-5) could be measured for H-2 and D-2 on Si(111...

  6. Complex Reaction Environments and Competing Reaction Mechanisms in Zeolite Catalysis: Insights from Advanced Molecular Dynamics

    NARCIS (Netherlands)

    De Wispelaere, K.; Ensing, B.; Ghysels, A.; Meijer, E.J.; van Van Speybroeck, V.

    2015-01-01

    The methanol-to-olefin process is a showcase example of complex zeolite-catalyzed chemistry. At real operating conditions, many factors affect the reactivity, such as framework flexibility, adsorption of various guest molecules, and competitive reaction pathways. In this study, the strength of first

  7. High-performance Platinum-free oxygen reduction reaction and hydrogen oxidation reaction catalyst in polymer electrolyte membrane fuel cell.

    Science.gov (United States)

    Chandran, Priji; Ghosh, Arpita; Ramaprabhu, Sundara

    2018-02-26

    The integration of polymer electrolyte membrane fuel cell (PEMFC) stack into vehicles necessitates the replacement of high-priced platinum (Pt)-based electrocatalyst, which contributes to about 45% of the cost of the stack. The implementation of high-performance and durable Pt metal-free catalyst for both oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) could significantly enable large-scale commercialization of fuel cell-powered vehicles. Towards this goal, a simple, scalable, single-step synthesis method was adopted to develop palladium-cobalt alloy supported on nitrogen-doped reduced graphene oxide (Pd 3 Co/NG) nanocomposite. Rotating ring-disk electrode (RRDE) studies for the electrochemical activity towards ORR indicates that ORR proceeds via nearly four-electron mechanism. Besides, the mass activity of Pd 3 Co/NG shows an enhancement of 1.6 times compared to that of Pd/NG. The full fuel cell measurements were carried out using Pd 3 Co/NG at the anode, cathode in conjunction with Pt/C and simultaneously at both anode and cathode. A maximum power density of 68 mW/cm 2 is accomplished from the simultaneous use of Pd 3 Co/NG as both anode and cathode electrocatalyst with individual loading of 0.5 mg/cm 2 at 60 °C without any backpressure. To the best of our knowledge, the present study is the first of its kind of a fully non-Pt based PEM full cell.

  8. Resonances and reactions from mean-field dynamics

    Directory of Open Access Journals (Sweden)

    Stevenson P. D.

    2016-01-01

    Full Text Available The time-dependent version of nuclear density functional theory, using functionals derived from Skyrme interactions, is able to approximately describe nuclear dynamics. We present time-dependent results of calculations of dipole resonances, concentrating on excitations of valence neutrons against a proton plus neutron core in the neutron-rich doubly-magic 132Sn nucleus, and results of collision dynamics, highlighting potential routes to ternary fusion, with the example of a collision of 48Ca+48Ca+208Pb resulting in a compound nucleus of element 120 stable against immediate fission.

  9. Gas dynamic reaction process and system for laser chemistry

    International Nuclear Information System (INIS)

    Garbuny, M.

    1979-01-01

    A reaction system is disclosed wherein a moving, unidirectional stream of an activatable gaseous species is produced, the individual members of which have the forward components of their velocities at least 10 times greater than the lateral components of their velocities. The stream is irradiated with substantially monochromatic light having a frequency which activates at least some of the individual members of the species. The activated members can then be reacted with another stream or otherwise utilized

  10. A coupled mechanical-chemical model for reflecting the influence of stress on oxidation reactions in thermal barrier coating

    Science.gov (United States)

    Chen, Lin; Yueming, Li

    2018-06-01

    In this paper, a coupled mechanical-chemical model is established based on the thermodynamic framework, in which the contribution of chemical expansion to free energy is introduced. The stress-dependent chemical potential equilibrium at the gas-solid interface and the stress gradient-dependent diffusion equation as well as a so-called generalized force which is conjugate to the oxidation rate are derived from the proposed model, which could reflect the influence of stresses on the oxidation reaction. Based on the proposed coupled mechanical-chemical model, a user element subroutine is developed in ABAQUS. The numerical simulation of the high temperature oxidation in the thermal barrier coating is carried out to verify the accuracy of the proposed model, and then the influence of stresses on the oxidation reaction is investigated. In thermally grown oxide, the considerable stresses would be induced by permanent volumetric swelling during the oxidation. The stresses play an important role in the chemical potential equilibrium at the gas-solid interface and strongly affect the oxidation reaction. The gradient of the stresses, however, only occurs in the extremely thin oxidation front layer, which plays a very limited role in the oxidation reaction. The generalized force could be divided into the stress-dependent and the stress-independent parts. Comparing with the stress-independent part, the stress-dependent part is smaller, which has little influence on oxidation reaction.

  11. Core-shell rhodium sulfide catalyst for hydrogen evolution reaction / hydrogen oxidation reaction in hydrogen-bromine reversible fuel cell

    Science.gov (United States)

    Li, Yuanchao; Nguyen, Trung Van

    2018-04-01

    Synthesis and characterization of high electrochemical active surface area (ECSA) core-shell RhxSy catalysts for hydrogen evolution oxidation (HER)/hydrogen oxidation reaction (HOR) in H2-Br2 fuel cell are discussed. Catalysts with RhxSy as shell and different percentages (5%, 10%, and 20%) of platinum on carbon as core materials are synthesized. Cyclic voltammetry is used to evaluate the Pt-equivalent mass specific ECSA and durability of these catalysts. Transmission electron microscopy (TEM), X-ray Photoelectron spectroscopy (XPS) and Energy-dispersive X-ray spectroscopy (EDX) techniques are utilized to characterize the bulk and surface compositions and to confirm the core-shell structure of the catalysts, respectively. Cycling test and polarization curve measurements in the H2-Br2 fuel cell are used to assess the catalyst stability and performance in a fuel cell. The results show that the catalysts with core-shell structure have higher mass specific ECSA (50 m2 gm-Rh-1) compared to a commercial catalyst (RhxSy/C catalyst from BASF, 6.9 m2 gm-Rh-1). It also shows better HOR/HER performance in the fuel cell. Compared to the platinum catalyst, the core-shell catalysts show more stable performance in the fuel cell cycling test.

  12. Reactions of calcium orthosilicate and barium zirconate with oxides and sulfates of various elements

    Science.gov (United States)

    Zaplatynsky, I.

    1979-01-01

    Calcium orthosilicate and barium zirconate were evaluated as the insulation layer of thermal barrier coatings for air cooled gas turbine components. Their reactions with various oxides and sulfates were studied at 1100 C and 1300 C for times ranging up to 400 and 200 hours, respectively. These oxides and sulfates represent potential impurities or additives in gas turbine fuels and in turbine combustion air, as well as elements of potential bond coat alloys. The phase compositions of the reaction products were determined by X-ray diffraction analysis. BaZrO3 and 2CaO-SiO2 both reacted with P2O5, V2O5, Cr2O3, Al2O3, and SiO2. In addition, 2CaO-SiO2 reacted with Na2O, BaO, MgO, and CoO and BaZrO3 reacted with Fe2O3.

  13. A consistent reaction scheme for the selective catalytic reduction of nitrogen oxides with ammonia

    DEFF Research Database (Denmark)

    Janssens, Ton V.W.; Falsig, Hanne; Lundegaard, Lars Fahl

    2015-01-01

    For the first time, the standard and fast selective catalytic reduction of NO by NH3 are described in a complete catalytic cycle, that is able to produce the correct stoichiometry, while only allowing adsorption and desorption of stable molecules. The standard SCR reaction is a coupling of the ac...... for standard SCR. Finally, the role of a nitrate/nitrite equilibrium and the possible in uence of Cu dimers and Brønsted sites are discussed, and an explanation is offered as to how a catalyst can be effective for SCR, while being a poor catalyst for NO oxidation to NO2....... spectroscopy (FTIR). A consequence of the reaction scheme is that all intermediates in fast SCR are also part of the standard SCR cycle. The calculated activation energy by density functional theory (DFT) indicates that the oxidation of an NO molecule by O2 to a bidentate nitrate ligand is rate determining...

  14. Caryophyllene driven diversity in an one-pot rearrangement of oxidation and transanular reactions

    Science.gov (United States)

    Tang, Hao-Yu; Quan, Lu-Lu; Yu, Jie; Zhang, Qiang; Gao, Jin-Ming

    2018-03-01

    Diversity oriented synthesis starting from natural products is a newly coming strategy to build diverse skeletons to meet the demands of high throughput screening in drug development. Caryophyllene was being considered as an ideal starting point to build divers natural-like sesquiterpenes due to its rich sources and build-in reactivity. In this paper, six new natural-like products (2-7) were synthesized form the natural cryophyllene oxide via cascade oxidation and transannular reactions in a one-pot procedure. Their structures were elucidated by exhaustive spectra method including 2D NMR and X-ray diffraction. Of the products, compounds 6 and 7 possess very similar skeleton to natural products. Our findings demonstrated that one-pot cascade reactions on macrocyclic natural products is a concise strategy to create diverse natural-like skeletons.

  15. Performance of the periodic pulse technique--4. Periodic pulse reaction kinetics of oxidative dehydrogenation of isobutyraldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Hattori, T.; Ii, M.; Murakami, Y.

    1980-07-01

    The periodic pulse method was used to study the reaction mechanism and kinetics of the oxidative dehydrogenation of isobutyraldehyde (IBA) by following the formation rates of methacrolein (MA), carbon monoxide and dioxide (CO/sub x/), and other products (P) as a function of pulse widths and reactant partial pressures at 350/sup 0/C over a 2:3 antimony oxide/molybdenum trioxide catalyst. The results were consistent with a mechanism according to which IBA reacts with oxygen retained by the catalyst to form MA, causing reduction of the catalyst. The IBA also adsorbed on the surface as an oxygenated species which either reacted with gas-phase oxygen to form CO/sub x/ or desorbed as an oxygenated P. The reduced catalyst surface was reoxidized by oxygen adsorption. Implications of catalyst tailoring for increased MA yields by improving the redox mechanism and inhibiting the surface reactions, are discussed.

  16. Reaction-transport simulations of non-oxidative methane conversion with continuous hydrogen removal: Homogeneous-heterogeneous methane reaction pathways

    International Nuclear Information System (INIS)

    Li, Lin; Borry, Richard W.; Iglesia, Enrique

    2000-01-01

    Detailed kinetic-transport models were used to explore thermodynamic and kinetic barriers in the non-oxidative conversion of CH4 via homogeneous and homogeneous-heterogeneous pathways and the effects of continuous hydrogen removal and of catalytic sites on attainable yields of useful C2-C10 products. The homogeneous kinetic model combines separately developed models for low-conversion pyrolysis and for chain growth to form large aromatics and carbon. The H2 formed in the reaction decreases CH4 pyrolysis rates and equilibrium conversions and it favors the formation of lighter products. The removal of H2 along tubular reactors with permeable walls increases reaction rates and equilibrium CH4 conversions. C2-C10 yields reach values greater than 90 percent at intermediate values of dimensionless transport rates (delta=1-10), defined as the ratio hydrogen transport and methane conversion rates. Homogeneous reactions require impractical residence times, even with H2 removal, because of slow initiation and chain transfer rates. The introduction of heterogeneous chain initiation pathways using surface sites that form methyl radicals eliminates the induction period without influencing the homogeneous product distribution. Methane conversion, however, occurs predominately in the chain transfer regime, within which individual transfer steps and the formation of C2 intermediates become limited by thermodynamic constraints. Catalytic sites alone cannot overcome these constraints. Catalytic membrane reactors with continuous H2 removal remove these thermodynamic obstacles and decrease the required residence time. Reaction rates become limited by homogeneous reactions of C2 products to form C6+ aromatics. Higher delta values lead to subsequent conversion of the desired C2-C10 products to larger polynuclear aromatics. We conclude that catalytic methane pyrolysis at the low temperatures required for restricted chain growth and the elimination of thermodynamics constraints via

  17. Direct Dynamics Simulation of the Thermal 3CH2 + 3O2 Reaction. Rate Constant and Product Branching Ratios.

    Science.gov (United States)

    Lakshmanan, Sandhiya; Pratihar, Subha; Machado, Francisco Bolivar Correto; Hase, William Louis

    2018-04-26

    The reaction of 3CH2 with 3O2 is of fundamental importance in combustion and the reaction is complex as a result of multiple extremely exothermic product channels. In the present study, direct dynamics simulations were performed to study the reaction on both the singlet and triplet potential energy surfaces (PESs). The simulations were performed at the UM06/6-311++G(d,p) level of theory. Trajectories were calculated at a temperature of 300 K and all reactive trajectories proceeded through the carbonyl oxide Criegee intermediate, CH2OO, on both the singlet and triplet PESs. The triplet surface leads to only one product channel, H2CO + O(3P), while the singlet surface leads to 8 product channels with their relative importance as: CO + H2O > CO + OH + H ~ H2CO + O(1D) > HCO + OH ~ CO2 + H2 ~ CO + H2 + O(1D) > CO2 + H + H > HCO + O(1D) + H. Reaction on the singlet PES is barrierless, consistent with experiment and the total rate constant on the singlet surface is 0.93 ± 0.22 x 10-12 cm3molecule-1s-1 in comparison to the recommended experimental rate constant of 3.3 x 10-12 cm3molecule-1s-1. The simulation product yields for the singlet PES are compared with experiment and the most significant differences are for H, CO2, and H2O. Reaction on the triplet surface is also barrierless, inconsistent with experiment. A discussion is given of the need for future calculations to address the: (1) barrier on the triplet PES for 3CH2 + 3O2 → 3CH2OO; (2) temperature dependence of the 3CH2 + 3O2 reaction rate constant and product branching ratios; and (3) possible non-RRKM dynamics of the 1CH2OO Criegee intermediate.

  18. Simulation of 3D mesoscale structure formation in concentrated aqueous solution of the triblock polymer surfactants (ethylene oxide)(13)(propylene oxide)(30)(ethylene oxide)(13) and (propylene oxide)(19)(ethylene oxide)(33)(propylene oxide)(19). Application of dynamic mean-field density functional theory

    NARCIS (Netherlands)

    van Vlimmeren, BAC; Maurits, NM; Zvelindovsky, AV; Sevink, GJA; Fraaije, JGEM

    1999-01-01

    We simulate the microphase separation dynamics of aqueous solutions of the triblock polymer surfactants (ethylene oxide)(13)(propylene oxide)(30)(ethylene oxide)(13) and (propylene oxide)(19)(ethylene oxide)(33)(propylene oxide)(19) by a dynamic variant of mean-field density functional theory for

  19. Investigation of the kinetics of the reactions of oxidation, nitration, and hydrogenation of uranium

    International Nuclear Information System (INIS)

    Adda, Y.

    1955-06-01

    Various physico-chemical methods have been used to investigate the kinetics of the oxidation hydridation and nitridation of uranium. The experimental results show that the kinetics of these reactions are influenced by many factors also the Pilling and Bedworth rule is valid only under very limited conditions. The disagreement between this rule and the experimental results could be explained by the existence of numerous mechanical faults in the compounds obtained by the dry corrosion of the metal. (author) [fr

  20. o-Iodoxybenzoic acid mediated oxidative desulfurization initiated domino reactions for synthesis of azoles.

    Science.gov (United States)

    Chaudhari, Pramod S; Pathare, Sagar P; Akamanchi, Krishnacharaya G

    2012-04-20

    A systematic exploration of thiophilic ability of o-iodoxybenzoic acid (IBX) for oxidative desulfurization to trigger domino reactions leading to new methodologies for synthesis of different azoles is described. A variety of highly substituted oxadiazoles, thiadiazoles, triazoles, and tetrazoles have been successfully synthesized in good to excellent yields, starting from readily accessible thiosemicarbazides, bis-diarylthiourea, 1,3-disubtituted thiourea, and thioamides. © 2012 American Chemical Society

  1. Reduction Dynamics of Doped Ceria, Nickel Oxide, and Cermet Composites Probed Using In Situ Raman Spectroscopy.

    Science.gov (United States)

    Maher, Robert C; Shearing, Paul R; Brightman, Edward; Brett, Dan J L; Brandon, Nigel P; Cohen, Lesley F

    2016-01-01

    The redox properties of gadolinium doped ceria (CGO) and nickel oxide (NiO) composite cermets underpin the operation of solid oxide electrochemical cells. Although these systems have been widely studied, a full comprehension of the reaction dynamics at the interface of these materials is lacking. Here, in situ Raman spectroscopic monitoring of the redox cycle is used to investigate the interplay between the dynamic and competing processes of hydrogen spillover and water dissociation on the doped ceria surface. In order to elucidate these mechanisms, the redox process in pure CGO and NiO is studied when exposed to wet and dry hydrogen and is compared to the cermet behavior. In dry hydrogen, CGO reduces relatively rapidly via a series of intermediate phases, while NiO reduces via a single-step process. In wet reducing atmospheres, however, the oxidation state of pure CGO is initially stabilized due to the dissociation of water by reduced Ce(III) and subsequent incorporation of oxygen into the structure. In the reduction process involving the composite cermet, the close proximity of the NiO improves the efficiency and speed of the composite reduction process. Although NiO is already incorporated into working cells, these observations suggest direct routes to further improve cell performance.

  2. Cholesterol photo-oxidation: A chemical reaction network for kinetic modeling.

    Science.gov (United States)

    Barnaba, Carlo; Rodríguez-Estrada, Maria Teresa; Lercker, Giovanni; García, Hugo Sergio; Medina-Meza, Ilce Gabriela

    2016-12-01

    In this work we studied the effect of polyunsaturated fatty acids (PUFAs) methyl esters on cholesterol photo-induced oxidation. The oxidative routes were modeled with a chemical reaction network (CRN), which represents the first application of CRN to the oxidative degradation of a food-related lipid matrix. Docosahexaenoic acid (DHA, T-I), eicosapentaenoic acid (EPA, T-II) and a mixture of both (T-III) were added to cholesterol using hematoporphyrin as sensitizer, and were exposed to a fluorescent lamp for 48h. High amounts of Type I cholesterol oxidation products (COPs) were recovered (epimers 7α- and 7β-OH, 7-keto and 25-OH), as well as 5β,6β-epoxy. Fitting the experimental data with the CRN allowed characterizing the associated kinetics. DHA and EPA exerted different effects on the oxidative process. DHA showed a protective effect to 7-hydroxy derivatives, whereas EPA enhanced side-chain oxidation and 7β-OH kinetic rates. The mixture of PUFAs increased the kinetic rates several fold, particularly for 25-OH. With respect to the control, the formation of β-epoxy was reduced, suggesting potential inhibition in the presence of PUFAs. Copyright © 2016 Elsevier Inc. All rights reserved.

  3. Oxidation of β-lactam antibiotics by peracetic acid: Reaction kinetics, product and pathway evaluation.

    Science.gov (United States)

    Zhang, Kejia; Zhou, Xinyan; Du, Penghui; Zhang, Tuqiao; Cai, Meiquan; Sun, Peizhe; Huang, Ching-Hua

    2017-10-15

    Peracetic acid (PAA) is a disinfection oxidant used in many industries including wastewater treatment. β-Lactams, a group of widely prescribed antibiotics, are frequently detected in wastewater effluents and surface waters. The reaction kinetics and transformation of seven β-lactams (cefalexin (CFX), cefadroxil (CFR), cefapirin (CFP), cephalothin (CFT), ampicillin (AMP), amoxicillin (AMX) and penicillin G (PG)) toward PAA were investigated to elucidate the behavior of β-lactams during PAA oxidation processes. The reaction follows second-order kinetics and is much faster at pH 5 and 7 than at pH 9 due to speciation of PAA. Reactivity to PAA follows the order of CFR ∼ CFX > AMP ∼ AMX > CFT ∼ CFP ∼ PG and is related to β-lactam's nucleophilicity. The thioether sulfur of β-lactams is attacked by PAA to generate sulfoxide products. Presence of the phenylglycinyl amino group on β-lactams can significantly influence electron distribution and the highest occupied molecular orbital (HOMO) location and energy in ways that enhance the reactivity to PAA. Reaction rate constants obtained in clean water matrix can be used to accurately model the decay of β-lactams by PAA in surface water matrix and only slightly overestimate the decay in wastewater matrix. Results of this study indicate that the oxidative transformation of β-lactams by PAA can be expected under appropriate wastewater treatment conditions. Copyright © 2017. Published by Elsevier Ltd.

  4. The oxidative response and viable reaction mechanism of the textile dyes by fenton reagent

    International Nuclear Information System (INIS)

    Masooda, Q.; Hijira, T.; Sitara, M.; Sehar, M.; Sundus, A.; Mohsin, A.

    2017-01-01

    The mechanism of the degradation of the Reactive Red 239 and Reactive Blue 19 by Fenton reagent was studied by advanced oxidation process in aqueous medium. The spectroscopic technique was adopted for the measurements of dye concentration. Moreover they were determined at 540 nm and 590 nm, respectively. Kinetics of the reaction was studied under the effect of concentration of reactive dyes, concentration of oxidant were followed under pseudo first order condition and found to influence the catalytic mechanism. The pH of the medium, vibrant response of several cations and anions and influence of ionic strength on the reaction kinetics were also monitored. Physical evidences for the degradation and mineralization of the dyes were evaluated by Lime water test, Ring Test and TLC test also confirmed the degradation of dye. Inhibitory effects of dyes were observed by CO3-, HCO3-, HPO42-, Cl-, I- Al3+ and Na+. Thermodynamic activation parameters in the oxidation reaction were studied and mode of mechanism was suggested on the basic of these parameters. This study explored the safe and eco friendly degradation of the textile dyes under Pseudo first order rate constant. It was observed that Fenton assisted degradation of the dyes under controlled conditions was found to be favorable for the treatment of textile wastewater. Moreover compared to other chemical methods it is effective and harmless to the environment. (author)

  5. Reaction and Aggregation Dynamics of Cell Surface Receptors

    Science.gov (United States)

    Wang, Michelle Dong

    This dissertation is composed of both theoretical and experimental studies of cell surface receptor reaction and aggregation. Project I studies the reaction rate enhancement due to surface diffusion of a bulk dissolved ligand with its membrane embedded target, using numerical calculations. The results show that the reaction rate enhancement is determined by ligand surface adsorption and desorption kinetic rates, surface and bulk diffusion coefficients, and geometry. In particular, we demonstrate that the ligand surface adsorption and desorption kinetic rates, rather than their ratio (the equilibrium constant), are important in rate enhancement. The second and third projects are studies of acetylcholine receptor clusters on cultured rat myotubes using fluorescence techniques after labeling the receptors with tetramethylrhodamine -alpha-bungarotoxin. The second project studies when and where the clusters form by making time-lapse movies. The movies are made from overlay of the pseudocolored total internal reflection fluorescence (TIRF) images of the cluster, and the schlieren images of the cell cultures. These movies are the first movies made using TIRF, and they clearly show the cluster formation from the myoblast fusion, the first appearance of clusters, and the eventual disappearance of clusters. The third project studies the fine structural features of individual clusters observed under TIRF. The features were characterized with six parameters by developing a novel fluorescence technique: spatial fluorescence autocorrelation. These parameters were then used to study the feature variations with age, and with treatments of drugs (oligomycin and carbachol). The results show little variation with age. However, drug treatment induced significant changes in some parameters. These changes were different for oligomycin and carbachol, which indicates that the two drugs may eliminate clusters through different mechanisms.

  6. Global dynamics of a reaction-diffusion system

    Directory of Open Access Journals (Sweden)

    Yuncheng You

    2011-02-01

    Full Text Available In this work the existence of a global attractor for the semiflow of weak solutions of a two-cell Brusselator system is proved. The method of grouping estimation is exploited to deal with the challenge in proving the absorbing property and the asymptotic compactness of this type of coupled reaction-diffusion systems with cubic autocatalytic nonlinearity and linear coupling. It is proved that the Hausdorff dimension and the fractal dimension of the global attractor are finite. Moreover, the existence of an exponential attractor for this solution semiflow is shown.

  7. Comparison of dynamical aspects of nonadiabatic electron, proton, and proton-coupled electron transfer reactions

    International Nuclear Information System (INIS)

    Hatcher, Elizabeth; Soudackov, Alexander; Hammes-Schiffer, Sharon

    2005-01-01

    The dynamical aspects of a model proton-coupled electron transfer (PCET) reaction in solution are analyzed with molecular dynamics simulations. The rate for nonadiabatic PCET is expressed in terms of a time-dependent probability flux correlation function. The impact of the proton donor-acceptor and solvent dynamics on the probability flux is examined. The dynamical behavior of the probability flux correlation function is dominated by a solvent damping term that depends on the energy gap correlation function. The proton donor-acceptor motion does not impact the dynamical behavior of the probability flux correlation function but does influence the magnitude of the rate. The approximations previously invoked for the calculation of PCET rates are tested. The effects of solvent damping on the proton donor-acceptor vibrational motion are found to be negligible, and the short-time solvent approximation, in which only equilibrium fluctuations of the solvent are considered, is determined to be valid for these types of reactions. The analysis of PCET reactions is compared to previous analyses of single electron and proton transfer reactions. The dynamical behavior is qualitatively similar for all three types of reactions, but the time scale of the decay of the probability flux correlation function is significantly longer for single proton transfer than for PCET and single electron transfer due to a smaller solvent reorganization energy for proton transfer

  8. Seasonal Oxygen Dynamics in a Thermokarst Bog in Interior Alaska: Implications for Rates of Methane Oxidation

    Science.gov (United States)

    Neumann, R. B.; Moorberg, C.; Wong, A.; Waldrop, M. P.; Turetsky, M. R.

    2015-12-01

    Methane is a potent greenhouse gas, and wetlands represent the largest natural source of methane to the atmosphere. However, much of the methane generated in anoxic wetlands never gets emitted to the atmosphere; up to >90% of generated methane can get oxidized to carbon dioxide. Thus, oxidation is an important methane sink and changes in the rate of methane oxidation can affect wetland methane emissions. Most methane is aerobically oxidized at oxic-anoxic interfaces where rates of oxidation strongly depend on methane and oxygen concentrations. In wetlands, oxygen is often the limiting substrate. To improve understanding of belowground oxygen dynamics and its impact on methane oxidation, we deployed two planar optical oxygen sensors in a thermokarst bog in interior Alaska. Previous work at this site indicated that, similar to other sites, rates of methane oxidation decrease over the growing season. We used the sensors to track spatial and temporal patterns of oxygen concentrations over the growing season. We coupled these in-situ oxygen measurements with periodic oxygen injection experiments performed against the sensor to quantify belowground rates of oxygen consumption. We found that over the season, the thickness of the oxygenated water layer at the peatland surface decreased. Previous research has indicated that in sphagnum-dominated peatlands, like the one studied here, rates of methane oxidation are highest at or slightly below the water table. It is in these saturated but oxygenated locations that both methane and oxygen are available. Thus, a seasonal reduction in the thickness of the oxygenated water layer could restrict methane oxidation. The decrease in thickness of the oxygenated layer coincided with an increase in the rate of oxygen consumption during our oxygen injection experiments. The increase in oxygen consumption was not explained by temperature; we infer it was due to an increase in substrate availability for oxygen consuming reactions and

  9. Competitive Pressure: Competitive Dynamics as Reactions to Multiple Rivals

    OpenAIRE

    Zucchini, Leon; Kretschmer, Tobias

    2011-01-01

    Competitive dynamics research has focused primarily on interactions between dyads of firms. Drawing on the awareness-motivation-capability framework and strategic group theory we extend this by proposing that firms’ actions are influenced by perceived competitive pressure resulting from actions by several rivals. We predict that firms’ action magnitude is influenced by the total number of rival actions accumulating in the market, and that this effect is moderated by strategic group membership...

  10. Oxidative removal of quinclorac by permanganate through a rate-limiting [3 + 2] cycloaddition reaction.

    Science.gov (United States)

    Song, Dean; Cheng, Hanyang; Jiang, Xiaohua; Sun, Huiqing; Kong, Fanyu; Liang, Rongning; Qiang, Zhimin; Liu, Huijuan; Qu, Jiuhui

    2018-04-05

    Quinclorac, a widely used herbicide in agriculture, has been recognized as an emerging environmental pollutant owing to its long persistence and potential risk to humans. However, no related information is available on the degradation of quinclorac by employing oxidants. Herein, the reactivity of quinclorac with permanganate was systematically investigated in water by combining experimental and computational approaches. The reaction followed overall second-order kinetics pointing to a bimolecular rate-limiting step. The second-order rate constant was found to be 3.47 × 10-3 M-1 s-1 at 25 °C, which was independent of pH over the range from 5 to 9 and was dependent on temperature over the range from 19 to 35 °C. The initial product was identified by UPLC-Q-TOF-MS to be mono-hydroxylated quinclorac, which was more susceptible to further oxidation. The result could be supported by the complete simulation of the reaction process in DFT calculations, indicating the [3 + 2] cycloaddition oxidation of the benzene ring in the rate-limiting step. The plausible mechanism was then proposed, accompanied by the analysis of the HOMO indicating the hydroxylation position and of the ESP suggesting a more electron-rich moiety. Considering the high effectiveness and low toxicity, permanganate oxidation was considered to be a very promising technique for removing quinclorac from aquatic environments.

  11. Nucleon induced reaction by anti-symmetrized molecular dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Tosaka, Yoshiharu [Fujitsu Labs. Ltd., Kawasaki, Kanagawa (Japan); Ono, Akira; Horiuchi, Hisashi

    1998-07-01

    Neutron soft error is a phenomenon, for example, to change memory information of LSI from 0 to 1 by introducing a lot of charge depend on product ions by nuclear reaction between neutrons of second cosmic rays and nuclei of Si in LSI. To study the phenomena, the information such as energy, angular and mass distribution of product ions by n+{sup 28}Si reaction from 20 to 500 MeV incident energy were necessary. 180 MeV p+{sup 27}Al, having large amount of data of heavy recoil nucleus, was investigated. On AMD, A = 1,24-27 ion were produced at the initial collision (before 100 fm/c), after that the mass distribution was not changed, indicating stable excited nucleus. However, on AMD-V, the excited nuclei were destructed in course of time. A = 1,2,4,18 and 21-27 ion were produced at 120 fm/c, but almost kinds of ions less than 27 produced at 320 fm/c. After decay, difference between results of AMD and AMD-V was small and both reproduced the experimental values. AMD-V gave better result of product cross section and differential cross section. (S.Y.)

  12. Oxidative coupling of methane. Still a challenge for catalyst development and reaction engineering

    Energy Technology Data Exchange (ETDEWEB)

    Schomaecker, R.; Arnd, S.; Beck, B. [Technical Univ. of Berlin (Germany). Dept. of Chemistry] [and others

    2013-11-01

    The oxidative coupling of methane to ethylene offers great industrial potential, because it would broaden the feedstock basis for chemical industry. Because methane is the most stable hydrocarbon, its activation requires high temperatures and it is a great scientific challenge to overcome the apparent yield limit of about 25%. This barrier has never been exceeded since the beginning of OCM research more than 20 years ago. Results and Discussion: This challenge is one of the key projects of the Cluster of Excellence UNICAT and requires joined efforts and contributions from many disciplines, because this reaction shows a combined surface/gas phase reaction mechanism which results in very unusual and complex dependencies on the reaction conditions. Although dozens of materials are known to catalyze the reaction, the selection of a catalyst suitable for an industrial process is difficult, due to severe stability problems of many materials. Li/MgO was chosen by the UNICAT-team as model catalyst, because of the extended literature about it. But it shows uncontrollable deactivation, no matter what precursor and method were used for its preparation. Nevertheless, it is a suitable catalyst for fundamental studies, due to its formal chemical simplicity. A key result of the joined research activities was the disproval of the Lunsford mechanism and the elucidation of the real function of lithium as a surface modifier creating a rough and defect-rich surface. For the development of an OCM process another catalyst, Na{sub 2}WO{sub 4}/Mn/SiO{sub 2}, was chosen from the rich literature on OCM. Although less is known about its structure and the reaction mechanism at this catalyst, its stability was the most important reason to select it for further engineering studies. Kinetic isotope measurements and studies in a TAP reactor demonstrate the similarity of the reaction mechanisms at both catalysts, despite the completely different materials. The selectivity is largely controlled by

  13. Citric acid-modified Fenton's reaction for the oxidation of chlorinated ethylenes in soil solution systems.

    Science.gov (United States)

    Seol, Yongkoo; Javandel, Iraj

    2008-06-01

    Fenton's reagent, a solution of hydrogen peroxide and ferrous iron catalyst, is used for an in situ chemical oxidation of organic contaminants. Sulfuric acid is commonly used to create an acidic condition needed for catalytic oxidation. Fenton's reaction often involves pressure buildup and precipitation of reaction products, which can cause safety hazards and diminish efficiency. We selected citric acid, a food-grade substance, as an acidifying agent to evaluate its efficiencies for organic contaminant removal in Fenton's reaction, and examined the impacts of using citric acid on the unwanted reaction products. A series of batch and column experiments were performed with varying H2O2 concentrations to decompose selected chlorinated ethylenes. Either dissolved iron from soil or iron sulfate salt was added to provide the iron catalyst in the batch tests. Batch experiments revealed that both citric and sulfuric acid systems achieved over 90% contaminant removal rates, and the presence of iron catalyst was essential for effective decontamination. Batch tests with citric acid showed no signs of pressure accumulation and solid precipitations, however the results suggested that an excessive usage of H2O2 relative to iron catalysts (Fe2+/H2O2<1/330) would result in lowering the efficiency of contaminant removal by iron chelation in the citric acid system. Column tests confirmed that citric acid could provide suitable acidic conditions to achieve higher than 55% contaminant removal rates.

  14. Ozonization, Amination and Photoreduction of Graphene Oxide for Triiodide Reduction Reaction: An Experimental and Theoretical Study

    International Nuclear Information System (INIS)

    Jing, Hongyu; Ren, Suzhen; Shi, Yantao; Song, Xuedan; Yang, Ying; Guo, Yanan; An, Yonglin; Hao, Ce

    2017-01-01

    This work proposes a mild and environmentally-friendly approach to prepare a highly efficient functional graphene (termed as AGO-hv) using methods of ozone oxidation, solvothermal synthesis, and photoreduction. The use of ozone oxidation in the first step can effectively increase the interlaminar distance between graphite oxide sheets, and create active sites for nucleophilic attack on the epoxy carbon from ammonia. The amino groups were successfully grafted on the surface of graphene as evidenced by the amidation reaction, with a maximum nitrogen content of 10.46 wt% and a C/N molar ratio of 8.46. After further photoreduction of the aminated graphite oxide (AGO), the residual oxygen functionalities, such as C-OH, were effectively removed and the conductivity of the graphene sheet was further recovered. The dye-sensitized solar cell (DSC) exhibited a power conversion efficiency (PCE) of 7.51% based on AGO-hv counter electrode (CE), close to that of Pt counterpart (7.79%). The experimental results indicated that the amidation and photoreduction processes were significantly facilitated by the initial ozonization of graphene oxide, and this process significantly improved the electrochemical activity and the conductivity of graphene oxide. Density functional theory (DFT) calculations revealed that AGO-hv had the lowest ionization energy (a better electron-donating ability) and also suitable binding energy with I atoms as well. The combination of ozonization, amination and photoreduction is an efficient route to obtain electrocatalysts with desired compositional distributions and performance for triiodide reduction reaction in DSCs.

  15. Development of tight-binding, chemical-reaction-dynamics simulator for combinatorial computational chemistry

    International Nuclear Information System (INIS)

    Kubo, Momoji; Ando, Minako; Sakahara, Satoshi; Jung, Changho; Seki, Kotaro; Kusagaya, Tomonori; Endou, Akira; Takami, Seiichi; Imamura, Akira; Miyamoto, Akira

    2004-01-01

    Recently, we have proposed a new concept called 'combinatorial computational chemistry' to realize a theoretical, high-throughput screening of catalysts and materials. We have already applied our combinatorial, computational-chemistry approach, mainly based on static first-principles calculations, to various catalysts and materials systems and its applicability to the catalysts and materials design was strongly confirmed. In order to realize more effective and efficient combinatorial, computational-chemistry screening, a high-speed, chemical-reaction-dynamics simulator based on quantum-chemical, molecular-dynamics method is essential. However, to the best of our knowledge, there is no chemical-reaction-dynamics simulator, which has an enough high-speed ability to perform a high-throughput screening. In the present study, we have succeeded in the development of a chemical-reaction-dynamics simulator based on our original, tight-binding, quantum-chemical, molecular-dynamics method, which is more than 5000 times faster than the regular first-principles, molecular-dynamics method. Moreover, its applicability and effectiveness to the atomistic clarification of the methanol-synthesis dynamics at reaction temperature were demonstrated

  16. Photoinduced Cross-Linking of Dynamic Poly(disulfide) Films via Thiol Oxidative Coupling.

    Science.gov (United States)

    Feillée, Noémi; Chemtob, Abraham; Ley, Christian; Croutxé-Barghorn, Céline; Allonas, Xavier; Ponche, Arnaud; Le Nouen, Didier; Majjad, Hicham; Jacomine, Léandro

    2016-01-01

    Initially developed as an elastomer with an excellent record of barrier and chemical resistance properties, poly(disulfide) has experienced a revival linked to the dynamic nature of the S-S covalent bond. A novel photobase-catalyzed oxidative polymerization of multifunctional thiols to poly(disulfide) network is reported. Based solely on air oxidation, the single-step process is triggered by the photodecarboxylation of a xanthone acetic acid liberating a strong bicyclic guanidine base. Starting with a 1 μm thick film based on trithiol poly(ethylene oxide) oligomer, the UV-mediated oxidation of thiols to disulfides occurs in a matter of minutes both selectively, i.e., without overoxidation, and quantitatively as assessed by a range of spectroscopic techniques. Thiolate formation and film thickness determine the reaction rates and yield. Spatial control of the photopolymerization serves to generate robust micropatterns, while the reductive cleavage of S-S bridges allows the recycling of 40% of the initial thiol groups. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Quasi-elastic reactions: an interplay of reaction dynamics and nuclear structure

    Directory of Open Access Journals (Sweden)

    Recchia F.

    2011-10-01

    Full Text Available Multinucleon transfer reactions have been investigated in 40Ar+208Pb with the Prisma+Clara set-up. The experimental differential cross sections of different neutron transfer channels have been obtained at three different angular settings taking into account the transmission through the spectrometer. The experimental yields of the excited states have been determined via particle-γ coincidences. In odd Ar isotopes, we reported a signif cant population of 11/2− states, reached via neutron transfer. Their structure matches a stretched conf guration of the valence neutron coupled to vibration quanta.

  18. Multimillion atom simulations of dynamics of oxidation of an aluminum nanoparticle and nanoindentation on ceramics.

    Science.gov (United States)

    Vashishta, Priya; Kalia, Rajiv K; Nakano, Aiichiro

    2006-03-02

    We have developed a first-principles-based hierarchical simulation framework, which seamlessly integrates (1) a quantum mechanical description based on the density functional theory (DFT), (2) multilevel molecular dynamics (MD) simulations based on a reactive force field (ReaxFF) that describes chemical reactions and polarization, a nonreactive force field that employs dynamic atomic charges, and an effective force field (EFF), and (3) an atomistically informed continuum model to reach macroscopic length scales. For scalable hierarchical simulations, we have developed parallel linear-scaling algorithms for (1) DFT calculation based on a divide-and-conquer algorithm on adaptive multigrids, (2) chemically reactive MD based on a fast ReaxFF (F-ReaxFF) algorithm, and (3) EFF-MD based on a space-time multiresolution MD (MRMD) algorithm. On 1920 Intel Itanium2 processors, we have demonstrated 1.4 million atom (0.12 trillion grid points) DFT, 0.56 billion atom F-ReaxFF, and 18.9 billion atom MRMD calculations, with parallel efficiency as high as 0.953. Through the use of these algorithms, multimillion atom MD simulations have been performed to study the oxidation of an aluminum nanoparticle. Structural and dynamic correlations in the oxide region are calculated as well as the evolution of charges, surface oxide thickness, diffusivities of atoms, and local stresses. In the microcanonical ensemble, the oxidizing reaction becomes explosive in both molecular and atomic oxygen environments, due to the enormous energy release associated with Al-O bonding. In the canonical ensemble, an amorphous oxide layer of a thickness of approximately 40 angstroms is formed after 466 ps, in good agreement with experiments. Simulations have been performed to study nanoindentation on crystalline, amorphous, and nanocrystalline silicon nitride and silicon carbide. Simulation on nanocrystalline silicon carbide reveals unusual deformation mechanisms in brittle nanophase materials, due to

  19. Biodegradation at Dynamic Plume Fringes: Mixing Versus Reaction Control

    Science.gov (United States)

    Cirpka, O. A.; Eckert, D.; Griebler, C.; Haberer, C.; Kürzinger, P.; Bauer, R.; Mellage, A.

    2014-12-01

    Biodegradation of continuously emitted plumes is known to be most pronounced at the plume fringe, where mixing of contaminated water and ambient groundwater, containing dissolved electron acceptors, stimulates microbial activity. Under steady-state conditions, physical mixing of contaminant and electron acceptor by transverse dispersion was shown to be the major bottleneck for biodegradation, with plume lengths scaling inversely with the bulk transverse dispersivity in quasi two-dimensional settings. Under these conditions, the presence of suitable microbes is essential but the biokinetic parameters do not play an important role. When the location of the plume shifts (caused, e.g., by a fluctuating groundwater table), however, the bacteria are no more situated at the plume fringe and biomass growth, decay, activation and deactivation determine the time lag until the fringe-controlled steady state is approached again. During this time lag, degradation is incomplete. The objective of the presented study was to analyze to which extent flow and transport dynamics diminish effectiveness of fringe-controlled biodegradation and which microbial processes and related biokinetic parameters determine the system response in overall degradation to hydraulic fluctuations. We performed experiments in quasi-two-dimensional flow through microcosms on aerobic toluene degradation by Pseudomonas putida F1. Plume dynamics were simulated by vertical alteration of the toluene plume position and experimental results were analyzed by reactive-transport modeling. We found that, even after disappearance of the toluene plume for two weeks, the majority of microorganisms stayed attached to the sediment and regained their full biodegradation potential within two days after reappearance of the toluene plume. Our results underline that besides microbial growth and maintenance (often subsumed as "biomass decay") microbial dormancy (that is, change into a metabolically inactive state) and

  20. Transcriptional dynamics with time-dependent reaction rates

    Science.gov (United States)

    Nandi, Shubhendu; Ghosh, Anandamohan

    2015-02-01

    Transcription is the first step in the process of gene regulation that controls cell response to varying environmental conditions. Transcription is a stochastic process, involving synthesis and degradation of mRNAs, that can be modeled as a birth-death process. We consider a generic stochastic model, where the fluctuating environment is encoded in the time-dependent reaction rates. We obtain an exact analytical expression for the mRNA probability distribution and are able to analyze the response for arbitrary time-dependent protocols. Our analytical results and stochastic simulations confirm that the transcriptional machinery primarily act as a low-pass filter. We also show that depending on the system parameters, the mRNA levels in a cell population can show synchronous/asynchronous fluctuations and can deviate from Poisson statistics.

  1. Transcriptional dynamics with time-dependent reaction rates

    International Nuclear Information System (INIS)

    Nandi, Shubhendu; Ghosh, Anandamohan

    2015-01-01

    Transcription is the first step in the process of gene regulation that controls cell response to varying environmental conditions. Transcription is a stochastic process, involving synthesis and degradation of mRNAs, that can be modeled as a birth–death process. We consider a generic stochastic model, where the fluctuating environment is encoded in the time-dependent reaction rates. We obtain an exact analytical expression for the mRNA probability distribution and are able to analyze the response for arbitrary time-dependent protocols. Our analytical results and stochastic simulations confirm that the transcriptional machinery primarily act as a low-pass filter. We also show that depending on the system parameters, the mRNA levels in a cell population can show synchronous/asynchronous fluctuations and can deviate from Poisson statistics. (paper)

  2. Dynamical hindrance to compound nucleus formation in heavy ion reactions

    International Nuclear Information System (INIS)

    Blocki, J.; Feldmeier, H.; Swiatecki, W.J.

    1987-01-01

    A large number of dynamical trajectories corresponding to colliding nuclei, as represented by an idealized, sharp-surfaced liquid-drop model with one-body dissipation are examined. The objective was to delineate quantitatively, within this model, the behaviour of the extra-extra-push energy E XX in its dependence on the mass /or charge/ numbers of the colliding nuclei. Qualitatively, the results are as anticipated on the basis of earlier studies: the appearance of a dynamical limitation on compound nucleus formation beyond a certain threshold locus in the A 1 . A 2 plane, with the energy E XX rising smoothly but rapidly beyond the threshold. The reduction of the two-dimensional function E XX /A 1 ,A 2 / to a one-dimensional function of a mean fissility x m appears possible as a rough approximation. As expected, the mean fissility x and the entrance channel fissility x 0 . The optimum choice appears to be one in which x is given about twice the weight of x 0

  3. Valence force fields and the lattice dynamics of beryllium oxide

    International Nuclear Information System (INIS)

    Ramani, R.; Mani, K.K.; Singh, R.P.

    1976-01-01

    The lattice dynamics of beryllium oxide have been studied using a rigid-ion model, with short-range forces represented by a valence force field. Various existing calculations on group-IV elements using such a field have been examined as a prelude to transference of force constants from diamond to beryllium oxide. The effects of ionicity on the force constants have been included in the form of scale factors. It is shown that no satisfactory fit to the long-wavelength data on BeO can be found with transferred force constants. However, adequate least-squares fits can be found both with four- and six-parameter valence force fields, the discrepancy with experiment being large only for one optical mode at the Brillouin-zone center. Dispersion curves along Δ and Σ are presented and are in fair agreement with experiment, deviations arising essentially from the quality of the fit to the long-wavelength data. The bond-bending interactions are found to play a significant role and arguments have been presented to show that the inclusion of further angle-angle interactions would yield a very satisfactory picture of the dynamics

  4. Nonlinear electromechanical modelling and dynamical behavior analysis of a satellite reaction wheel

    Science.gov (United States)

    Aghalari, Alireza; Shahravi, Morteza

    2017-12-01

    The present research addresses the satellite reaction wheel (RW) nonlinear electromechanical coupling dynamics including dynamic eccentricity of brushless dc (BLDC) motor and gyroscopic effects, as well as dry friction of shaft-bearing joints (relative small slip) and bearing friction. In contrast to other studies, the rotational velocity of the flywheel is considered to be controllable, so it is possible to study the reaction wheel dynamical behavior in acceleration stages. The RW is modeled as a three-phases BLDC motor as well as flywheel with unbalances on a rigid shaft and flexible bearings. Improved Lagrangian dynamics for electromechanical systems is used to obtain the mathematical model of the system. The developed model can properly describe electromechanical nonlinear coupled dynamical behavior of the satellite RW. Numerical simulations show the effectiveness of the presented approach.

  5. Time-resolved imaging of purely valence-electron dynamics during a chemical reaction

    DEFF Research Database (Denmark)

    Hockett, Paul; Bisgaard, Christer Z.; Clarkin, Owen J.

    2011-01-01

    Chemical reactions are manifestations of the dynamics of molecular valence electrons and their couplings to atomic motions. Emerging methods in attosecond science can probe purely electronic dynamics in atomic and molecular systems(1-6). By contrast, time-resolved structural-dynamics methods...... such as electron(7-10) or X-ray diffraction(11) and X-ray absorption(12) yield complementary information about the atomic motions. Time-resolved methods that are directly sensitive to both valence-electron dynamics and atomic motions include photoelectron spectroscopy(13-15) and high-harmonic generation(16......,17): in both cases, this sensitivity derives from the ionization-matrix element(18,19). Here we demonstrate a time-resolved molecular-frame photoelectron-angular-distribution (TRMFPAD) method for imaging the purely valence-electron dynamics during a chemical reaction. Specifically, the TRMFPADs measured during...

  6. Oxidative Dehydrogenation on Nanocarbon: Insights into the Reaction Mechanism and Kinetics via in Situ Experimental Methods.

    Science.gov (United States)

    Qi, Wei; Yan, Pengqiang; Su, Dang Sheng

    2018-03-20

    Sustainable and environmentally benign catalytic processes are vital for the future to supply the world population with clean energy and industrial products. The replacement of conventional metal or metal oxide catalysts with earth abundant and renewable nonmetallic materials has attracted considerable research interests in the field of catalysis and material science. The stable and efficient catalytic performance of nanocarbon materials was discovered at the end of last century, and these materials are considered as potential alternatives for conventional metal-based catalysts. With its rapid development in the past 20 years, the research field of carbon catalysis has been experiencing a smooth transition from the discovery of novel nanocarbon materials or related new reaction systems to the atomistic-level mechanistic understanding on the catalytic process and the subsequent rational design of the practical catalytic reaction systems. In this Account, we summarize the recent progress in the kinetic and mechanistic studies on nanocarbon catalyzed alkane oxidative dehydrogenation (ODH) reactions. The paper attempts to extract general concepts and basic regularities for carbon catalytic process directing us on the way for rational design of novel efficient metal-free catalysts. The nature of the active sites for ODH reactions has been revealed through microcalorimetric analysis, ambient pressure X-ray photoelectron spectroscopy (XPS) measurement, and in situ chemical titration strategies. The detailed kinetic analysis and in situ catalyst structure characterization suggests that carbon catalyzed ODH reactions involve the redox cycles of the ketonic carbonyl-hydroxyl pairs, and the key physicochemical parameters (activation energy, reaction order, and rate/equilibrium constants, etc.) of the carbon catalytic systems are proposed and compared with conventional transition metal oxide catalysts. The proposal of the intrinsic catalytic activity (TOF) provides the

  7. Reaction of uranium oxides with chlorine and carbon or carbon monoxide to prepare uranium chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Haas, P.A.; Lee, D.D.; Mailen, J.C.

    1991-11-01

    The preferred preparation concept of uranium metal for feed to an AVLIS uranium enrichment process requires preparation of uranium tetrachloride (UCI{sub 4}) by reacting uranium oxides (UO{sub 2}/UO{sub 3}) and chlorine (Cl{sub 2}) in a molten chloride salt medium. UO{sub 2} is a very stable metal oxide; thus, the chemical conversion requires both a chlorinating agent and a reducing agent that gives an oxide product which is much more stable than the corresponding chloride. Experimental studies in a quartz reactor of 4-cm ID have demonstrated the practically of some chemical flow sheets. Experimentation has illustrated a sequence of results concerning the chemical flow sheets. Tests with a graphite block at 850{degrees}C demonstrated rapid reactions of Cl{sub 2} and evolution of carbon dioxide (CO{sub 2}) as a product. Use of carbon monoxide (CO) as the reducing agent also gave rapid reactions of Cl{sub 2} and formation of CO{sub 2} at lower temperatures, but the reduction reactions were slower than the chlorinations. Carbon powder in the molten salt melt gave higher rates of reduction and better steady state utilization of Cl{sub 2}. Addition of UO{sub 2} feed while chlorination was in progress greatly improved the operation by avoiding the plugging effects from high UO{sub 2} concentrations and the poor Cl{sub 2} utilizations from low UO{sub 2} concentrations. An UO{sub 3} feed gave undesirable effects while a feed of UO{sub 2}-C spheres was excellent. The UO{sub 2}-C spheres also gave good rates of reaction as a fixed bed without any molten chloride salt. Results with a larger reactor and a bottom condenser for volatilized uranium show collection of condensed uranium chlorides as a loose powder and chlorine utilizations of 95--98% at high feed rates. 14 refs., 7 figs., 14 tabs.

  8. Contribution to the study of the oxidation reaction of the carbon oxide in contact with catalysts issued from the decomposition of nickel hydro-aluminates at various temperatures

    International Nuclear Information System (INIS)

    Samaane, Mikhail

    1966-01-01

    Addressing the study of the oxidation reaction of carbon oxide which produces carbon dioxide, this research thesis reports the study of this reaction in presence of catalysts (2NiO + Al 2 O 3 , NiAl 2 O 4 and NiO + NiAl 2 O 4 ) issued from the decomposition of nickel hydro-aluminates at different temperatures. The first part describes experimental techniques and the nature of materials used in this study. The second part reports the study of the catalytic activity of the 2NiO+Al 2 O 3 catalyst during the oxidation of CO. Preliminary studies are also reported: structure and texture of nickel hydro-aluminate which is the raw material used to produce catalysts, activation of this compound to develop the catalytic activity in CO oxidation, chemisorption of CO, O 2 and CO 2 on the 2NiO+Al 2 O 3 solid, interaction of adsorbed gases at the solid surface, and kinetic study of the oxidation reaction. The third part reports the study of the catalytic activity in the oxidation reaction of CO of spinel catalysts (NiAl 2 O 4 and NiO+NiAl 2 O 4 ) obtained by calcination of nickel hydro-aluminates at high temperature. The formation of the spinel phase, the chemisorption of CO, O 2 and CO 2 on NiAl 2 O 4 , and the kinetic of the oxidation reaction are herein studied

  9. Spectroscopy and reaction dynamics of collision complexes containing hydroxyl radicals

    Energy Technology Data Exchange (ETDEWEB)

    Lester, M.I. [Univ. of Pennsylvania, Philadelphia (United States)

    1993-12-01

    The DOE supported work in this laboratory has focused on the spectroscopic characterization of the interaction potential between an argon atom and a hydroxyl radical in the ground X{sup 2}II and excited A {sup 2}{summation}{sup +} electronic states. The OH-Ar system has proven to be a test case for examining the interaction potential in an open-shell system since it is amenable to experimental investigation and theoretically tractable from first principles. Experimental identification of the bound states supported by the Ar + OH (X {sup 2}II) and Ar + OH(A {sup 2}{summation}{sup +}) potentials makes it feasible to derive realistic potential energy surfaces for these systems. The experimentally derived intermolecular potentials provide a rigorous test of ab initio theory and a basis for understanding the dramatically different collision dynamics taking place on the ground and excited electronic state surfaces.

  10. Pico-second laser spectroscopy and reaction dynamics in liquids

    International Nuclear Information System (INIS)

    Mialocq, Jean-Claude

    1984-01-01

    The dynamic relaxation of excited singlet states of molecules and ions in liquid solution is investigated using picosecond laser spectroscopy. The more efficient process for the deactivation of the first excited singlet state of pinacyanol is internal conversion S 1 → S 0 between iso-energetic states. At low viscosity, the rate constant is inversely proportional to the macroscopic viscosity and depends on the relaxation of the angle between the quinoline end groups around the polymethinic chain. Electron photodetachment by 265 nm excitation of the ferrocyanide and phenolate anions and photoionisation of neutral molecules, phenol, indole and tryptophan in polar solvents give rise to the solvated electron formation. The mono-or bi-photonic nature of the ejection process and the solvent relaxation around the excess electron are analyzed. (author) [fr

  11. Modelling of chalcopyrite oxidation reactions in the Outokumpu flash smelting process

    Energy Technology Data Exchange (ETDEWEB)

    Ahokainen, T.; Jokilaakso, A. [Helsinki Univ. of Technology, Otaniemi (Finland)

    1996-12-31

    A mathematical model for simulating oxidation reactions of chalcopyrite particles together with momentum, heat and mass transfer between particle and gas phase in a flash smelting furnace reaction shaft is presented. In simulation, the equations governing the gas flow are solved numerically with a commercial fluid flow package, Phoenics. The particle phase is introduced into the gas flow by a Particle Source In Cell (PSIC) - technique, where a number of discrete particles is tracked in a gas flow and the relevant source terms for momentum, mass, and heat transfer are added to the gas phase equations. The gas phase equations used are elliptic in nature and the fluid turbulence is described by the (k-{epsilon}) -model. Thermal gas phase radiation is simulated with a six-flux radiation model. The chemical reactions of concentrate particles are assumed to happen at two sharp interfaces, and a shrinking core model is applied to describe the mass transfer of chemical species through the reaction product layer. In a molten state, the oxygen consumption is controlled by a film penetration concept. The reacting concentrate particles are a mixture of chalcopyrite and silica. Also a certain amount of pure inert silica is fed to the process as flux. In the simulations the calculation domain includes the concentrate burner and a cylindrical reaction shaft of an industrial scale flash smelting furnace. Some examples about the simulations carried out by the combustion model are presented. (author)

  12. Modelling of chalcopyrite oxidation reactions in the Outokumpu flash smelting process

    Energy Technology Data Exchange (ETDEWEB)

    Ahokainen, T; Jokilaakso, A [Helsinki Univ. of Technology, Otaniemi (Finland)

    1997-12-31

    A mathematical model for simulating oxidation reactions of chalcopyrite particles together with momentum, heat and mass transfer between particle and gas phase in a flash smelting furnace reaction shaft is presented. In simulation, the equations governing the gas flow are solved numerically with a commercial fluid flow package, Phoenics. The particle phase is introduced into the gas flow by a Particle Source In Cell (PSIC) - technique, where a number of discrete particles is tracked in a gas flow and the relevant source terms for momentum, mass, and heat transfer are added to the gas phase equations. The gas phase equations used are elliptic in nature and the fluid turbulence is described by the (k-{epsilon}) -model. Thermal gas phase radiation is simulated with a six-flux radiation model. The chemical reactions of concentrate particles are assumed to happen at two sharp interfaces, and a shrinking core model is applied to describe the mass transfer of chemical species through the reaction product layer. In a molten state, the oxygen consumption is controlled by a film penetration concept. The reacting concentrate particles are a mixture of chalcopyrite and silica. Also a certain amount of pure inert silica is fed to the process as flux. In the simulations the calculation domain includes the concentrate burner and a cylindrical reaction shaft of an industrial scale flash smelting furnace. Some examples about the simulations carried out by the combustion model are presented. (author)

  13. The Effect of Temperature on Selectivity in the Oscillatory Mode of the Phenylacetylene Oxidative Carbonylation Reaction.

    Science.gov (United States)

    Parker, Julie; Novakovic, Katarina

    2017-08-05

    Reaction temperature plays a major role in product selectivity in the oscillatory mode of the palladium-catalyzed phenylacetylene oxidative carbonylation reaction. At 40 °C, dimethyl (2Z)-2-phenyl-2-butenedioate is the major product whereas at 0 °C the major product is 5,5-dimethoxy-3-phenyl-2(5H)-furanone. The occurrence of oscillations in pH coincides with an increase in the rate of phenylacetylene consumption and associated product formation. Experiments were performed isothermally in a reaction calorimeter to correlate reactant consumption and product formation with the occurrence of pH oscillations and the heat released by the reaction. An increase in the size of the pH drop in a single oscillation correlates with an increase in energy, indicating that this section of a single oscillation relates to reactant consumption. Based on these observations, a reaction pathway responsible for product formation is provided. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  14. Limonene ozonolysis in the presence of nitric oxide: Gas-phase reaction products and yields

    Science.gov (United States)

    Ham, Jason E.; Harrison, Joel C.; Jackson, Stephen R.; Wells, J. R.

    2016-05-01

    The reaction products from limonene ozonolysis were investigated using the new carbonyl derivatization agent, O-tert-butylhydroxylamine hydrochloride (TBOX). With ozone (O3) as the limiting reagent, five carbonyl compounds were detected. The yields of the carbonyl compounds are discussed with and without the presence of a hydroxyl radical (OHrad) scavenger, giving insight into the influence secondary OH radicals have on limonene ozonolysis products. The observed reaction product yields for limonaketone (LimaKet), 7-hydroxyl-6-oxo-3-(prop-1-en-2-yl)heptanal (7H6O), and 2-acetyl-5-oxohexanal (2A5O) were unchanged suggesting OHrad generated by the limonene + O3 reaction does not contribute to their formation. The molar yields of 3-isopropenyl-6-oxo-heptanal (IPOH) and 3-acetyl-6-oxoheptanal (3A6O) decreased by 68% and >95%; respectively, when OHrad was removed. This suggests that OHrad radicals significantly impact the formation of these products. Nitric oxide (NO) did not significantly affect the molar yields of limonaketone or IPOH. However, NO (20 ppb) considerably decreased the molar reaction product yields of 7H6O (62%), 2A5O (63%), and 3A6O (47%), suggesting NO reacted with peroxyl intermediates, generated during limonene ozonolysis, to form other carbonyls (not detected) or organic nitrates. These studies give insight into the transformation of limonene and its reaction products that can lead to indoor exposures.

  15. Adsorption and redox reactions of heavy metals on synthesized Mn oxide minerals

    International Nuclear Information System (INIS)

    Feng Xionghan; Zhai Limei; Tan Wenfeng; Liu Fan; He Jizheng

    2007-01-01

    Several Mn oxide minerals commonly occurring in soils were synthesized by modified or optimized methods. The morphologies, structures, compositions and surface properties of the synthesized Mn oxide minerals were characterized. Adsorption and redox reactions of heavy metals on these minerals in relation to the mineral structures and surface properties were also investigated. The synthesized birnessite, todorokite, cryptomelane, and hausmannite were single-phased minerals and had the typical morphologies from analyses of XRD and TEM/ED. The PZCs of the synthesized birnessite, todorokite and cryptomelane were 1.75, 3.50 and 2.10, respectively. The magnitude order of their surface variable negative charge was: birnessite ≥ cryptomelane > todorokite. The hausmannite had a much higher PZC than others with the least surface variable negative charge. Birnessite exhibited the largest adsorption capacity on heavy metals Pb 2+ , Cu 2+ , Co 2+ , Cd 2+ and Zn 2+ , while hausmannite the smallest one. Birnessite, cryptomelane and todorokite showed the greatest adsorption capacity on Pb 2+ among the tested heavy metals. Hydration tendency (pK 1 ) of the heavy metals and the surface variable charge of the Mn minerals had significant impacts on the adsorption. The ability in Cr(III) oxidation and concomitant release of Mn 2+ varied greatly depending on the structure, composition, surface properties and crystallinity of the minerals. The maximum amounts of Cr(III) oxidized by the Mn oxide minerals in order were (mmol/kg): birnessite (1330.0) > cryptomelane (422.6) > todorokite (59.7) > hausmannite (36.6). - The characteristics of heavy metal adsorption and Cr(III) oxidation on Mn oxide minerals are determined by their structure, composition, surface property and crystallinity

  16. Reaction mechanism of CO oxidation on Cu2O(111): A density functional study

    Science.gov (United States)

    Sun, Bao-Zhen; Chen, Wen-Kai; Xu, Yi-Jun

    2010-10-01

    The possible reaction mechanisms for CO oxidation on the perfect Cu2O(111) surface have been investigated by performing periodic density functional theoretical calculations. We find that Cu2O(111) is able to facilitate the CO oxidation with different mechanisms. Four possible mechanisms are explored (denoted as MER1, MER2, MLH1, and MLH2, respectively): MER1 is CO(gas)+O2(ads)-->CO2(gas) MER2 is CO(gas)+O2(ads)-->CO3(ads)-->O(ads)+CO2(gas) MLH1 refers to CO(ads)+O2(ads)-->O(ads)+CO2(ads) and MLH2 refers to CO(ads)+O2(ads)-->OOCO(ads)-->O(ads)+CO2(ads). Our transition state calculations clearly reveal that MER1 and MLH2 are both viable; but MER1 mechanism preferentially operates, in which only a moderate energy barrier (60.22 kJ/mol) needs to be overcome. When CO oxidation takes place along MER2 path, it is facile for CO3 formation, but is difficult for its decomposition, thereby CO3 species can stably exist on Cu2O(111). Of course, the reaction of CO with lattice O of Cu2O(111) is also considered. However, the calculated barrier is 600.00 kJ/mol, which is too large to make the path feasible. So, we believe that on Cu2O(111), CO reacts with adsorbed O, rather than lattice O, to form CO2. This is different from the usual Mars-van Krevene mechanism. The present results enrich our understanding of the catalytic oxidation of CO by copper-based and metal-oxide catalysts.

  17. Heterogeneous Reaction of SO2 on Manganese Oxides: the Effect of Crystal Structure and Relative Humidity.

    Science.gov (United States)

    Yang, Weiwei; Zhang, Jianghao; Ma, Qingxin; Zhao, Yan; Liu, Yongchun; He, Hong

    2017-07-03

    Manganese oxides from anthropogenic sources can promote the formation of sulfate through catalytic oxidation of SO 2 . In this study, the kinetics of SO 2 reactions on MnO 2 with different morphologies (α, β, γ and δ) was investigated using flow tube reactor and in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). Under dry conditions, the reactivity towards SO 2 uptake was highest on δ-MnO 2 but lowest on β-MnO 2 , with a geometric uptake coefficient (γ obs ) of (2.42 ± 0.13) ×10 -2 and a corrected uptake coefficient (γ c ) of (1.48 ± 0.21) ×10 -6 for the former while γ obs of (3.35 ± 0.43) ×10 -3 and γ c of (7.46 ± 2.97) ×10 -7 for the latter. Under wet conditions, the presence of water altered the chemical form of sulfate and was in favor for the heterogeneous oxidation of SO 2 . The maximum sulfate formation rate was reached at 25% RH and 45% for δ-MnO 2 and γ-MnO 2 , respectively, possibly due to their different crystal structures. The results suggest that morphologies and RH are important factors influencing the heterogeneous reaction of SO 2 on mineral aerosols, and that aqueous oxidation process involving transition metals of Mn might be a potential important pathway for SO 2 oxidation in the atmosphere.

  18. Iron oxide nanotube layer fabricated with electrostatic anodization for heterogeneous Fenton like reaction

    Energy Technology Data Exchange (ETDEWEB)

    Jang, Jun-Won; Park, Jae-Woo, E-mail: jaewoopark@hanyang.ac.kr

    2014-05-01

    Highlights: • Iron oxide nanotube was newly fabricated with potentiostatic anodization of Fe{sup 0} foil. • Cyanide was oxidized more effectively with the iron oxide nanotube and H{sub 2}O{sub 2}, resulting in fast oxidation of cyanide and cyanate. • This nanotube of Fe{sub 2}O{sub 3} on Fe{sup 0} metal can replace conventional particulate iron catalysts in Fenton-like processes. - Abstract: Iron oxide nanotubes (INT) were fabricated with potentiostatic anodization of zero valent iron foil in 1 M Na{sub 2}SO{sub 4} containing 0.5 wt% NH{sub 4}F electrolyte, holding the potential at 20, 40, and 60 V for 20 min, respectively. Field emission scanning electron microscopy and X-ray diffractometry were used to evaluate the morphology and crystalline structure of the INT film. The potential of 40 V for 20 min was observed to be optimal to produce an optimal catalytic film. Cyanide dissolved in water was degraded through the Fenton-like reaction using the INT film with hydrogen peroxide (H{sub 2}O{sub 2}). In case of INT-40 V in the presence of H{sub 2}O{sub 2} 3%, the first-order rate constant was found to be 1.7 × 10{sup −2} min{sup −1}, and 1.2 × 10{sup −2} min{sup −1} with commercial hematite powder. Degradation of cyanide was much less with only H{sub 2}O{sub 2}. Therefore, this process proposed in this work can be an excellent alternative to traditional catalysts for Fenton-like reaction.

  19. Enhanced methanol electro-oxidation reaction on Pt-CoOx/MWCNTs hybrid electro-catalyst

    International Nuclear Information System (INIS)

    Nouralishahi, Amideddin; Rashidi, Ali Morad; Mortazavi, Yadollah; Khodadadi, Abbas Ali; Choolaei, Mohammadmehdi

    2015-01-01

    Highlights: • Promoting effects of Cobalt oxide on methanol electro-oxidation over Pt/MWCNTs are investigated. • Higher activity, about 2.9 times, and enhanced stability are observed on Pt-CoO x /MWCNTs. • Electrochemical active surface area of Pt nanoparticles is significantly improved upon CoO x addition. • Bi-functional mechanism is facilitated in presence of CoO x . - Abstract: The electro-catalytic behavior of Pt-CoO x /MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH 4  as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoO x , Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of CO ads on Pt active sites by the participation of CoO x . Compared to Pt/MWCNTs, Pt-CoO x /MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoO x /MWCNTs, at small overpotentials. However, at higher overpotentials, the oxidation of adsorbed oxygen-containing groups

  20. Visible-light photoredox catalyzed synthesis of pyrroloisoquinolines via organocatalytic oxidation/[3 + 2] cycloaddition/oxidative aromatization reaction cascade with Rose Bengal

    Directory of Open Access Journals (Sweden)

    Carlos Vila

    2014-05-01

    Full Text Available Pyrrolo[2,1-a]isoquinoline alkaloids have been prepared via a visible light photoredox catalyzed oxidation/[3 + 2] cycloaddition/oxidative aromatization cascade using Rose Bengal as an organo-photocatalyst. A variety of pyrroloisoquinolines have been obtained in good yields under mild and metal-free reaction conditions.

  1. IBX-mediated oxidation of unactivated cyclic amines: application in highly diastereoselective oxidative Ugi-type and aza-Friedel-Crafts reactions.

    Science.gov (United States)

    de Graaff, C; Bensch, L; van Lint, Matthijs J; Ruijter, E; Orru, R V A

    2015-10-28

    The first o-iodoxybenzoic acid (IBX) mediated oxidation of unactivated amines to imines is described. A range of meso-pyrrolidines were shown to be suitable substrates. The chemical space was further explored with one-pot oxidative Ugi-type and aza-Friedel-Crafts reactions, which proved to be highly diastereoselective.

  2. Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C-S Bond Cleavage: Reaction Development and Mechanism Study.

    Science.gov (United States)

    Du, Bingnan; Wang, Wenmin; Wang, Yang; Qi, Zhenghang; Tian, Jiaqi; Zhou, Jie; Wang, Xiaochen; Han, Jianlin; Ma, Jing; Pan, Yi

    2018-02-16

    A Cu-catalyzed cascade oxidative radical process of β-keto sulfones with alcohols has been achieved by using oxygen as an oxidant. In this reaction, β-keto sulfones were converted into sulfinate esters under the oxidative conditions via cleavage of C-S bond. Experimental and computational studies demonstrate that a new pathway is involved in this reaction, which proceeds through the formation of the key four-coordinated Cu II intermediate, O-O bond homolysis induced C-S bond cleavage and Cu-catalyzed esterification to form the final products. This reaction provides a new strategy to sulfonate esters and enriches the research content of C-S bond cleavage and transformations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Understanding the insight into the mechanisms and dynamics of the Cl-initiated oxidation of (CH3)3CC(O)X and the subsequent reactions in the presence of NO and O2 (X = F, Cl, and Br).

    Science.gov (United States)

    Bai, Feng-Yang; Lv, Shuang; Ma, Yuan; Liu, Chun-Yu; He, Chun-Fang; Pan, Xiu-Mei

    2017-03-01

    In this work, the density functional and high-level ab initio theories are adopted to investigate the mechanisms and kinetics of reaction of (CH 3 ) 3 CC(O)X (X = F, Cl, and Br) with atomic chlorine. Rate coefficients for the reactions of chlorine atom with (CH 3 ) 3 CC(O)F (k 1 ), (CH 3 ) 3 CC(O)Cl (k 2 ), and (CH 3 ) 3 CC(O)Br (k 3 ) are calculated using canonical variational transition state theory coupled with small curvature tunneling method over a wide range of temperatures from 250 to 1000 K. The dynamic calculations are performed by the variational transition state theory with the interpolated single-point energies method at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-311++G(d,p) level of theory. Computed rate constant is in good line with the available experimental value. The rate constants for the title reactions are in this order: k 1 Br) are estimated, and it shows that (CH 3 ) 3 CC(O)F have larger GWP value than that of (CH 3 ) 3 CC(O)Cl and (CH 3 ) 3 CC(O)Br. Due to the presence of Cl and Br atoms, the environmental impact of (CH 3 ) 3 CC(O)Cl and (CH 3 ) 3 CC(O)Br may be given more concerns. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Ground Reaction Forces Generated During Rhythmical Squats as a Dynamic Loads of the Structure

    Science.gov (United States)

    Pantak, Marek

    2017-10-01

    Dynamic forces generated by moving persons can lead to excessive vibration of the long span, slender and lightweight structure such as floors, stairs, stadium stands and footbridges. These dynamic forces are generated during walking, running, jumping and rhythmical body swaying in vertical or horizontal direction etc. In the paper the mathematical models of the Ground Reaction Forces (GRFs) generated during squats have been presented. Elaborated models was compared to the GRFs measured during laboratory tests carried out by author in wide range of frequency using force platform. Moreover, the GRFs models were evaluated during dynamic numerical analyses and dynamic field tests of the exemplary structure (steel footbridge).

  5. Dynamical resonances in the fluorine atom reaction with the hydrogen molecule.

    Science.gov (United States)

    Yang, Xueming; Zhang, Dong H

    2008-08-01

    [Reaction: see text]. The concept of transition state has played a crucial role in the field of chemical kinetics and reaction dynamics. Resonances in the transition state region are important in many chemical reactions at reaction energies near the thresholds. Detecting and characterizing isolated reaction resonances, however, have been a major challenge in both experiment and theory. In this Account, we review the most recent developments in the study of reaction resonances in the benchmark F + H 2 --> HF + H reaction. Crossed molecular beam scattering experiments on the F + H 2 reaction have been carried out recently using the high-resolution, highly sensitive H-atom Rydberg tagging technique with HF rovibrational states almost fully resolved. Pronounced forward scattering for the HF (nu' = 2) product has been observed at the collision energy of 0.52 kcal/mol in the F + H 2 (j = 0) reaction. Quantum dynamical calculations based on two new potential energy surfaces, the Xu-Xie-Zhang (XXZ) surface and the Fu-Xu-Zhang (FXZ) surface, show that the observed forward scattering of HF (nu' = 2) in the F + H 2 reaction is caused by two Feshbach resonances (the ground resonance and first excited resonance). More interestingly, the pronounced forward scattering of HF (nu' = 2) at 0.52 kcal/mol is enhanced considerably by the constructive interference between the two resonances. In order to probe the resonance potential more accurately, the isotope substituted F + HD --> HF + D reaction has been studied using the D-atom Rydberg tagging technique. A remarkable and fast changing dynamical picture has been mapped out in the collision energy range of 0.3-1.2 kcal/mol for this reaction. Quantum dynamical calculations based on the XXZ surface suggest that the ground resonance on this potential is too high in comparison with the experimental results of the F + HD reaction. However, quantum scattering calculations on the FXZ surface can reproduce nearly quantitatively the resonance

  6. Investigation of the complex reaction coordinate of acid catalyzed amide hydrolysis from molecular dynamics simulations

    International Nuclear Information System (INIS)

    Zahn, Dirk

    2004-01-01

    The rate-determining step of acid catalyzed peptide hydrolysis is the nucleophilic attack of a water molecule to the carbon atom of the amide group. Therein the addition of the hydroxyl group to the amide carbon atom involves the association of a water molecule transferring one of its protons to an adjacent water molecule. The protonation of the amide nitrogen atom follows as a separate reaction step. Since the nucleophilic attack involves the breaking and formation of several bonds, the underlying reaction coordinate is rather complex. We investigate this reaction step from path sampling Car-Parrinello molecular dynamics simulations. This approach does not require the predefinition of reaction coordinates and is thus particularly suited for investigating reaction mechanisms. From our simulations the most relevant components of the reaction coordinate are elaborated. Though the C···O distance of the oxygen atom of the water molecule performing the nucleophilic attack and the corresponding amide carbon atom is a descriptor of the reaction progress, a complete picture of the reaction coordinate must include all three molecules taking part in the reaction. Moreover, the proton transfer is found to depend on favorable solvent configurations. Thus, also the arrangement of non-reacting, i.e. solvent water molecules needs to be considered in the reaction coordinate

  7. 1,3-Dipolar cycloaddition reactions of nitrile oxides in the synthesis of natural compounds and their analogues

    International Nuclear Information System (INIS)

    Kotyatkina, Anna I; Zhabinsky, Vladimir N; Khripach, Vladimir A

    2001-01-01

    The published data on the use of 1,3-dipolar cycloaddition reactions of nitrile oxides in the synthesis of natural compounds and their analogues are systematised and reviewed. The bibliography includes 145 references.

  8. The analysis of magnesium oxide hydration in three-phase reaction system

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Xiaojia; Guo, Lin; Chen, Chen; Liu, Quan; Li, Tie; Zhu, Yimin, E-mail: ntp@dlmu.edu.cn

    2014-05-01

    In order to investigate the magnesium oxide hydration process in gas–liquid–solid (three-phase) reaction system, magnesium hydroxide was prepared by magnesium oxide hydration in liquid–solid (two-phase) and three-phase reaction systems. A semi-empirical model and the classical shrinking core model were used to fit the experimental data. The fitting result shows that both models describe well the hydration process of three-phase system, while only the semi-empirical model right for the hydration process of two-phase system. The characterization of the hydration product using X-Ray diffraction (XRD) and scanning electron microscope (SEM) was performed. The XRD and SEM show hydration process in the two-phase system follows common dissolution/precipitation mechanism. While in the three-phase system, the hydration process undergo MgO dissolution, Mg(OH){sub 2} precipitation, Mg(OH){sub 2} peeling off from MgO particle and leaving behind fresh MgO surface. - Graphical abstract: There was existence of a peeling-off process in the gas–liquid–solid (three-phase) MgO hydration system. - Highlights: • Magnesium oxide hydration in gas–liquid–solid system was investigated. • The experimental data in three-phase system could be fitted well by two models. • The morphology analysis suggested that there was existence of a peel-off process.

  9. Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Dawei [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA; Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory Physical Chemistry Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen Fujian 361005 China; Kou, Ronghui [X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Ren, Yang [X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Sun, Cheng-Jun [X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Zhao, Hu [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA; Zhang, Ming-Jian [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA; School of Advanced Materials, Peking University Shenzhen Graduate School, Shenzhen Guangdong 518055 P. R. China; Li, Yan [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Huq, Ashifia [Chemical and Engineering Materials Division, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA; Ko, J. Y. Peter [The Cornell High Energy Synchrotron Source, Cornell University, Ithaca NY 14853 USA; Pan, Feng [School of Advanced Materials, Peking University Shenzhen Graduate School, Shenzhen Guangdong 518055 P. R. China; Sun, Yang-Kook [Department of Energy Engineering, Hanyang University, Seoul 133-791 South Korea; Yang, Yong [Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory Physical Chemistry Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen Fujian 361005 China; Amine, Khalil [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Bai, Jianming [National Synchrotron Light Source II, Brookhaven National Laboratory, Upton NY 11973 USA; Chen, Zonghai [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Wang, Feng [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA

    2017-08-25

    Nickel-rich layered transition metal oxides, LiNi1-x(MnCo)(x)O-2 (1-x >= 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi0.7Mn0.15Co0.15O2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strong temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs.

  10. Chemical dynamics in the gas phase: Time-dependent quantum mechanics of chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Gray, S.K. [Argonne National Laboratory, IL (United States)

    1993-12-01

    A major goal of this research is to obtain an understanding of the molecular reaction dynamics of three and four atom chemical reactions using numerically accurate quantum dynamics. This work involves: (i) the development and/or improvement of accurate quantum mechanical methods for the calculation and analysis of the properties of chemical reactions (e.g., rate constants and product distributions), and (ii) the determination of accurate dynamical results for selected chemical systems, which allow one to compare directly with experiment, determine the reliability of the underlying potential energy surfaces, and test the validity of approximate theories. This research emphasizes the use of recently developed time-dependent quantum mechanical methods, i.e. wave packet methods.

  11. Reductive and oxidative reactions with inorganic colloids in aqueous solution initiated by ultrasound

    International Nuclear Information System (INIS)

    Mulvaney, P.C.; Sostaric, J.Z.; Ashokkumar, M.; Grieser, F.

    1998-01-01

    Full text: The absorption of ultrasound in an aqueous solution can lead to the formation of H and OH radicals which can act as redox species or react with solutes to produce secondary radicals which themselves may participate in electron transfer reactions. The radical formation occurs through the growth then rapid collapse of microbubbles a process that produces localised hot spots with an internal temperature of the order of 5000 K. We have examined two colloidal systems one involving the reductive dissolution of MnO 2 colloids and the other the oxidative dissolution of CdS colloids. In the case of MnO 2 dissolution we found that the reduction of the colloidal metal oxide was considerably enhanced in the presence of aliphatic alcohols in solution and the longer the alkyl chain length on the alcohol the greater its effect. The dissolution of CdS colloids which we ascribe to the reaction of H 2 O 2 and O 2 - with the metal sulfide lo yield Cd 2+ and S could be significantly retarded by the presence of excess S 2- in solution. The mechanisms involved in these two dissolution processes will he presented. Our results clearly show that sonochemical reactions are quite efficient in colloidal solutions and this fact needs to be considered when using sonication to disperse colloidal material in solution, a common practice among colloid chemists

  12. The Nernst equation applied to oxidation-reduction reactions in myoglobin and hemoglobin. Evaluation of the parameters.

    Science.gov (United States)

    Saroff, Harry A

    Analyses of the binding of oxygen to monomers such as myoglobin employ the Mass Action equation. The Mass Action equation, as such, is not directly applicable for the analysis of the binding of oxygen to oligomers such as hemoglobin. When the binding of oxygen to hemoglobin is analyzed, models incorporating extensions of mass action are employed. Oxidation-reduction reactions of the heme group in myoglobin and hemoglobin involve the binding and dissociation of electrons. This reaction is described with the Nernst equation. The Nernst equation is applicable only to a monomeric species even if the number of electrons involved is greater than unity. To analyze the oxidation-reduction reaction in a molecule such as hemoglobin a model is required which incorporates extensions of the Nernst equation. This communication develops models employing the Nernst equation for oxidation-reduction reactions analogous to those employed for hemoglobin in the analysis of the oxygenation (binding of oxygen) reaction.

  13. The Role of Electronic Excitations on Chemical Reaction Dynamics at Metal, Semiconductor and Nanoparticle Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Tully, John C. [Yale Univ., New Haven, CT (United States)

    2017-06-10

    Chemical reactions are often facilitated and steered when carried out on solid surfaces, essential for applications such as heterogeneous catalysis, solar energy conversion, corrosion, materials processing, and many others. A critical factor that can determine the rates and pathways of chemical reactions at surfaces is the efficiency and specificity of energy transfer; how fast does energy move around and where does it go? For reactions on insulator surfaces energy transfer generally moves in and out of vibrations of the adsorbed molecule and the underlying substrate. By contrast, on metal surfaces, metallic nanoparticles and semiconductors, another pathway for energy flow opens up, excitation and de-excitation of electrons. This so-called “nonadiabatic” mechanism often dominates the transfer of energy and can directly impact the course of a chemical reaction. Conventional computational methods such as molecular dynamics simulation do not account for this nonadiabatic behavior. The current DOE-BES funded project has focused on developing the underlying theoretical foundation and the computational methodology for the prediction of nonadiabatic chemical reaction dynamics at surfaces. The research has successfully opened up new methodology and new applications for molecular simulation. In particular, over the last three years, the “Electronic Friction” theory, pioneered by the PI, has now been developed into a stable and accurate computational method that is sufficiently practical to allow first principles “on-the-fly” simulation of chemical reaction dynamics at metal surfaces.

  14. Carbon supported ultrafine gold phosphorus nanoparticles as highly efficient electrocatalyst for alkaline ethanol oxidation reaction

    International Nuclear Information System (INIS)

    Li, Tongfei; Fu, Gengtao; Su, Jiahui; Wang, Yi; Lv, Yinjie; Zou, Xiuyong; Zhu, Xiaoshu; Xu, Lin; Sun, Dongmei; Tang, Yawen

    2017-01-01

    Graphical abstract: We develop a new kind of carbon supported gold-phosphorus (Au-P/C) electrocatalyst by a facile and novel phosphorus reduction method, and demonstrate the Au-P/C is a highly active and stable electrocatalyst for the ethanol oxidation reaction. - Highlights: • Au-P/C catalyst is synthesized by a facile and novel white-phosphorus reduce method. • AuP particles with ultrafine particle-size are uniformly dispersed on carbon support. • Au-P/C catalyst exhibits much higher content of P 0 than reported metal/P catalysts. • Au-P/C catalysts show excellent catalytic properties for ethanol oxidation reaction. - Abstract: Herein, we develop a new kind of carbon supported gold-phosphorus (Au-P/C) electrocatalyst for the alkaline ethanol oxidation reaction (EOR). The Au-P/C catalysts with different Au/P ratio (i.e., AuP/C, Au 3 P 2 /C and Au 4 P 3 /C) can be obtained by a facile and novel hot-reflux method with white phosphorus (P 4 ) as reductant and ethanol as solvent. The crystal structure, composition and particle-size of the Au-P/C catalysts are investigated by X-ray diffraction (XRD), Energy Dispersive Spectrometer (EDS), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), etc. The results demonstrate that Au-P/C catalysts present an alloy phase with the high content of P, ultrafine particle-size and high dispersity on carbon support, which results in excellent electrocatalytic activity and stability towards the EOR compared with that of the free-phosphorus Au/C catalyst. In addition, among the various Au-P/C catalysts with different Au/P ratio, the AuP/C sample exhibits the best electrocatalytic performance in comparison with other Au 3 P 2 /C and Au 4 P 3 /C samples.

  15. Synthesis and characterization of cobalt-nichel oxides for the oxygen formation reaction

    International Nuclear Information System (INIS)

    Morales G, P.

    2001-01-01

    In this work the compounds of cobalt and nickel oxides and the mixtures of cobalt-nickel were prepared which were characterized and evaluated as electrocatalysts in the oxygen release reaction in alkaline media. The compounds were synthesised by the sol-gel method: heated at 400 and 500 Centigrade. The compounds characterization was realized by thermogravimetry, X-ray diffraction and Scanning electron microscopy. As the Co 3 O 4 and the Ni O as the mixtures Ni O/Co 3 O 4 were obtained as a porous material with a small particle size, characteristics which are presented by cause of the low temperature of synthesis. The electrocatalytic evaluation for the synthesised compounds for the oxygen release reaction was realized by cyclic volt amperometry in a 0.5M KOH solution. The oxides mixtures presented a well electrocatalytic activity to be used in the electrochemical release of oxygen. The current density and the electrochemically active area, in all the cases of mixtures is very higher to the Co 3 O 4 and Ni O ones. Observing with greater clearness the synergic effects, in the obtained mixture at 400 C. The oxides mixtures heated at 400 C were stables for the oxygen formation reaction. Therefore it is be able to say that the Ni O/Co 3 O 4 mixture counts on a great reactive area: electrocatalytic characteristic desirable to be a material used as anode in the electrolysis of water, which increases the oxygen release in the anode and so the hydrogen release in the cathode. (Author)

  16. Influence of Adsorbed Water on the Oxygen Evolution Reaction on Oxides

    DEFF Research Database (Denmark)

    Siahrostami, Samira; Vojvodic, Aleksandra

    2015-01-01

    We study the interface between adsorbed water and stoichiometric, defect-free (110) rutile oxide surfaces of TiO2, RuO2, and IrO2 in order to understand how water influences the stabilities of the intermediates of the oxygen evolution reaction (OER). In our model the water is treated as explicitly...... molecules binding to bridging oxygens. The third chain interacts weakly and predominantly with the H2O molecules of the second layer, resembling bulk water. We find that the stability of the water layer close to the oxide surface is almost the same as the one found on flat metal surfaces, such as the Pt(111...... of RuO2 and IrO2, while it is increased by similar to 0.4 eV for TiO2....

  17. Investigation of lipid oxidation and non-enzymatic browning reactions in marine PL emulsions

    DEFF Research Database (Denmark)

    Lu, Henna Fung Sieng; Nielsen, Nina Skall; Baron, Caroline P.

    Marine phospholipids (PL) have received much attention recently due to their numerous advantages. One of these advantages is their better resistance towards oxidation as compared to fish oil. In addition to the antioxidative properties of α-tocopherol and phospholipids, the better oxidative...... stability of marine PL might be attributed to antioxidative properties of pyrroles formed between oxidised lipids with amine groups from phosphatidylethanolamine (PE) or residues amino acids that are present in marine PL. The main objective of this study was to investigate if the presence of amine group...... of amino acids (leucine, methionine and lysine) from 2 authentic standards (PC and PE) and 2 purified marine PL (LC and MPL) through sonication method. Emulsions were incubated at 60 ºC for 0, 2, 4 and 6 days. Non-enzymatic browning reactions were investigated through measurement of i) Strecker aldehydes...

  18. Reaction of Antimony-Uranium Composite Oxide in the Chlorination Treatment of Waste Catalyst - 13521

    Energy Technology Data Exchange (ETDEWEB)

    Sawada, Kayo [EcoTopia Science Institute (Japan); Hirabayashi, Daisuke; Enokida, Youichi [Department of Materials, Physics and Energy Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Japan)

    2013-07-01

    The effect of oxygen gas concentration on the chlorination treatment of antimony-uranium composite oxide catalyst waste was investigated by adding different concentrations of oxygen at 0-6 vol% to its chlorination agent of 0.6 or 6 vol% hydrogen chloride gas at 1173 K. The addition of oxygen tended to prevent the chlorination of antimony in the oxide. When 6 vol% hydrogen chloride gas was used, the addition of oxygen up to 0.1 vol% could convert the uranium contained in the catalyst to U{sub 3}O{sub 8} without any significant decrease in the reaction rate compared to that of the treatment without oxygen. (authors)

  19. Improved reaction sintered silicon nitride. [protective coatings to improve oxidation resistance

    Science.gov (United States)

    Baumgartner, H. R.

    1978-01-01

    Processing treatments were applied to as-nitrided reaction sintered silicon nitride (RSSN) with the purposes of improving strength after processing to above 350 MN/m2 and improving strength after oxidation exposure. The experimental approaches are divided into three broad classifications: sintering of surface-applied powders; impregnation of solution followed by further thermal processing; and infiltration of molten silicon and subsequent carburization or nitridation of the silicon. The impregnation of RSSN with solutions of aluminum nitrate and zirconyl chloride, followed by heating at 1400-1500 C in a nitrogen atmosphere containing silicon monoxide, improved RSSN strength and oxidation resistance. The room temperature bend strength of RSSN was increased nearly fifty percent above the untreated strength with mean absolute strengths up to 420 MN/m2. Strengths of treated samples that were measured after a 12 hour oxidation exposure in air were up to 90 percent of the original as-nitrided strength, as compared to retained strengths in the range of 35 to 60 percent for untreated RSSN after the same oxidation exposure.

  20. Reduced-graphene-oxide supported tantalum-based electrocatalysts: Controlled nitrogen doping and oxygen reduction reaction

    Science.gov (United States)

    Yang, Xiaoyun; Mo, Qijie; Guo, Yulin; Chen, Nana; Gao, Qingsheng

    2018-03-01

    Controlled N-doping is feasible to engineer the surface stoichiometry and the electronic configuration of metal-oxide electrocatalysts toward efficient oxygen reduction reactions (ORR). Taking reduced graphene oxide supported tantalum-oxides (TaOx/RGO) for example, this work illustrated the controlled N-doping in both metal-oxides and carbon supports, and the contribution to the improved ORR activity. The active N-doped TaOx/RGO electrocatalysts were fabricated via SiO2-assisted pyrolysis, in which the amount and kind of N-doping were tailored toward efficient electrocatalysis. The optimal nanocomposites showed a quite positive half-wave potential (0.80 V vs. RHE), the excellent long-term stability, and the outstanding tolerance to methanol crossing. The improvement in ORR was reasonably attributed to the synergy between N-doped TaOx and N-doped RGO. Elucidating the importance of controlled N-doping for electrocatalysis, this work will open up new opportunities to explore noble-metal-free materials for renewable energy applications.

  1. Characterization of Titanium Oxide Nanoparticles Obtained by Hydrolysis Reaction of Ethylene Glycol Solution of Alkoxide

    Directory of Open Access Journals (Sweden)

    Naofumi Uekawa

    2012-01-01

    Full Text Available Transparent and stable sols of titanium oxide nanoparticles were obtained by heating a mixture of ethylene glycol solution of titanium tetraisopropoxide (TIP and a NH3 aqueous solution at 368 K for 24 h. The concentration of NH3 aqueous solution affected the structure of the obtained titanium oxide nanoparticles. For NH3 aqueous solution concentrations higher than 0.2 mol/L, a mixture of anatase TiO2 nanoparticles and layered titanic acid nanoparticles was obtained. The obtained sol was very stable without formation of aggregated precipitates and gels. Coordination of ethylene glycol to Ti4+ ions inhibited the rapid hydrolysis reaction and aggregation of the obtained nanoparticles. The obtained titanium oxide nanoparticles had a large specific surface area: larger than 350 m2/g. The obtained titanium oxide nanoparticles showed an enhanced adsorption towards the cationic dye molecules. The selective adsorption corresponded to presence of layered titanic acid on the obtained anatase TiO2 nanoparticles.

  2. The electrochemical transfer reactions and the structure of the iron|oxide layer|electrolyte interface

    International Nuclear Information System (INIS)

    Petrović, Željka; Metikoš-Huković, Mirjana; Babić, Ranko

    2012-01-01

    The thickness, barrier (protecting) and semiconducting properties of the potentiostatically formed oxide films on the pure iron electrode in an aqueous borate buffer solution were investigated by electrochemical quartz crystal nanobalance (EQCN), electrochemical impedance spectroscopy (EIS), and Mott–Schottky (MS) analysis. The thicknesses of the prepassive Fe(II)hydroxide layer (up to monolayer) nucleated on the bare iron surface and the passive Fe(II)/Fe(III) layer (up to 2 nm), deposited on the top of the first one, were determined using in situ gravimetry. Electronic properties of iron prepassive and passive films as well as ionic and electronic transfer reactions at the film|solution interface were discussed on the basis of a band structure model of the surface oxide film and the potential distribution at the interface. The anodic oxide film formation and cathodic decomposition are coupled processes and their reversible inter-conversion is mediated by the availability of free charge carriers on the electrode|solution interface. The structure of the reversible double layer at the iron oxide|solution interface was discussed based on the concept of the specific adsorption of the imidazolium cation on the negatively charged electrode surface at pH > pH pzc .

  3. Reaction products between Bi-Sr-Ca-Cu-oxide thick films and alumina substrates

    International Nuclear Information System (INIS)

    Alarco, J.A.; Ilushechkin, A.; Yamashita, T.; Bhargava, A.; Barry, J.; Mackinnon, I.D.R.

    1997-01-01

    The structure and composition of reaction products between Bi-Sr-Ca-Cu-oxide (BSCCO) thick films and alumina substrates have been characterized using a combination of electron diffraction, scanning electron microscopy and energy dispersive X-ray spectrometry (EDX). Sr and Ca are found to be the most reactive cations with alumina. Sr 4 Al 6 O 12 SO 4 is formed between the alumina substrates and BSCCO thick films prepared from paste with composition close to Bi-2212 (and Bi-2212+10 wt.% Ag). For paste with composition close to Bi(Pb)-2223 +20 wt.% Ag, a new phase with f.c.c. structure, lattice parameter about a=24.5 A and approximate composition Al 3 Sr 2 CaBi 2 CuO x has been identified in the interface region. Understanding and control of these reactions is essential for growth of high quality BSCCO thick films on alumina. (orig.)

  4. Convection and reaction in a diffusive boundary layer in a porous medium: nonlinear dynamics.

    Science.gov (United States)

    Andres, Jeanne Therese H; Cardoso, Silvana S S

    2012-09-01

    We study numerically the nonlinear interactions between chemical reaction and convective fingering in a diffusive boundary layer in a porous medium. The reaction enhances stability by consuming a solute that is unstably distributed in a gravitational field. We show that chemical reaction profoundly changes the dynamics of the system, by introducing a steady state, shortening the evolution time, and altering the spatial patterns of velocity and concentration of solute. In the presence of weak reaction, finger growth and merger occur effectively, driving strong convective currents in a thick layer of solute. However, as the reaction becomes stronger, finger growth is inhibited, tip-splitting is enhanced and the layer of solute becomes much thinner. Convection enhances the mass flux of solute consumed by reaction in the boundary layer but has a diminishing effect as reaction strength increases. This nonlinear behavior has striking differences to the density fingering of traveling reaction fronts, for which stronger chemical kinetics result in more effective finger merger owing to an increase in the speed of the front. In a boundary layer, a strong stabilizing effect of reaction can maintain a long-term state of convection in isolated fingers of wavelength comparable to that at onset of instability.

  5. Enhanced reversibility and durability of a solid oxide Fe-air redox battery by carbothermic reaction derived energy storage materials.

    Science.gov (United States)

    Zhao, Xuan; Li, Xue; Gong, Yunhui; Huang, Kevin

    2014-01-18

    The recently developed solid oxide metal-air redox battery is a new technology capable of high-rate chemistry. Here we report that the performance, reversibility and stability of a solid oxide iron-air redox battery can be significantly improved by nanostructuring energy storage materials from a carbothermic reaction.

  6. A study of the accelerated zircaloy-4 oxidation reaction with H2O/H2 mixture gas

    International Nuclear Information System (INIS)

    Kim, Y. S.; Cho, I. J.

    2001-01-01

    A study of the Zircaloy-4 reaction with H 2 O/H 2 mixture gas is carried out by using TGA (Thermo Gravimetric Apparatus) to estimate the hydrogen embrittlement which can possibly cause catastrophic nuclear fuel rod failure. Reaction rates are measured as a function of H 2 /H 2 O. In the experiments reaction temperature is set at 500 .deg. C and total pressure of the mixture gas is maintained at 1 atm. Experimental results reveal that hydriding and oxidation reaction are competing. In early stage, hydriding kinetics is faster than oxidation, however, oxidant in H 2 O forms oxide on the surface as steam environment is maintained, thus, this growing oxide begins to protect the zirconium base metal against hydrogen permeation. In this second stage, the total kinetic rate follows enhanced oxidation kinetics. In the final stage, it is observed that the oxide is broken down and massive hydriding takes place through the mechanical defects in the oxide, whose kinetics is similar to pure hydriding kinetics. These results are confirmed by SEM and EDX analysis along with hydrogen concentration measurements

  7. Selective oxidations in microstructured catalytic reactions - A review and an overview of own work on fuel processing for fuel cells

    NARCIS (Netherlands)

    Hessel, V.; Kolb, G.A.; Cominos, V.; Loewe, H.; Nikolaidis, G.; Zapf, R.; Ziogas, A.; Schouten, J.C.; Delsman, E.R.; Croon, de M.H.J.M.; Santamaria, J.; Iglesia, de la O.; Mallada, R.

    2006-01-01

    This review is concerned about catalytic gas-phase oxidation reactions in microreactors, typically being performed in wall-coated microchannels. Not included are liquid and gas-liquid oxidations which are typically done in reactor designs different from the ones considered here. The first part of

  8. A Practical Quantum Mechanics Molecular Mechanics Method for the Dynamical Study of Reactions in Biomolecules.

    Science.gov (United States)

    Mendieta-Moreno, Jesús I; Marcos-Alcalde, Iñigo; Trabada, Daniel G; Gómez-Puertas, Paulino; Ortega, José; Mendieta, Jesús

    2015-01-01

    Quantum mechanics/molecular mechanics (QM/MM) methods are excellent tools for the modeling of biomolecular reactions. Recently, we have implemented a new QM/MM method (Fireball/Amber), which combines an efficient density functional theory method (Fireball) and a well-recognized molecular dynamics package (Amber), offering an excellent balance between accuracy and sampling capabilities. Here, we present a detailed explanation of the Fireball method and Fireball/Amber implementation. We also discuss how this tool can be used to analyze reactions in biomolecules using steered molecular dynamics simulations. The potential of this approach is shown by the analysis of a reaction catalyzed by the enzyme triose-phosphate isomerase (TIM). The conformational space and energetic landscape for this reaction are analyzed without a priori assumptions about the protonation states of the different residues during the reaction. The results offer a detailed description of the reaction and reveal some new features of the catalytic mechanism. In particular, we find a new reaction mechanism that is characterized by the intramolecular proton transfer from O1 to O2 and the simultaneous proton transfer from Glu 165 to C2. Copyright © 2015 Elsevier Inc. All rights reserved.

  9. Dynamic Characteristics and Model for Centralization Reaction of Acidic Tailings From Heap Leaching of Uranium Ore

    International Nuclear Information System (INIS)

    Ding Dexin; Liu Yulong; Li Guangyue; Wang Youtuan

    2010-01-01

    Centralization tests were carried out on acidic tailings from heap leaching of uranium ore by using CaO, NaOH and NH 4 OH. The variations of pH with time were measured for the three centralization systems and the dynamic models for the systems were set up by regressing the measured data. The centralization process consists of the fast reaction phase representing the reaction between the centralization agent and the acid on the surface of the tailing's particles and the slow diffusion-reaction phase representing the diffusion-reaction between the centralization agent and the acid within the tailing's particles. The non-linear coupling and feedback function model for the diffusion-reaction of the centralization agent can reflect the process and mode of the centralization reaction. There is a non-linear oscillation in the variation of pH within the centralization systems. The dynamic model for the tailing's centralization reaction can fit the pH variation within the centralization systems. (authors)

  10. The direct oxidative diene cyclization and related reactions in natural product synthesis

    Directory of Open Access Journals (Sweden)

    Juliane Adrian

    2016-09-01

    Full Text Available The direct oxidative cyclization of 1,5-dienes is a valuable synthetic method for the (diastereoselective preparation of substituted tetrahydrofurans. Closely related reactions start from 5,6-dihydroxy or 5-hydroxyalkenes to generate similar products in a mechanistically analogous manner. After a brief overview on the history of this group of transformations and a survey on mechanistic and stereochemical aspects, this review article provides a summary on applications in natural product synthesis. Moreover, current limitations and future directions in this area of chemistry are discussed.

  11. Dynamic global model of oxide Czochralski process with weighing control

    Science.gov (United States)

    Mamedov, V. M.; Vasiliev, M. G.; Yuferev, V. S.

    2011-03-01

    A dynamic model of oxide Czochralski growth with weighing control has been developed for the first time. A time-dependent approach is used for the calculation of temperature fields in different parts of a crystallization set-up and convection patterns in a melt, while internal radiation in crystal is considered in a quasi-steady approximation. A special algorithm is developed for the calculation of displacement of a triple point and simulation of a crystal surface formation. To calculate variations in the heat generation, a model of weighing control with a commonly used PID regulator is applied. As an example, simulation of the growth process of gallium-gadolinium garnet (GGG) crystals starting from the stage of seeding is performed.

  12. Reaction pathway and oxidation mechanisms of dibutyl phthalate by persulfate activated with zero-valent iron

    Energy Technology Data Exchange (ETDEWEB)

    Li, Huanxuan [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); Wan, Jinquan, E-mail: ppjqwan@scut.edu.cn [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); State Key Lab Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640 (China); Ma, Yongwen [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); State Key Lab Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640 (China); Wang, Yan [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China)

    2016-08-15

    This study investigated reaction pathway and oxidation mechanisms of dibutyl phthalate (DBP) by persulfate (PS) activated with zero-valent iron (ZVI). The DBP degradation was studied at three pH values (acidic, neutral and basic) in the presence of different organic scavengers. Using a chemical probe method, both sulfate radical (SO{sub 4}·{sup −}) and hydroxyl radical (·OH) were found to be primary oxidants at pH 3.0 and pH 7.0, respectively while ·OH was the major specie to oxidize DBP at pH 11.0. A similar result was found in an experiment of Electron Spin Resonance spin-trapping where in addition to ·OH, superoxide radical (O{sub 2}·{sup −}) was detected at pH 11.0. The transformation of degradation products including dimethyl phthalate (DMP), diethyl phthalate (DEP), phthalic anhydride, and acetophenone exhibited diverse variation during the reaction processes. The phthalic anhydride concentration appeared to be maximum at all pHs. Another eleven intermediate products were also found at pH 3.0 by GC–MS and HPLC analysis, and their degradation mechanisms and pathways were proposed. It was suggested that dealkylation, hydroxylation, decarboxylation and hydrogen extraction were the dominant degradation mechanisms of DBP at pH 3.0. - Highlights: • Both SO{sub 4}{sup −}· and ·OH were found to be the major active species at pH 3.0 and pH 7.0. • ·OH and ·O2– were the primary oxidants pH 11.0. • The intermediate products were investigated as well as the degradation pathway. • Dealkylation, hydroxylation, decarboxylation, H-extraction were the major mechanisms.

  13. Proceedings of the Workshop on open problems in heavy ion reaction dynamics at VIVITRON energies

    International Nuclear Information System (INIS)

    Beck, F.A.

    1993-01-01

    Some problems of heavy ion reaction dynamics at the VIVITRON tandem accelerator and the experimental facilities are discussed at the meeting. Topics include light dinuclear systems, collision dynamics at low energies, fission evaporation and fusion of heavy nuclei and others. Most documents consist of transparencies presented at the workshop, texts of papers are missing. All items are indexed and abstracted for the INIS database. (K.A.)

  14. Proceedings of the Workshop on open problems in heavy ion reaction dynamics at VIVITRON energies

    Energy Technology Data Exchange (ETDEWEB)

    Beck, F. A.

    1993-07-01

    Some problems of heavy ion reaction dynamics at the VIVITRON tandem accelerator and the experimental facilities are discussed at the meeting. Topics include light dinuclear systems, collision dynamics at low energies, fission evaporation and fusion of heavy nuclei and others. Most documents consist of transparencies presented at the workshop, texts of papers are missing. All items are indexed and abstracted for the INIS database. (K.A.).

  15. Kinetics of transuranium element oxidation-reduction reactions in solution; Cinetique des reactions d'oxydo-reduction des elements transuraniens en solution

    Energy Technology Data Exchange (ETDEWEB)

    Gourisse, D. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1966-09-01

    A review of the kinetics of U, Np, Pu, Am oxidation-reduction reactions is proposed. The relations between the different activation thermodynamic functions (compensatory effect, formal entropy of the activated complex, magnitude of reactions velocities) are considered. The effects of acidity, ionic strength deuterium and mixed solvents polarity on reactions rates are described. The effect of different anions on reactions rates are explained by variations of the reaction standard free energy and variations of the activation free energy (coulombic interactions) resulting from the complexation of dissolved species by these anions. (author) [French] Une revue systematique de la cinetique des reactions d'oxydo-reduction des elements U, Np, Pu, Am, en solution perchlorique est proposee. Des considerations relatives aux grandeurs thermodynamiques d'activation associees aux actes elementaires (effet de compensation, entropie standard des complexes actives, rapidite des reactions) sont developpees. L'influence de l'acidite, de la force ionique, de l'eau lourde et de la polarite des solvants mixtes sur la vitesse des reactions est decrite. Enfin l'influence des differents anions sur la vitesse des reactions est expliquee par les variations de l'enthalpie libre standard de la reaction et de l'enthalpie libre d'activation (travail des forces electrostatiques) resultant de la complexation des especes dissoutes dans la solution. (auteur)

  16. Kinetics of transuranium element oxidation-reduction reactions in solution; Cinetique des reactions d'oxydo-reduction des elements transuraniens en solution

    Energy Technology Data Exchange (ETDEWEB)

    Gourisse, D [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1966-09-01

    A review of the kinetics of U, Np, Pu, Am oxidation-reduction reactions is proposed. The relations between the different activation thermodynamic functions (compensatory effect, formal entropy of the activated complex, magnitude of reactions velocities) are considered. The effects of acidity, ionic strength deuterium and mixed solvents polarity on reactions rates are described. The effect of different anions on reactions rates are explained by variations of the reaction standard free energy and variations of the activation free energy (coulombic interactions) resulting from the complexation of dissolved species by these anions. (author) [French] Une revue systematique de la cinetique des reactions d'oxydo-reduction des elements U, Np, Pu, Am, en solution perchlorique est proposee. Des considerations relatives aux grandeurs thermodynamiques d'activation associees aux actes elementaires (effet de compensation, entropie standard des complexes actives, rapidite des reactions) sont developpees. L'influence de l'acidite, de la force ionique, de l'eau lourde et de la polarite des solvants mixtes sur la vitesse des reactions est decrite. Enfin l'influence des differents anions sur la vitesse des reactions est expliquee par les variations de l'enthalpie libre standard de la reaction et de l'enthalpie libre d'activation (travail des forces electrostatiques) resultant de la complexation des especes dissoutes dans la solution. (auteur)

  17. Reaction intermediates in the catalytic Gif-type oxidation from nuclear inelastic scattering

    Energy Technology Data Exchange (ETDEWEB)

    Rajagopalan, S., E-mail: rajagopalan78@hotmail.com [Indira Gandhi Centre for Atomic Research, Materials Science Group (India); Asthalter, T., E-mail: t.asthalter@web.de [Universität Stuttgart, Institute of Physical Chemistry (Germany); Rabe, V.; Laschat, S. [Universität Stuttgart, Institute of Organic Chemistry (Germany)

    2016-12-15

    Nuclear inelastic scattering (NIS) of synchrotron radiation, also known as nuclear resonant vibrational spectroscopy (NRVS), has been shown to provide valuable insights into metal-centered vibrations at Mössbauer-active nuclei. We present a study of the iron-centered vibrational density of states (VDOS) during the first step of the Gif-type oxidation of cyclohexene with a novel trinuclear Fe{sub 3}(μ{sub 3}-O) complex as catalyst precursor. The experiments were carried out on shock-frozen solutions for different combinations of reactants: Fe{sub 3}(μ{sub 3}-O) in pyridine solution, Fe{sub 3}(μ{sub 3}-O) plus Zn/acetic acid in pyridine without and with addition of either oxygen or cyclohexene, and Fe{sub 3}(μ{sub 3}-O)/Zn/acetic acid/pyridine/cyclohexene (reaction mixture) for reaction times of 1 min, 5 min, and 30 min. The projected VDOS of the Fe atoms was calculated on the basis of pseudopotential density functional calculations. Two possible reaction intermediates were identified as [Fe{sup (III)}(C{sub 5}H{sub 5}N){sub 2}(O{sub 2}CCH{sub 3}){sub 2}]{sup +} and Fe{sup (II)}(C{sub 5}H{sub 5}N){sub 4}(O{sub 2}CCH{sub 3}){sub 2}, yielding evidence that NIS (NRVS) allows to identify the presence of iron-centered intermediates also in complex reaction mixtures.

  18. Oxidative degradation of triclosan by potassium permanganate: Kinetics, degradation products, reaction mechanism, and toxicity evaluation.

    Science.gov (United States)

    Chen, Jing; Qu, Ruijuan; Pan, Xiaoxue; Wang, Zunyao

    2016-10-15

    In this study, we systematically investigated the potential applicability of potassium permanganate for removal of triclosan (TCS) in water treatment. A series of kinetic experiments were carried out to study the influence of various factors, including the pH, oxidant doses, temperature, and presence of typical anions (Cl(-), SO4(2-), NO3(-)), humic acid (HA), and fulvic acid (FA) on triclosan removal. The optimal reaction conditions were: pH = 8.0, [TCS]0:[KMnO4]0 = 1:2.5, and T = 25 °C, where 20 mg/L of TCS could be completely degraded in 120 s. However, the rate of TCS (20 μg/L) oxidation by KMnO4 ([TCS]0:[KMnO4]0 = 1:2.5) was 1.64 × 10(-3) mg L(-1)·h(-1), lower than that at an initial concentration of 20 mg/L (2.24 × 10(3) mg L(-1)·h(-1)). A total of eleven products were detected by liquid chromatography-quadrupole-time-of-flight-mass spectrometry (LC-Q-TOF-MS) analysis, including phenol and its derivatives, benzoquinone, an organic acid, and aldehyde. Two main reaction pathways involving CO bond cleavage (-C(8)O(7)-) and benzene ring opening (in the less chlorinated benzene ring) were proposed, and were further confirmed based on frontier electron density calculations and point charges. Furthermore, the changes in the toxicity of the reaction solution during TCS oxidation by KMnO4 were evaluated by using both the luminescent bacteria Photobacterium phosphoreum and the water flea Daphnia magna. The toxicity of 20 mg/L triclosan to D. magna and P. phosphoreum after 60 min was reduced by 95.2% and 43.0%, respectively. Phenol and 1,4-benzoquinone, the two representative degradation products formed during permanganate oxidation, would yield low concentrations of DBPs (STHMFP, 20.99-278.97 μg/mg; SHAAFP, 7.86 × 10(-4)-45.77 μg/mg) after chlorination and chloramination. Overall, KMnO4 can be used as an effective oxidizing agent for TCS removal in water and wastewater treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Rapid Removal of Tetrabromobisphenol A by Ozonation in Water: Oxidation Products, Reaction Pathways and Toxicity Assessment.

    Directory of Open Access Journals (Sweden)

    Ruijuan Qu

    Full Text Available Tetrabromobisphenol A (TBBPA is one of the most widely used brominated flame retardants and has attracted more and more attention. In this work, the parent TBBPA with an initial concentration of 100 mg/L was completely removed after 6 min of ozonation at pH 8.0, and alkaline conditions favored a more rapid removal than acidic and neutral conditions. The presence of typical anions and humic acid did not significantly affect the degradation of TBBPA. The quenching test using isopropanol indicated that direct ozone oxidation played a dominant role during this process. Seventeen reaction intermediates and products were identified using an electrospray time-of-flight mass spectrometer. Notably, the generation of 2,4,6-tribromophenol was first observed in the degradation process of TBBPA. The evolution of reaction products showed that ozonation is an efficient treatment for removal of both TBBPA and intermediates. Sequential transformation of organic bromine to bromide and bromate was confirmed by ion chromatography analysis. Two primary reaction pathways that involve cleavage of central carbon atom and benzene ring cleavage concomitant with debromination were thus proposed and further justified by calculations of frontier electron densities. Furthermore, the total organic carbon data suggested a low mineralization rate, even after the complete removal of TBBPA. Meanwhile, the acute aqueous toxicity of reaction solutions to Photobacterium Phosphoreum and Daphnia magna was rapidly decreased during ozonation. In addition, no obvious difference in the attenuation of TBBPA was found by ozone oxidation using different water matrices, and the effectiveness in natural waters further demonstrates that ozonation can be adopted as a promising technique to treat TBBPA-contaminated waters.

  20. Rapid Removal of Tetrabromobisphenol A by Ozonation in Water: Oxidation Products, Reaction Pathways and Toxicity Assessment

    Science.gov (United States)

    Wang, Xinghao; Huang, Qingguo; Lu, Junhe; Wang, Liansheng; Wang, Zunyao

    2015-01-01

    Tetrabromobisphenol A (TBBPA) is one of the most widely used brominated flame retardants and has attracted more and more attention. In this work, the parent TBBPA with an initial concentration of 100 mg/L was completely removed after 6 min of ozonation at pH 8.0, and alkaline conditions favored a more rapid removal than acidic and neutral conditions. The presence of typical anions and humic acid did not significantly affect the degradation of TBBPA. The quenching test using isopropanol indicated that direct ozone oxidation played a dominant role during this process. Seventeen reaction intermediates and products were identified using an electrospray time-of-flight mass spectrometer. Notably, the generation of 2,4,6-tribromophenol was first observed in the degradation process of TBBPA. The evolution of reaction products showed that ozonation is an efficient treatment for removal of both TBBPA and intermediates. Sequential transformation of organic bromine to bromide and bromate was confirmed by ion chromatography analysis. Two primary reaction pathways that involve cleavage of central carbon atom and benzene ring cleavage concomitant with debromination were thus proposed and further justified by calculations of frontier electron densities. Furthermore, the total organic carbon data suggested a low mineralization rate, even after the complete removal of TBBPA. Meanwhile, the acute aqueous toxicity of reaction solutions to Photobacterium Phosphoreum and Daphnia magna was rapidly decreased during ozonation. In addition, no obvious difference in the attenuation of TBBPA was found by ozone oxidation using different water matrices, and the effectiveness in natural waters further demonstrates that ozonation can be adopted as a promising technique to treat TBBPA-contaminated waters. PMID:26430733

  1. No evidence found for Diels-Alder reaction products in soybean oil oxidized at the frying temperature by NMR study

    Science.gov (United States)

    It has been generally accepted that the Diels-Alder reaction mechanism is one of the major reaction mechanisms to produce dimers and polymers during heating process of vegetable oil. Soybean oil oxidized at 180 °C for 24 hrs with 1.45 surface area-to-volume ratio showed 36.1% polymer peak area in g...

  2. pH-Controlled Oxidation of an Aromatic Ketone: Structural Elucidation of the Products of Two Green Chemical Reactions

    Science.gov (United States)

    Ballard, C. Eric

    2010-01-01

    A laboratory experiment emphasizing the structural elucidation of organic compounds has been developed as a discovery exercise. The "unknown" compounds are the products of the pH-controlled oxidation of 4'-methoxyacetophenone with bleach. The chemoselectivity of this reaction is highly dependent on the pH of the reaction media: under basic…

  3. Oxidation and metal-insertion in molybdenite surfaces: evaluation of charge-transfer mechanisms and dynamics

    Directory of Open Access Journals (Sweden)

    Shutthanandan V

    2008-06-01

    Full Text Available Abstract Molybdenum disulfide (MoS2, a layered transition-metal dichalcogenide, has been of special importance to the research community of geochemistry, materials and environmental chemistry, and geotechnical engineering. Understanding the oxidation behavior and charge-transfer mechanisms in MoS2 is important to gain better insight into the degradation of this mineral in the environment. In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications. Furthermore, a detailed investigation of thermal oxidation behavior and metal-insertion will provide a basis to further explore and model the mechanism of adsorption of metal ions onto geomedia. The present work was performed to understand thermal oxidation and metal-insertion processes of molybdenite surfaces. The analysis was performed using atomic force microscopy (AFM, scanning electron microscopy (SEM, transmission electron microscopy (TEM, Rutherford backscattering spectrometry (RBS, and nuclear reaction analysis (NRA. Structural studies using SEM and TEM indicate the local-disordering of the structure as a result of charge-transfer process between the inserted lithium and the molybdenite layer. Selected area electron diffraction measurements indicate the large variations in the diffusivity of lithium confirming that the charge-transfer is different along and perpendicular to the layers in molybdenite. Thermal heating of molybenite surface in air at 400°C induces surface oxidation, which is slow during the first hour of heating and then increases significantly. The SEM results indicate that the crystals formed on the molybdenite surface as a result of thermal oxidation exhibit regular thin-elongated shape. The average size and density of the crystals on the surface is dependent on the time of annealing; smaller size and high density during the first one-hour and

  4. Oxidation and metal-insertion in molybdenite surfaces: evaluation of charge-transfer mechanisms and dynamics.

    Science.gov (United States)

    Ramana, C V; Becker, U; Shutthanandan, V; Julien, C M

    2008-06-05

    Molybdenum disulfide (MoS2), a layered transition-metal dichalcogenide, has been of special importance to the research community of geochemistry, materials and environmental chemistry, and geotechnical engineering. Understanding the oxidation behavior and charge-transfer mechanisms in MoS2 is important to gain better insight into the degradation of this mineral in the environment. In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications. Furthermore, a detailed investigation of thermal oxidation behavior and metal-insertion will provide a basis to further explore and model the mechanism of adsorption of metal ions onto geomedia.The present work was performed to understand thermal oxidation and metal-insertion processes of molybdenite surfaces. The analysis was performed using atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Rutherford backscattering spectrometry (RBS), and nuclear reaction analysis (NRA).Structural studies using SEM and TEM indicate the local-disordering of the structure as a result of charge-transfer process between the inserted lithium and the molybdenite layer. Selected area electron diffraction measurements indicate the large variations in the diffusivity of lithium confirming that the charge-transfer is different along and perpendicular to the layers in molybdenite. Thermal heating of molybenite surface in air at 400 degrees C induces surface oxidation, which is slow during the first hour of heating and then increases significantly. The SEM results indicate that the crystals formed on the molybdenite surface as a result of thermal oxidation exhibit regular thin-elongated shape. The average size and density of the crystals on the surface is dependent on the time of annealing; smaller size and high density during the first one-hour and significant

  5. Redox reaction between graphene oxide and In powder to prepare In2O3/reduced graphene oxide hybrids for supercapacitors

    Science.gov (United States)

    Xu, Xiaoyang; Wu, Tao; Xia, Fengling; Li, Yi; Zhang, Congcong; Zhang, Lei; Chen, Mingxi; Li, Xichuan; Zhang, Li; Liu, Yu; Gao, Jianping

    2014-11-01

    A facile and quick route for the chemical reduction of graphene oxide (GO) using In powder as a reductant has been established. The reduction of GO by In powder is traced by UV-visible absorption spectroscopy, and the obtained reduced graphene oxide (rGO) is analyzed. The In3+ ions produced during the reaction between the GO and the In powder are chemically transformed to In2O3 and then form In2O3/rGO hybrids. The In2O3/rGO hybrids are used as electrode materials and their electrochemical performance are studied using cyclic voltammetry and galvanostatic charge/discharge. The In2O3/rGO hybrids demonstrate excellent electrochemical performance and their highest specific capacitance is 178.8 F g-1 which is much higher than that of either In2O3 or rGO. In addition, the In2O3/rGO hybrids are also very stable.

  6. Growth dynamics and composition of tubular structures in a reaction-precipitation system

    Science.gov (United States)

    Pagano, Jason John

    Self-organization in reaction precipitation systems occurs in many physical, chemical, biological, and geological systems. In particular, chemical reactions provide a wealth of examples for this intriguing process. Permanent tubular structures arise from the interplay of chemical and transport phenomena such as diffusion and fluid flow. These astonishing tubular structures are prevalent throughout nature. Examples include black smokers at hydrothermal vents, silica tubes in setting cement, soda-straw stalactites in caves, and biological structures such as the outer skeleton of certain algae. In this work, the aim is to establish and understand a laboratory scale model by examining the, seemingly simple, precipitation reaction between sodium silicate and copper sulfate as well as zinc sulfate. The tubular precipitation structures in so-called silica gardens are known to many scientists and non-scientists alike. However, little is known regarding their growth dynamics and chemical composition. We devised an injection technique which provides control over parameters that are not accessible in the classic silica garden system. For the example of cupric sulfate injection into waterglass solution, we identify three distinct growth regimes (jetting, popping, and budding) and study their concentration dependent transitions. Here we describe the composition and morphology of the tube material using techniques such as electron microscopy and vibrational spectroscopy. Specifically, we find that the tube wall consists of metal hydroxide that is stabilized by a thin, exterior silica layer. After synthesis the tubes can be further modified by using chemical and/or physical means. A second study aims to understand tubule formation under "reverse" conditions. More specifically, waterglass is being injected into lighter cupric sulfate solution. In these experiments, single, downward growing precipitation tubes are created. Four distinct growth regimes are observed and their

  7. Chemical Characterization and Reactivity Testing of Fuel-Oxidizer Reaction Product (Test Report)

    Science.gov (United States)

    1996-01-01

    The product of incomplete reaction of monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) propellants, or fuel-oxidizer reaction product (FORP), has been hypothesized as a contributory cause of an anomaly which occurred in the chamber pressure (PC) transducer tube on the Reaction Control Subsystem (RCS) aft thruster 467 on flight STS-51. A small hole was found in the titanium-alloy PC tube at the first bend below the pressure transducer. It was surmised that the hole may have been caused by heat and pressure resulting from ignition of FORP. The NASA Johnson Space Center (JSC) White Sands Test Facility (WSTF) was requested to define the chemical characteristics of FORP, characterize its reactivity, and simulate the events in a controlled environment which may have lead to the Pc-tube failure. Samples of FORP were obtained from the gas-phase reaction of MMH with NTO under laboratory conditions, the pulsed firings of RCS thrusters with modified PC tubes using varied oxidizer or fuel lead times, and the nominal RCS thruster firings at WSTF and Kaiser-Marquardt. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), ion chromatography (IC), inductively coupled plasma (ICP) spectrometry, thermogravimetric analysis (TGA) coupled to FTIR (TGA/FTIR), and mechanical impact testing were used to qualitatively and quantitatively characterize the chemical, thermal, and ignition properties of FORP. These studies showed that the composition of FORP is variable but falls within a limited range of compositions that depends on the fuel loxidizer ratio at the time of formation, composition of the post-formation atmosphere (reducing or oxidizing), and reaction or postreaction temperature. A typical composition contains methylhydrazinium nitrate (MMHN), ammonium nitrate (AN), methylammonium nitrate (MAN), and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. The thermal decomposition

  8. Kinetics modeling and reaction mechanism of ferrate(VI) oxidation of benzotriazoles.

    Science.gov (United States)

    Yang, Bin; Ying, Guang-Guo; Zhang, Li-Juan; Zhou, Li-Jun; Liu, Shan; Fang, Yi-Xiang

    2011-03-01

    Benzotriazoles (BTs) are high production volume chemicals with broad application in various industrial processes and in households, and have been found to be omnipresent in aquatic environments. We investigated oxidation of five benzotriazoles (BT: 1H-benzotriazole; 5MBT: 5-methyl-1H-benzotriazole; DMBT: 5,6-dimethyl-1H-benzotriazole hydrate; 5CBT: 5-chloro-1H-benzotriazole; HBT: 1-hydroxybenzotriazole) by aqueous ferrate (Fe(VI)) to determine reaction kinetics as a function of pH (6.0-10.0), and interpreted the reaction mechanism of Fe(VI) with BTs by using a linear free-energy relationship. The pK(a) values of BT and DMBT were also determined using UV-Visible spectroscopic method in order to calculate the species-specific rate constants, and they were 8.37 ± 0.0 and 8.98 ± 0.08 respectively. Each of BTs reacted moderately with Fe(VI) with the k(app) ranged from 7.2 to 103.8 M(-1)s(-1) at pH 7.0 and 24 ± 1 °C. When the molar ratio of Fe(VI) and BTs increased up to 30:1, the removal rate of BTs reached about >95% in buffered milli-Q water or secondary wastewater effluent. The electrophilic oxidation mechanism of the above reaction was illustrated by using a linear free-energy relationship between pH-dependence of species-specific rate constants and substituent effects (σ(p)). Fe(VI) reacts initially with BTs by electrophilic attack at the 1,2,3-triazole moiety of BT, 5MBT, DMBT and 5CBT, and at the N-OH bond of HBT. Moreover, for BT, 5MBT, DMBT and 5CBT, the reactions with the species HFeO(4)(-) predominantly controled the reaction rates. For HBT, the species H(2)FeO(4) with dissociated HBT played a major role in the reaction. The results showed that Fe(VI) has the ability to degrade benzotriazoles in water. Copyright © 2011 Elsevier Ltd. All rights reserved.

  9. The Influence of FeO on the Reaction between Fe–Al–Ca Alloy and Al2O3–CaO–FeO Oxide during Heat Treatment at 1473 K

    Directory of Open Access Journals (Sweden)

    Chengsong Liu

    2017-04-01

    Full Text Available Oxygen diffusion from oxides to an alloy during heat treatment could influence the properties of the alloy and oxides. To clarify the influence of FeO on the solid-state reactions between Al2O3–CaO–FeO oxide and Fe–Al–Ca alloy during heat treatment at 1473 K, three diffusion couples with different FeO concentrations in the oxide were produced. The diffusion couples were subjected to several procedures successively including an oxide pre-melting experiment using a confocal scanning laser microscope to obtain good contact between the alloy and oxide, vacuum sealing to protect the specimens from oxidation, heat treatment, and electron probe X-ray microanalysis. The effects of the FeO content in the oxide on the morphology of the interface between the alloy and oxide, change of elements in the alloy, widths of the particle precipitation zone (PPZ and aluminum-depleted zone (ADZ, and size distribution of the particles in the alloy, were investigated and discussed. Based on the Wagner equation of internal oxidation of metals, a modified dynamic model to calculate the PPZ width was established to help understand the mechanism of the solid-state reactions and element diffusion between the Fe–Al–Ca alloy and Al2O3–CaO–FeO oxide with different FeO concentrations.

  10. REACTION PRODUCTS AND CORROSION OF MOLYBDENUM ELECTRODE IN GLASS MELT CONTAINING ANTIMONY OXIDES AND SODIUM SULFATE

    Directory of Open Access Journals (Sweden)

    JIŘÍ MATĚJ

    2012-09-01

    Full Text Available The products on the interface of a molybdenum electrode and glass melt were investigated primarily at 1400°C in three model glass melts without ingredients, with 1 % Sb2O3 and with 1 % Sb2O3 and 0.5 % SO3 (wt. %, both under and without load by alternating current. Corrosion of the molybdenum electrode in glass melt without AC load is higher by one order of magnitude if antimony oxides are present. The corrosion continues to increase if sulfate is present in addition to antimony oxides. Isolated antimony droplets largely occur on the electrode-glass melt interface, and numerous droplets are also dissipated in the surrounding glass if only antimony oxides are present in the glass melt. A comparatively continuous layer of antimony occurs on the interface if SO3 is also present, antimony being always in contact with molybdenum sulfide. Almost no antimony droplets are dissipated in the glass melt. The total amount of precipitated antimony also increases. The presence of sulfide on the interface likely facilitates antimony precipitation. The reaction of molybdenum with antimony oxides is inhibited in sites covered by an antimony layer. The composition of sulfide layers formed at 1400°C approximates that of Mo2S3. At 1100°C, the sulfide composition approximates that of MoS4. Corrosion multiplies in the glass melt without additions through the effect of AC current, most molybdenum being separated in the form of metallic particles. Corrosion also increases in the glass melt containing antimony oxides. This is due to increased corrosion in the neighborhood of the separated antimony droplets. This mechanism also results in the loosening of molybdenum particles. The amount of precipitated antimony also increases through the effect of the AC current. AC exerts no appreciable effect on either corrosion, the character of the electrode-glass interface, or antimony precipitation in the glass melt containing SO3.

  11. Electrocatalytic Activity of Carbonized Nanostructured Polyanilines for Oxidation Reactions: Sensing of Nitrite Ions and Ascorbic Acid

    International Nuclear Information System (INIS)

    Micić, Darko; Šljukić, Biljana; Zujovic, Zoran; Travas-Sejdic, Jadranka; Ćirić-Marjanović, Gordana

    2014-01-01

    Highlights: • Carbonized PANIs prepared from various nanostructured PANI precursors • Electroanalytical performances of carbonized PANIs evaluated using voltammetry • Study of carbonized PANIs physico-chemical properties related to electroactivity • The lowest over-potential for NO 2 − oxidation at c-PANI (+0.87 V vs. SCE) • The lowest over-potential for ascorbic acid oxidation at both c-PANI and c-PANI-SSA - Abstract: A comparative study of the electrocatalytic activity of nitrogen-containing carbon nanomaterials, prepared by the carbonization of nanostructured polyaniline (PANI) salts, for the electrooxidation reactions is presented. Nanostructured PANI salts were synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in an aqueous solution in the presence of 5-sulfosalicylic acid (PANI-SSA), 3,5-dinitrosalicylic acid (PANI-DNSA) as well as without added acid (PANI), and subsequently carbonized to c-PANI-SSA, c-PANI-DNSA and c-PANI, respectively. Glassy carbon tip was modified with nanostructured c-PANIs and used for the investigation of sensing of nitrite and ascorbic acid in aqueous solutions as model analytes by linear sweep voltammetry. All three types of the investigated c-PANIs gave excellent response to the nitrite ions and ascorbic acid electrooxidation. The lowest peak potential for nitrite ion oxidation exhibited c-PANI (+0.87 V vs. SCE), and for ascorbic acid oxidation both c-PANI and c-PANI-SSA (ca. + 0.13 V vs. SCE). Electrochemical data were correlated with structural and textural data obtained by Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, elemental and nitrogen sorption analysis

  12. Soft tissue deformation modelling through neural dynamics-based reaction-diffusion mechanics.

    Science.gov (United States)

    Zhang, Jinao; Zhong, Yongmin; Gu, Chengfan

    2018-05-30

    Soft tissue deformation modelling forms the basis of development of surgical simulation, surgical planning and robotic-assisted minimally invasive surgery. This paper presents a new methodology for modelling of soft tissue deformation based on reaction-diffusion mechanics via neural dynamics. The potential energy stored in soft tissues due to a mechanical load to deform tissues away from their rest state is treated as the equivalent transmembrane potential energy, and it is distributed in the tissue masses in the manner of reaction-diffusion propagation of nonlinear electrical waves. The reaction-diffusion propagation of mechanical potential energy and nonrigid mechanics of motion are combined to model soft tissue deformation and its dynamics, both of which are further formulated as the dynamics of cellular neural networks to achieve real-time computational performance. The proposed methodology is implemented with a haptic device for interactive soft tissue deformation with force feedback. Experimental results demonstrate that the proposed methodology exhibits nonlinear force-displacement relationship for nonlinear soft tissue deformation. Homogeneous, anisotropic and heterogeneous soft tissue material properties can be modelled through the inherent physical properties of mass points. Graphical abstract Soft tissue deformation modelling with haptic feedback via neural dynamics-based reaction-diffusion mechanics.

  13. The Crossed-Beam Scattering Method in Studies of Ion-Molecule Reaction Dynamics

    Czech Academy of Sciences Publication Activity Database

    Herman, Zdeněk

    2001-01-01

    Roč. 212, - (2001), s. 413-443 ISSN 1387-3806 R&D Projects: GA ČR GA203/00/0632 Institutional research plan: CEZ:AV0Z4040901 Keywords : ion-molecule reaction dynamics * ion scattering * experimental methods Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.176, year: 2001

  14. Dynamics of chemical reactions of multiply-charged cations: Information from beam scattering experiments

    Czech Academy of Sciences Publication Activity Database

    Herman, Zdeněk

    2015-01-01

    Roč. 378, FEB 2015 (2015), s. 113-126 ISSN 1387-3806 Institutional support: RVO:61388955 Keywords : Multiply-charged ions * Dynamics of chemical reactions * Beam scattering Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.183, year: 2015

  15. Optically Controlled Electron-Transfer Reaction Kinetics and Solvation Dynamics : Effect of Franck-Condon States

    NARCIS (Netherlands)

    Gupta, Kriti; Patra, Aniket; Dhole, Kajal; Samanta, Alok Kumar; Ghosh, Swapan K.

    2017-01-01

    Experimental results for optically controlled electron-transfer reaction kinetics (ETRK) and nonequilibrium solvation dynamics (NESD) of Coumarin 480 in DMPC vesicle show their dependence on excitation wavelength λex. However, the celebrated Marcus theory and linear-response-theory-based approaches

  16. Dynamical Behaviors of Stochastic Reaction-Diffusion Cohen-Grossberg Neural Networks with Delays

    Directory of Open Access Journals (Sweden)

    Li Wan

    2012-01-01

    Full Text Available This paper investigates dynamical behaviors of stochastic Cohen-Grossberg neural network with delays and reaction diffusion. By employing Lyapunov method, Poincaré inequality and matrix technique, some sufficient criteria on ultimate boundedness, weak attractor, and asymptotic stability are obtained. Finally, a numerical example is given to illustrate the correctness and effectiveness of our theoretical results.

  17. National array of neutron detectors (NAND) a versatile setup for studies on reaction dynamics

    International Nuclear Information System (INIS)

    Golda, K.S.; Singh, R.P.; Zacharias, J.; Archunan, M.; Kothari, A.; Barua, P.; Gupta, Arti; Venkataramanan, S.; Suman, S.K.; Kumar, Rajesh; Kumar, Pankaj; Jhingan, A.; Sugathan, P.; Datta, S.K.; Chatterjee, Mihir; Bhowmik, R.K.; Singh, Hardev; Behera, B.; Kumar, A.; Singh, G.; Ranjit; Mandal, S.

    2006-01-01

    National Array of Neutron Detectors (NAND) is a large array of neutron detectors being setup at Inter University Accelerator Centre. The primary motive behind the development of this array, is the study of reaction dynamics in the energy domain near the Coulomb barrier

  18. Molecular dynamics simulation of the first electron transfer step in the oxygen reduction reaction

    NARCIS (Netherlands)

    Hartnig, C.B.; Koper, M.T.M.

    2002-01-01

    We present a molecular dynamics simulation of solvent reorganization in the first electron transfer step in the oxygen reduction reaction, i.e. O2+e-¿O2-, modeled as taking place in the outer Helmholtz plane. The first electron transfer step is usually considered the rate-determining step from many

  19. Quantum state-resolved gas/surface reaction dynamics probed by reflection absorption infrared spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Chen Li [Department of Dynamics at Surfaces, Max Planck Institute for Biophysical Chemistry, Am Fassberg 11, Goettingen (Germany); Ueta, Hirokazu; Beck, Rainer D. [Laboratoire de Chimie Physique Moleculaire, Ecole Polytechnique Federale de Lausanne (Switzerland); Bisson, Regis [Aix-Marseille Universite, PIIM, CNRS, UMR 7345, 13397 Marseille (France)

    2013-05-15

    We report the design and characterization of a new molecular-beam/surface-science apparatus for quantum state-resolved studies of gas/surface reaction dynamics combining optical state-specific reactant preparation in a molecular beam by rapid adiabatic passage with detection of surface-bound reaction products by reflection absorption infrared spectroscopy (RAIRS). RAIRS is a non-invasive infrared spectroscopic detection technique that enables online monitoring of the buildup of reaction products on the target surface during reactant deposition by a molecular beam. The product uptake rate obtained by calibrated RAIRS detection yields the coverage dependent state-resolved reaction probability S({theta}). Furthermore, the infrared absorption spectra of the adsorbed products obtained by the RAIRS technique provide structural information, which help to identify nascent reaction products, investigate reaction pathways, and determine branching ratios for different pathways of a chemisorption reaction. Measurements of the dissociative chemisorption of methane on Pt(111) with this new apparatus are presented to illustrate the utility of RAIRS detection for highly detailed studies of chemical reactions at the gas/surface interface.

  20. Hydrogen poisoning of the CO oxidation reaction on Pt and Pd under ultrahigh vacuum conditions

    International Nuclear Information System (INIS)

    Strozier, J.A.

    1977-01-01

    The poisoning by hydrogen of the catalyzed oxidation of CO on Pt and Pd under ultrahigh vacuum conditions was investigated. ac pulsing techniques are used in which the pressure of the reactant CO in the reaction chamber is modulated periodically by means of a fast piezoelectric ultrahigh vacuum valve, and the ac component of the product CO 2 is recorded mass spectroscopically by phase-sensitive techniques. The ac CO 2 production rate is measured as a function of hydrogen pressure (1 - 10 x 10 -9 toor) at constant CO and O 2 pressures (approximately equal to 5 x 10 -8 torr), and constant temperature (approximately equal to 700 K). Exact theoretical calculations of CO 2 production rates were carried out employing several models, i.e., oxygen burn-off by hydrogen, incorporating both the Eley-Rideal and Langmuir-Hinshelwood mechanisms. From a comparison with the experimental results, the probable reaction is of the Langmuir-Hinshelwood type and the relevant rate constant is also determined. These results are compared with other results in the literature on hydrogen oxidation on the surface of Pt

  1. Catalytic activity of calcium-based mixed metal oxides nanocatalysts in transesterification reaction of palm oil

    Science.gov (United States)

    Hassan, Noraakinah; Ismail, Kamariah Noor; Hamid, Ku Halim Ku; Hadi, Abdul

    2017-12-01

    Nowadays, biodiesel has become the forefront development as an alternative diesel fuel derived from biological sources such as oils of plant and fats. Presently, the conventional transesterification of vegetable oil to biodiesel gives rise to some technological problem. In this sense, heterogeneous nanocatalysts of calcium-based mixed metal oxides were synthesized through sol-gel method. It was found that significant increase of biodiesel yield, 91.75 % was obtained catalyzed by CaO-NbO2 from palm oil compared to pure CaO of 53.99 % under transesterification conditions (methanol/oil ratio 10:1, reaction time 3 h, catalyst concentration 4 wt%, reaction temperature 60 °C, and mixing speed of 600 rpm). The phase structure and crystallinity as well as the texture properties of the prepared catalysts were characterized by X-ray Diffraction (XRD) and the textural properties were characterized by N2 adsorption-desorption analysis. Sol-gel method has been known as versatile method in controlling the structural and chemical properties of the catalyst. Calcium-based mixed oxide synthesized from sol-gel method was found to exist as smaller crystallite size with high surface area.

  2. S-Nitroglutathione, a product of the reaction between peroxynitrite and glutathione that generates nitric oxide.

    Science.gov (United States)

    Balazy, M; Kaminski, P M; Mao, K; Tan, J; Wolin, M S

    1998-11-27

    Peroxynitrite (ONOO-) has been shown in studies on vascular relaxation and guanylate cyclase activation to react with glutathione (GSH), generating an intermediate product that promotes a time-dependent production of nitric oxide (NO). In this study, reactions of ONOO- with GSH produced a new substance, which was characterized by liquid chromatography, ultraviolet spectroscopy, and electrospray tandem mass spectrometry. The mass spectrometric data provided evidence that the product of this reaction was S-nitroglutathione (GSNO2) and that S-nitrosoglutathione (GSNO) was not a detectable product of this reaction. Further evidence was obtained by comparison of the spectral and chromatographic properties with synthetic standards prepared by reaction of GSH with nitrosonium or nitronium borofluorates. Both the synthetic and ONOO-/GSH-derived GSNO2 generated a protonated ion, GSNO2H+, at m/z 353, which was unusually resistant to decomposition under collision activation, and no fragmentation was observed at collision energy of 25 eV. In contrast, an ion at m/z 337 (GSNOH+), generated from the synthetic GSNO, readily fragmented with the abundant loss of NO at 9 eV. Reactions of ONOO- with GSH resulted in the generation of NO, which was detected by the head space/NO-chemiluminescence analyzer method. The generation of NO was inhibited by the presence of glucose and/or CO2 in the buffers employed. Synthetic GSNO2 spontaneously generated NO in a manner that was not significantly altered by glucose or CO2. Thus, ONOO- reacts with GSH to form GSNO2, and GSNO2 decomposes in a manner that generates NO.

  3. Oxidative modification of methionine80 in cytochrome c by reaction with peroxides.

    Science.gov (United States)

    Nugraheni, Ari Dwi; Ren, Chunguang; Matsumoto, Yorifumi; Nagao, Satoshi; Yamanaka, Masaru; Hirota, Shun

    2018-05-01

    The Met80-heme iron bond of cytochrome c (cyt c) is cleaved by the interaction of cyt c with cardiolipin (CL) in membranes. The Met80 dissociation enhances the peroxidase activity of cyt c and triggers cyt c release from mitochondrion to the cytosol at the early stage of apoptosis. This paper demonstrates the selective oxidation of Met80 for the reaction of ferric cyt c with a peroxide, meta-chloroperbenzoic acid (mCPBA), in the presence of CL-containing liposomes by formation of a ferryl species (Compound I). After the reaction of cyt c with mCPBA in the presence of 1,2-dioloeyl-sn-glycero-3-phosphocholine (DOPC) liposomes containing CL, the electrospray ionization mass spectrum of the peptide fragments, obtained by digestion of cyt c with lysyl endopeptidase, exhibited a peak at m/z = 795.45; whereas, this peak was not observed for the peptide fragments obtained after the reaction in the presence of DOPC liposomes not containing CL. According to the tandem mass spectrum of the m/z = 795.45 peptide fragment, Met80 was modified with a 16 Da mass increase. The purified Met80-modified cyt c exhibited a peroxidase activity more than 5-fold higher than that of the unmodified protein. Transient absorption bands around 650 nm were generated by the reactions with mCPBA for ferric wild-type cyt c in the presence of CL-containing DOPC liposomes and ferric Y67F cyt c in the absence of liposomes. The formation and decomposition rates of the 650-nm absorption species increased and decreased, respectively, by increasing the mCPBA concentration in the reaction, indicating transient formation of Compound I. Copyright © 2018 Elsevier Inc. All rights reserved.

  4. Association of Nitric Oxide Synthase2 gene polymorphisms with leprosy reactions in northern Indian population.

    Science.gov (United States)

    Dubey, Amit; Biswas, Sanjay Kumar; Sinha, Ekata; Chakma, Joy Kumar; Kamal, Raj; Arora, Mamta; Sagar, Harish; Natarajan, Mohan; Bhagyawant, Sameer S; Mohanty, Keshar Kunja

    2017-07-01

    The pathogen Mycobacterium leprae causes leprosy that affects mainly skin and nerves. Polymorphisms of certain genes are substantiated to be associated with the susceptibility/resistance to leprosy. The present investigation addressed the association of Nitric Oxide Synthase2 gene polymorphisms and leprosy in a population from northern part of India. A total of 323 leprosy cases and 288 healthy controls were genotyped for four NOS2 promoter variants (rs1800482, rs2779249, rs8078340 and rs2301369) using FRET technology in Real Time PCR. None of these SNPs in promoter sites was associated with susceptibility/resistance to leprosy. NOS2 rs1800482 was found to be monomorphic with GG genotype. However, NOS2-1026T allele was observed to be in higher frequency with leprosy cases (BL and LL) who were not suffering from any reactional episodes compared to cases with ENL reaction {OR=0.30, 95% CI (0.10-0.86), p=0.024}. NOS2-1026GT genotype was more prevalent in cases without reaction (BT, BB and BL) compared to RR reactional patients {OR=0.38, 95% CI (0.17-0.86), p=0.02}. Although haplotype analysis revealed that no haplotype was associated with leprosy susceptibility/resistance with statistical significance, GTG haplotype was noted to be more frequent in healthy controls. These SNPs are observed to be in linkage disequilibrium. Although, these SNPs are not likely to influence leprosy vulnerability, -1026G>T SNP was indicated to have noteworthy role in leprosy reactions. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Predictors of chronic ankle instability: Analysis of peroneal reaction time, dynamic balance and isokinetic strength.

    Science.gov (United States)

    Sierra-Guzmán, Rafael; Jiménez, Fernando; Abián-Vicén, Javier

    2018-05-01

    Previous studies have reported the factors contributing to chronic ankle instability, which could lead to more effective treatments. However, factors such as the reflex response and ankle muscle strength have not been taken into account in previous investigations. Fifty recreational athletes with chronic ankle instability and 55 healthy controls were recruited. Peroneal reaction time in response to sudden inversion, isokinetic evertor muscle strength and dynamic balance with the Star Excursion Balance Test and the Biodex Stability System were measured. The relationship between the Cumberland Ankle Instability Tool score and performance on each test was assessed and a backward multiple linear regression analysis was conducted. Participants with chronic ankle instability showed prolonged peroneal reaction time, poor performance in the Biodex Stability System and decreased reach distance in the Star Excursion Balance Test. No significant differences were found in eversion and inversion peak torque. Moderate correlations were found between the Cumberland Ankle Instability Tool score and the peroneal reaction time and performance on the Star Excursion Balance Test. Peroneus brevis reaction time and the posteromedial and lateral directions of the Star Excursion Balance Test accounted for 36% of the variance in the Cumberland Ankle Instability Tool. Dynamic balance deficits and delayed peroneal reaction time are present in participants with chronic ankle instability. Peroneus brevis reaction time and the posteromedial and lateral directions of the Star Excursion Balance Test were the main contributing factors to the Cumberland Ankle Instability Tool score. No clear strength impairments were reported in unstable ankles. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Direct synthesis of bimetallic PtCo mesoporous nanospheres as efficient bifunctional electrocatalysts for both oxygen reduction reaction and methanol oxidation reaction

    Science.gov (United States)

    Wang, Hongjing; Yu, Hongjie; Li, Yinghao; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

    2018-04-01

    The engineering of electrocatalysts with high performance for cathodic and/or anodic catalytic reactions is of great urgency for the development of direct methanol fuel cells. Pt-based bimetallic alloys have recently received considerable attention in the field of fuel cells because of their superior catalytic performance towards both fuel molecule electro-oxidation and oxygen reduction. In this work, bimetallic PtCo mesoporous nanospheres (PtCo MNs) with uniform size and morphology have been prepared by a one-step method with a high yield. The as-made PtCo MNs show superior catalytic activities for both oxygen reduction reaction and methanol oxidation reaction relative to Pt MNs and commercial Pt/C catalyst, attributed to their mesoporous structure and bimetallic composition.

  7. Effect of loading rate on dynamic fracture of reaction bonded silicon nitride

    Science.gov (United States)

    Liaw, B. M.; Kobayashi, A. S.; Emery, A. F.

    1986-01-01

    Wedge-loaded, modified tapered double cantilever beam (WL-MTDCB) specimens under impact loading were used to determine the room temperature dynamic fracture response of reaction bonded silicon nitride (RBSN). The crack extension history, with the exception of the terminal phase, was similar to that obtained under static loading. Like its static counterpart, a distinct crack acceleration phase, which was not observed in dynamic fracture of steel and brittle polymers, was noted. Unlike its static counterpart, the crack continued to propagate at nearly its terminal velocity under a low dynamic stress intensity factor during the terminal phase of crack propagation. These and previously obtained results for glass and RBSN show that dynamic crack arrest under a positive dynamic stress intensity factor is unlikely in static and impact loaded structural ceramics.

  8. Synthesizing new types of ultrathin 2D metal oxide nanosheets via half-successive ion layer adsorption and reaction

    Science.gov (United States)

    Gao, Linjie; Li, Yaguang; Xiao, Mu; Wang, Shufang; Fu, Guangsheng; Wang, Lianzhou

    2017-06-01

    Two-dimensional (2D) metal oxide nanosheets have demonstrated their great potential in a broad range of applications. The existing synthesis strategies are mainly preparing 2D nanosheets from layered and specific transition metal oxides. How to prepare the other types of metal oxides as ultrathin 2D nanosheets remains unsolved, especially for metal oxides containing alkali, alkaline earth metal, and multiple metal elements. Herein, we developed a half-successive ion layer adsorption and reaction (SILAR) method, which could synthesize those types of metal oxides as ultrathin 2D nanosheets. The synthesized 2D metal oxides nanosheets are within 1 nm level thickness and 500 m2 · g-1 level surface area. This method allows us to develop many new types of ultrathin 2D metal oxides nanosheets that have never been prepared before.

  9. Synthesis of highly active and dual-functional electrocatalysts for methanol oxidation and oxygen reduction reactions

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Qi; Zhang, Geng; Xu, Guangran; Li, Yingjun [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Liu, Baocang [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Gong, Xia [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Zheng, Dafang [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Zhang, Jun [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Wang, Qin, E-mail: qinwang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China)

    2016-12-15

    Graphical abstract: Ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities (NDs) catalysts, are successfully synthesized by using a facile method. The as-obtained ternary catalysts manifest superior catalytic activity and stability both in terms of surface and mass specific activities toward the methanol oxidation and oxygen reduction reactions, as compared to the binary catalysts and the commercial Pt/C catalysts. - Highlights: • Ternary RuMPt catalysts are synthesized by using a facile method. • The catalysts manifest superior catalytic activity towards the MOR and ORR. • High activities are attributed to enhanced electron density and synergistic effects. - Abstract: The promising Pt-based ternary catalyst is crucial for polymer electrolyte membrane fuel cells (PEMFCs) due to improving catalytic activity and durability for both methanol oxidation reaction and oxygen reduction reaction. In this work, a facile strategy is used for the synthesis ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities catalysts. The ternary RuMPt alloys exhibit enhanced specific and mass activity, positive half-wave potential, and long-term stability, compared with binary Pt-based alloy and the commercial Pt/C catalyst, which is attributed to the high electron density and upshifting of the d-band center for Pt atoms, and synergistic catalytic effects among Pt, M, and Ru atoms by introducing a transition metal. Impressively, the ternary RuCoPt catalyst exhibits superior mass activity (801.59 mA mg{sup −1}) and positive half-wave potential (0.857 V vs. RHE) towards MOR and ORR, respectively. Thus, the RuMPt nanocomposite is a very promising material to be used as dual electrocatalyst in the application of PEMFCs.

  10. Metallic oxides for desulphurization catalyst reaction; Oxidos metalicos mistos como catalisadores para reacoes de dessulfurizacao

    Energy Technology Data Exchange (ETDEWEB)

    Medeiros, R.L.B.A.; Melo, D.M.A.; Melo, M.A.F. [Universidade Federal do Rio Grande do Norte, Natal, RN (Brazil); Souza, K.S.G.M. [Universidade Federal da Paraiba - Departamento de Engenharia Quimica, PB (Brazil); Barros, J.M.F. [Universidade Federal de Campina Grande - Campos Cuite, PB (Brazil)

    2010-07-01

    The mixed metal oxides constitute an important class of catalytic materials widely investigated in different fields of applications. Studies of rare earth nickelates have been carried by several researchers in order to investigate the structural stability afforded by oxide formed and the existence of catalytic properties at room temperature. So, this study aims synthesize the nano sized catalyst of nickelate of lanthanum doped with strontium (La(1- x)Sr{sub x}NiO4-{sigma}; x = 0,2 and 0,3), through the Pechini method and your characterization for subsequent application in the desulfurization of thiophene reaction. The precursor solutions were calcined at 300 degree C/2h for pyrolysis of polyester and later calcinations occurred at temperatures of 500 - 1000 degree C. The resulting powders were characterized by thermogravimetric analysis (TG / DTG), surface area for adsorption of N{sub 2} by BET method, Xray diffraction (XRD), scanning electron microscopy (HR{sub S}EM) and spectrometry dispersive energy (EDS). The results of XRD had show that the perovskites obtained consist of two phases (LSN and NiO) and from 700 degree C have crystalline structure. The results of SEM evidenced the obtainment of nano metric powders. The results of BET show that the powders have surface area within the range used in catalysis (5-50m{sup 2}/g). The characterization of active sites was performed by reaction of desulfurization of thiophene at room temperature and 200 degree C, the relation F/W equal to 0,7 mol h{sup -1}m{sub c}at {sup -1}. The products of the reaction were separated by gas chromatography and identified by the selective detection PFPD sulfur. All samples had presented conversion above 95%. (author)

  11. Changes in oxidative potential of soil and fly ash after reaction with gaseous nitric acid

    Science.gov (United States)

    Zhan, Ying; Ginder-Vogel, Matthew; Shafer, Martin M.; Rudich, Yinon; Pardo, Michal; Katra, Itzhak; Katoshevski, David; Schauer, James J.

    2018-01-01

    The goal of this study was to examine the impact of simulated atmospheric aging on the oxidative potential of inorganic aerosols comprised primarily of crustal materials. Four soil samples and one coal fly ash sample were artificially aged in the laboratory through exposure to the vapor from 15.8 M nitric acid solution for 24 h at room temperature. Native and acid-aged samples were analyzed with a cellular macrophage and acellular dithionthreitol assays to determine oxidative potential. Additionally, the samples were analyzed to determine the concentration of 50 elements, both total and the water-soluble fraction of these elements by Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICMS) and crystalline mineral composition using X-ray Diffraction (XRD). The results show that reactions with gaseous nitric acid increase the water-soluble fraction of many elements, including calcium, iron, magnesium, zinc, and lead. The mineral composition analysis documented that calcium-rich minerals present in the soils (e.g., calcite) are converted into different chemical forms, such as calcium nitrate (Ca(NO3)2). The nitric acid aging process, which can occur in the atmosphere, leads to a 200-600% increase in oxidative potential, as measured by cellular and acellular assays. This laboratory study demonstrates that the toxic effects of aged versus freshly emitted atmospheric dust may be quite different. In addition, the results suggest that mineralogical analysis of atmospheric dust may be useful in understanding its degree of aging.

  12. Sintering uranium oxide in the reaction product of hydrogen-carbon dioxide mixtures

    International Nuclear Information System (INIS)

    De Hollander, W.R.; Nivas, Y.

    1975-01-01

    Compacted pellets of uranium oxide alone or containing one or more additives such as plutonium dioxide, gadolinium oxide, titanium dioxide, silica, and alumina are heated to 900 to 1599 0 C in the presence of a mixture of hydrogen and carbon dioxide, either alone or with an inert carrier gas and held at the desired temperature in this atmosphere to sinter the pellets. The sintered pellets are then cooled in an atmosphere having an oxygen partial pressure of 10 -4 to 10 -18 atm of oxygen such as dry hydrogen, wet hydrogen, dry carbon monoxide, wet carbon monoxide, inert gases such as nitrogen, argon, helium, and neon and mixtures of ayny of the foregoing including a mixture of hydrogen and carbon dioxide. The ratio of hydrogen to carbon dioxide in the gas mixture fed to the furnace is controlled to give a ratio of oxygen to uranium atoms in the sintered particles within the range of 1.98:1 to about 2.10:1. The water vapor present in the reaction products in the furnace atmosphere acts as a hydrolysis agent to aid removal of fluoride should such impurity be present in the uranium oxide. (U.S.)

  13. Ethanol Oxidation Reaction Using PtSn/C+Ce/C Electrocatalysts: Aspects of Ceria Contribution

    International Nuclear Information System (INIS)

    De Souza, R.F.B.; Silva, J.C.M.; Assumpção, M.H.M.T.; Neto, A.O.; Santos, M.C.

    2014-01-01

    The ethanol oxidation reaction (EOR) was investigated using PtSn/C + Ce/C electrocatalysts in different mass ratios (58:42, 53:47, and 42:58) prepared using the polymeric precursor method. Transmission electron microscopy (TEM) experiments showed particles sizes in the range of 3 to 7 nm. Changes in the net parameters observed for Pt suggest the incorporation of Sn into the Pt crystalline network with the formation of an alloy mixture with the SnO 2 phase. Among the PtSn/C + Ce/C catalysts investigated, the 53:47 composition showed the highest activity towards the EOR. In this case, the j versus t curves obtained in the presence of ethanol in acidic media exhibited a current density 90% higher than that observed with the commercial PtSn/C (ETEK). Correspondingly, during the experiments performed on single direct ethanol fuel cells, the maximum power density obtained using PtSn/C + Ce/C (53:47) as the anode was approximately 60% higher than that obtained using the commercial catalyst. FTIR data showed that the observed behavior for ethanol oxidation may be explained in terms of a synergic effect of bifunctional mechanism with electronic effects, in addition to a chemical effect of ceria that provides oxygen-containing species to oxidize acetaldehyde to acetic acid

  14. Iron-Induced Activation of Ordered Mesoporous Nickel Cobalt Oxide Electrocatalyst for the Oxygen Evolution Reaction.

    Science.gov (United States)

    Deng, Xiaohui; Öztürk, Secil; Weidenthaler, Claudia; Tüysüz, Harun

    2017-06-28

    Herein, ordered mesoporous nickel cobalt oxides prepared by the nanocasting route are reported as highly active oxygen evolution reaction (OER) catalysts. By using the ordered mesoporous structure as a model system and afterward elevating the optimal catalysts composition, it is shown that, with a simple electrochemical activation step, the performance of nickel cobalt oxide can be significantly enhanced. The electrochemical impedance spectroscopy results indicated that charge transfer resistance increases for Co 3 O 4 spinel after an activation process, while this value drops for NiO and especially for CoNi mixed oxide significantly, which confirms the improvement of oxygen evolution kinetics. The catalyst with the optimal composition (Co/Ni 4/1) reaches a current density of 10 mA/cm 2 with an overpotential of a mere 336 mV and a Tafel slope of 36 mV/dec, outperforming benchmarked and other reported Ni/Co-based OER electrocatalysts. The catalyst also demonstrates outstanding durability for 14 h and maintained the ordered mesoporous structure. The cyclic voltammograms along with the electrochemical measurements in Fe-free KOH electrolyte suggest that the activity boost is attributed to the generation of surface Ni(OH) 2 species that incorporate Fe impurities from the electrolyte. The incorporation of Fe into the structure is also confirmed by inductively coupled plasma optical emission spectrometry.

  15. Reaction modelling of Iron Oxide Bromination in the UT-3 thermochemical cycle for Hydrogen production from water

    International Nuclear Information System (INIS)

    Amir-Rusli

    1996-01-01

    Analysis modelling of the iron oxide bromination had been carried out using experiment data from the iron oxide bromination in the UT-3 thermochemical cycle. Iron oxide in the form of pellets were made of the calcination of the mixture of iron oxide, silica, graphite and cellulose at 1473 K. Thermobalance reactor was used to study the kinetic reactions of the iron oxide bromination at a temperature of 473 K for 2 - 6 hours. The data collected from the experiments were used as input for the common models. However, none of these models could not explain the result of the experiments. A new model, a combination of two kinetic reactions : exposed particle and coated particle was created and worked successfully

  16. CO oxidation on PtSn nanoparticle catalysts occurs at the interface of Pt and Sn oxide domains formed under reaction conditions

    KAUST Repository

    Michalak, William D.

    2014-04-01

    The barrier to CO oxidation on Pt catalysts is the strongly bound adsorbed CO, which inhibits O2 adsorption and hinders CO2 formation. Using reaction studies and in situ X-ray spectroscopy with colloidally prepared, monodisperse ∼2 nm Pt and PtSn nanoparticle catalysts, we show that the addition of Sn to Pt provides distinctly different reaction sites and a more efficient reaction mechanism for CO oxidation compared to pure Pt catalysts. To probe the influence of Sn, we intentionally poisoned the Pt component of the nanoparticle catalysts using a CO-rich atmosphere. With a reaction environment comprised of 100 Torr CO and 40 Torr O2 and a temperature range between 200 and 300 C, Pt and PtSn catalysts exhibited activation barriers for CO2 formation of 133 kJ/mol and 35 kJ/mol, respectively. While pure Sn is readily oxidized and is not active for CO oxidation, the addition of Sn to Pt provides an active site for O2 adsorption that is important when Pt is covered with CO. Sn oxide was identified as the active Sn species under reaction conditions by in situ ambient pressure X-ray photoelectron spectroscopy measurements. While chemical signatures of Pt and Sn indicated intermixed metallic components under reducing conditions, Pt and Sn were found to reversibly separate into isolated domains of Pt and oxidic Sn on the nanoparticle surface under reaction conditions of 100 mTorr CO and 40 mTorr O2 between temperatures of 200-275 C. Under these conditions, PtSn catalysts exhibited apparent reaction orders in O2 for CO 2 production that were 0.5 and lower with increasing partial pressures. These reaction orders contrast the first-order dependence in O 2 known for pure Pt. The differences in activation barriers, non-first-order dependence in O2, and the presence of a partially oxidized Sn indicate that the enhanced activity is due to a reaction mechanism that occurs at a Pt/Sn oxide interface present at the nanoparticle surface. © 2014 Published by Elsevier Inc.

  17. Degradation of Perfluorooctanoic Acid and Perfluoroctane Sulfonate by Enzyme Catalyzed Oxidative Humification Reactions

    Science.gov (United States)

    Huang, Q.

    2016-12-01

    Poly- and perfluoroalkyl substances (PFASs) are alkyl based chemicals having multiple or all hydrogens replaced by fluorine atoms, and thus exhibit high thermal and chemical stability and other unusual characteristics. PFASs have been widely used in a wide variety of industrial and consumer products, and tend to be environmentally persistent. Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) are two representative PFASs that have drawn particular attention because of their ubiquitous presence in the environment, resistance to degradation and toxicity to animals. This study examined the decomposition of PFOA and PFOS in enzyme catalyzed oxidative humification reactions (ECOHR), a class of reactions that are ubiquitous in the environment involved in natural organic humification. Reaction rates and influential factors were examined, and high-resolution mass spectrometry was used to identify possible products. Fluorides and partially fluorinated compounds were identified as likely products from PFOA and PFOS degradation, which were possibly formed via a combination of free radical decomposition, rearrangements and coupling processes. The findings suggest that PFOA and PFOS may be transformed during humification, and ECOHR can potentially be used for the remediation of these chemicals.

  18. A ring polymer molecular dynamics study of the isotopologues of the H + H2 reaction.

    Science.gov (United States)

    Suleimanov, Yury V; de Tudela, Ricardo Pérez; Jambrina, Pablo G; Castillo, Jesús F; Sáez-Rábanos, Vicente; Manolopoulos, David E; Aoiz, F Javier

    2013-03-14

    The inclusion of Quantum Mechanical (QM) effects such as zero point energy (ZPE) and tunneling in simulations of chemical reactions, especially in the case of light atom transfer, is an important problem in computational chemistry. In this respect, the hydrogen exchange reaction and its isotopic variants constitute an excellent benchmark for the assessment of approximate QM methods. In particular, the recently developed ring polymer molecular dynamics (RPMD) technique has been demonstrated to give very good results for bimolecular chemical reactions in the gas phase. In this work, we have performed a detailed RPMD study of the H + H(2) reaction and its isotopologues Mu + H(2), D + H(2) and Heμ + H(2), at temperatures ranging from 200 to 1000 K. Thermal rate coefficients and kinetic isotope effects have been computed and compared with exact QM calculations as well as with quasiclassical trajectories and experiment. The agreement with the QM results is good for the heaviest isotopologues, with errors ranging from 15% to 45%, and excellent for Mu + H(2), with errors below 15%. We have seen that RPMD is able to capture the ZPE effect very accurately, a desirable feature of any method based on molecular dynamics. We have also verified Richardson and Althorpe's prediction [J. O. Richardson and S. C. Althorpe, J. Chem. Phys., 2009, 131, 214106] that RPMD will overestimate thermal rates for asymmetric reactions and underestimate them for symmetric reactions in the deep tunneling regime. The ZPE effect along the reaction coordinate must be taken into account when assigning the reaction symmetry in the multidimensional case.

  19. High resolution X-ray photoelectron spectroscopy of styrene oxide adsorption and reaction on Ag(1 1 1)

    Science.gov (United States)

    Piao, H.; Enever, M. C. N.; Adib, K.; Hrbek, J.; Barteau, M. A.

    2004-11-01

    Synchrotron-based X-ray photoelectron spectroscopy (XPS) has been used to investigate the adsorption and reaction of styrene oxide on Ag(1 1 1). When adsorption is carried out at 250 K or above, ring opening of styrene oxide forms a stable surface oxametallacycle intermediate which eventually reacts at 485 K to regenerate styrene oxide. High resolution XPS is capable of distinguishing the oxametallacycle from molecularly adsorbed and condensed styrene oxide on the basis of different C1s peak separations. The observed separations are well accounted for by the results of DFT calculations.

  20. Effects of gas flow on oxidation reaction in liquid induced by He/O{sub 2} plasma-jet irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Nakajima, Atsushi; Uchida, Giichiro, E-mail: uchida@jwri.osaka-u.ac.jp; Takenaka, Kosuke; Setsuhara, Yuichi [Joining and Welding Research Institute, Osaka University, Ibaraki, Osaka 567-0047 (Japan); Kawasaki, Toshiyuki [Department of Mechanical and Electrical Engineering, Nippon Bunri University, Oita, Oita 870-0397 (Japan); Koga, Kazunori; Sarinont, Thapanut; Amano, Takaaki; Shiratani, Masaharu [Graduate School of Information Science and Electrical Engineering, Kyushu University, Fukuoka, Fukuoka 819-0395 (Japan)

    2015-07-28

    We present here analysis of oxidation reaction in liquid by a plasma-jet irradiation under various gas flow patterns such as laminar and turbulence flows. To estimate the total amount of oxidation reaction induced by reactive oxygen species (ROS) in liquid, we employ a KI-starch solution system, where the absorbance of the KI-starch solution near 600 nm behaves linear to the total amount of oxidation reaction in liquid. The laminar flow with higher gas velocity induces an increase in the ROS distribution area on the liquid surface, which results in a large amount of oxidation reaction in liquid. However, a much faster gas flow conversely results in a reduction in the total amount of oxidation reaction in liquid under the following two conditions: first condition is that the turbulence flow is triggered in a gas flow channel at a high Reynolds number of gas flow, which leads to a marked change of the spatial distribution of the ROS concentration in gas phase. Second condition is that the dimpled liquid surface is formed by strong gas flow, which prevents the ROS from being transported in radial direction along the liquid surface.

  1. Evaluation of the kinetic and thermodynamic parameters of oxidation reaction in biodiesel from a quaternary mixture of raw material

    Directory of Open Access Journals (Sweden)

    Karina Gomes Angilelli

    2017-05-01

    Full Text Available A mixture of vegetable oil and animal fat as raw materials was optimized by simplex-centroid mixture design to produce a type of biodiesel with good oxidative stability, flow properties and reaction yield. Further, kinetic and thermodynamic parameters of oxidation reaction were determined by the accelerated method at different temperatures. Biodiesel produced with sodium methoxide as catalyst presented 6.5°C of cloud point, 2.0°C of pour point, and oxidative stability at 110°C equal to 8.98h, with a reaction yield of 96.04%. Activation energy of the oxidation reaction was 81.03 kJ mol-1 for biodiesel produced with sodium hydroxide and 90.51 kJ mol-1 for sodium methoxide. The positive values for DH‡ and DG‡ indicate that the oxidation process is endothermic and endergonic. The less negative DS‡ for biodiesel produced with sodium methoxide (-28.87 JK-1 mol-1 showed that the process of degradation of this biofuel was slower than that produced with NaOH. The mixture of raw materials proposed, transesterified with the methoxide catalyst, resulted in a biofuel that resisted oxidation for longer periods, making unnecessary the addition of antioxidant

  2. Detailed dynamic solid oxide fuel cell modeling for electrochemical impedance spectra simulation

    Energy Technology Data Exchange (ETDEWEB)

    Hofmann, Ph. [Laboratory of Steam Boilers and Thermal Plants, School of Mechanical Engineering, Thermal Engineering Section, National Technical University of Athens, Heroon Polytechniou 9, 15780 Athens (Greece); Panopoulos, K.D. [Institute for Solid Fuels Technology and Applications, Centre for Research and Technology Hellas, 4th km. Ptolemais-Mpodosakeio Hospital, Region of Kouri, P.O. Box 95, GR 502, 50200 Ptolemais (Greece)

    2010-08-15

    This paper presents a detailed flexible mathematical model for planar solid oxide fuel cells (SOFCs), which allows the simulation of steady-state performance characteristics, i.e. voltage-current density (V-j) curves, and dynamic operation behavior, with a special capability of simulating electrochemical impedance spectroscopy (EIS). The model is based on physico-chemical governing equations coupled with a detailed multi-component gas diffusion mechanism (Dusty-Gas Model (DGM)) and a multi-step heterogeneous reaction mechanism implicitly accounting for the water-gas-shift (WGS), methane reforming and Boudouard reactions. Spatial discretization can be applied for 1D (button-cell approximation) up to quasi-3D (full size anode supported cell in cross-flow configuration) geometries and is resolved with the finite difference method (FDM). The model is built and implemented on the commercially available modeling and simulations platform gPROMS trademark. Different fuels based on hydrogen, methane and syngas with inert diluents are run. The model is applied to demonstrate a detailed analysis of the SOFC inherent losses and their attribution to the EIS. This is achieved by means of a step-by-step analysis of the involved transient processes such as gas conversion in the main gas chambers/channels, gas diffusion through the porous electrodes together with the heterogeneous reactions on the nickel catalyst, and the double-layer current within the electrochemical reaction zone. The model is an important tool for analyzing SOFC performance fundamentals as well as for design and optimization of materials' and operational parameters. (author)

  3. Oxidation of D-glucose and D-fructose with oxygen in aqueous, alkaline solutions. Part I. An integral reaction scheme

    NARCIS (Netherlands)

    de Wilt, H.G.J.; Kuster, B.F.M.

    1971-01-01

    The homogeneous oxidn. of D-glucose and D-fructose with O in aq., alk. solns. is studied, and a reaction scheme proposed to account for the obsd. reaction products. Formation of enolate anions is followed by non-oxidative reactions (involving double-bond migration and cleavage) and by oxidative

  4. Reaction

    African Journals Online (AJOL)

    abp

    19 oct. 2017 ... Reaction to Mohamed Said Nakhli et al. concerning the article: "When the axillary block remains the only alternative in a 5 year old child". .... Bertini L1, Savoia G, De Nicola A, Ivani G, Gravino E, Albani A et al ... 2010;7(2):101-.

  5. Capturing Chemistry in Action with Electrons: Realization of Atomically Resolved Reaction Dynamics.

    Science.gov (United States)

    Ischenko, Anatoly A; Weber, Peter M; Miller, R J Dwayne

    2017-08-23

    One of the grand challenges in chemistry has been to directly observe atomic motions during chemical processes. The depiction of the nuclear configurations in space-time to understand barrier crossing events has served as a unifying intellectual theme connecting the different disciplines of chemistry. This challenge has been cast as an imaging problem in which the technical issues reduce to achieving not only sufficient simultaneous space-time resolution but also brightness for sufficient image contrast to capture the atomic motions. This objective has been met with electrons as the imaging source. The review chronicles the first use of electron structural probes to study reactive intermediates, to the development of high bunch charge electron pulses with sufficient combined spatial-temporal resolution and intensity to literally light up atomic motions, as well as the means to characterize the electron pulses in terms of temporal brightness and image reconstruction. The use of femtosecond Rydberg spectroscopy as a novel means to use internal electron scattering within the molecular reference frame to obtain similar information on reaction dynamics is also discussed. The focus is on atomically resolved chemical reaction dynamics with pertinent references to work in other areas and forms of spectroscopy that provide additional information. Effectively, we can now directly observe the far-from-equilibrium atomic motions involved in barrier crossing and categorize chemistry in terms of a power spectrum of a few dominant reaction modes. It is this reduction in dimensionality that makes chemical reaction mechanisms transferrable to seemingly arbitrarily complex (large N) systems, up to molecules as large as biological macromolecules (N > 1000 atoms). We now have a new way to reformulate reaction mechanisms using an experimentally determined dynamic mode basis that in combination with recent theoretical advances has the potential to lead to a new conceptual basis for

  6. Coarse-grained molecular dynamics simulations of polymerization with forward and backward reactions.

    Science.gov (United States)

    Krajniak, Jakub; Zhang, Zidan; Pandiyan, Sudharsan; Nies, Eric; Samaey, Giovanni

    2018-06-11

    We develop novel parallel algorithms that allow molecular dynamics simulations in which byproduct molecules are created and removed because of the chemical reactions during the molecular dynamics simulation. To prevent large increases in the potential energy, we introduce the byproduct molecules smoothly by changing the non-bonded interactions gradually. To simulate complete equilibrium reactions, we allow the byproduct molecules attack and destroy created bonds. Modeling of such reactions are, for instance, important to study the pore formation due to the presence of e.g. water molecules or development of polymer morphology during the process of splitting off byproduct molecules. Another concept that could be studied is the degradation of polymeric materials, a very important topic in a recycling of polymer waste. We illustrate the method by simulating the polymerization of polyethylene terephthalate (PET) at the coarse-grained level as an example of a polycondensation reaction with water as a byproduct. The algorithms are implemented in a publicly available software package and are easily accessible using a domain-specific language that describes chemical reactions in an input configuration file. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

  7. Classical molecular dynamics simulation of weakly-bound projectile heavy-ion reactions

    Directory of Open Access Journals (Sweden)

    Morker Mitul R.

    2015-01-01

    Full Text Available A 3-body classical molecular dynamics approach for heavy-ion reactions involving weakly bound projectiles is developed. In this approach a weakly bound projectile is constructed as a two-body cluster of the constituent tightly bound nuclei in a configuration corresponding to the observed breakup energy. This 3-body system with their individual nucleon configuration in their ground state is dynamically evolved for given initial conditions using the three-stage classical molecular dynamics approach (3S-CMD. Various levels of rigidbody constraints on the projectile constituents and the target are considered at appropriate stages. This 3-dimensional approach explicitly takes into account not only the long range Coulomb reorientation of the deformed collision partner but internal excitations and breakup probabilities at distances close to the barrier also. Dynamical simulations of 6Li+209Bi show all the possible reaction mechanism like complete fusion, incomplete fusion, scattering and breakup scattering. Complete fusion cross sections of 6Li+209Bi and 7Li+209Bi reactions are calculated in this approach with systematic relaxations of the rigid-body constraints on one or more constituent nuclei.

  8. Competition between abstraction and exchange channels in H + HCN reaction: Full-dimensional quantum dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Bin; Guo, Hua, E-mail: hguo@unm.edu [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)

    2013-12-14

    Dynamics of the title reaction is investigated on an ab initio based potential energy surface using a full-dimensional quantum wave packet method within the centrifugal sudden approximation. It is shown that the reaction between H and HCN leads to both the hydrogen exchange and hydrogen abstraction channels. The exchange channel has a lower threshold and larger cross section than the abstraction channel. It also has more oscillations due apparently to quantum resonances. Both channels are affected by long-lived resonances supported by potential wells. Comparison with experimental cross sections indicates underestimation of the abstraction barrier height.

  9. Methanol oxidation reaction on core-shell structured Ruthenium-Palladium nanoparticles: Relationship between structure and electrochemical behavior

    Science.gov (United States)

    Kübler, Markus; Jurzinsky, Tilman; Ziegenbalg, Dirk; Cremers, Carsten

    2018-01-01

    In this work the relationship between structural composition and electrochemical characteristics of Palladium(Pd)-Ruthenium(Ru) nanoparticles during alkaline methanol oxidation reaction is investigated. The comparative study of a standard alloyed and a precisely Ru-core-Pd-shell structured catalyst allows for a distinct investigation of the electronic effect and the bifunctional mechanism. Core-shell catalysts benefit from a strong electronic effect and an efficient Pd utilization. It is found that core-shell nanoparticles are highly active towards methanol oxidation reaction for potentials ≥0.6 V, whereas alloyed catalysts show higher current outputs in the lower potential range. However, differential electrochemical mass spectrometry (DEMS) experiments reveal that the methanol oxidation reaction on core-shell structured catalysts proceeds via the incomplete oxidation pathway yielding formaldehyde, formic acid or methyl formate. Contrary, the alloyed catalyst benefits from the Ru atoms at its surface. Those are found to be responsible for high methanol oxidation activity at lower potentials as well as for complete oxidation of CH3OH to CO2 via the bifunctional mechanism. Based on these findings a new Ru-core-Pd-shell-Ru-terrace catalyst was synthesized, which combines the advantages of the core-shell structure and the alloy. This novel catalyst shows high methanol electrooxidation activity as well as excellent selectivity for the complete oxidation pathway.

  10. Low energy ion-molecule reaction dynamics and chemiionization kinetics: Progress report, February 1, 1985-January 31, 1988

    International Nuclear Information System (INIS)

    Farrar, J.M.

    1988-01-01

    The research program at Rochester is devoted to an understanding of the dynamics of elementary gas phase ionic reactions by using the molecular beam methods. We seek to elucidate pathways for energy disposal in elementary reactions, with the goal of using this information to understand the topology of the potential surfaces which govern the reaction, applying the results to ionic channels in combustion systems. We have made significant accomplishments in several distinct areas of research in crossed beam studies of ion-neutral reaction dynamics in the past three years. Our research has focused on the following topics and has resulted in 15 publications and submissions to major journals, with several additional manuscripts in preparation: dynamics of gas phase proton transfer reactions, gas phase carbon and methyl cation chemistry, reactive scattering from double minimum potentials, reactions of highly vibrationally excited ions: NH 3 + + D 2 , and electron and proton transfer reactions of anions. 9 refs

  11. Dynamics of interface in three-dimensional anisotropic bistable reaction-diffusion system

    International Nuclear Information System (INIS)

    He Zhizhu; Liu, Jing

    2010-01-01

    This paper presents a theoretical investigation of dynamics of interface (wave front) in three-dimensional (3D) reaction-diffusion (RD) system for bistable media with anisotropy constructed by means of anisotropic surface tension. An equation of motion for the wave front is derived to carry out stability analysis of transverse perturbations, which discloses mechanism of pattern formation such as labyrinthine in 3D bistable media. Particularly, the effects of anisotropy on wave propagation are studied. It was found that, sufficiently strong anisotropy can induce dynamical instabilities and lead to breakup of the wave front. With the fast-inhibitor limit, the bistable system can further be described by a variational dynamics so that the boundary integral method is adopted to study the dynamics of wave fronts.

  12. Fuel-sodium reaction product formation in breached mixed-oxide fuel

    International Nuclear Information System (INIS)

    Bottcher, J.H.; Lambert, J.D.B.; Strain, R.V.; Ukai, S.; Shibahara, S.

    1988-01-01

    The run-beyond-cladding-breach (RBCB) operation of mixed-oxide LMR fuel pins has been studied for six years in the Experimental Breeder Reactor-II (EBR-II) as part of a joint program between the US Department of Energy and the Power Reactor and Nuclear Fuel Development Corporation of Japan. The formation of fuel-sodium reaction product (FSRP), Na 3 MO 4 , where M = U/sub 1-y/Pu/sub y/, in the outer fuel regions is the major phenomenon governing RBCB behavior. It increases fuel volume, decreases fuel stoichiometry, modifies fission-product distributions, and alters thermal performance of a pin. This paper describes the morphology of Na 3 MO 4 observed in 5.84-mm diameter pins covering a variety of conditions and RBCB times up to 150 EFPD's. 8 refs., 1 fig

  13. Transport phenomena in solid oxide fuel cell electrodes focusing on heat transfer related to chemical reactions

    International Nuclear Information System (INIS)

    Navasa, M; Andersson, M; Yuan, J; Sundén, B

    2012-01-01

    Solid oxide fuel cells (SOFCs) are widely studied for their advantages especially at high temperatures. However, operating at high temperatures represents a high cost due to the strict requirements the materials are expected to fulfill. Thus, the main goal in SOFC research has been to decrease the operating temperature so that the range of available materials is widened and hence, the operating cost can be reduced. In this paper, the different heat sources that contribute to the cell energy balance are presented with strong emphasis on the chemical reactions that take place in SOFCs. The knowledge of which heat sources or sinks taking place and their locations within the SOFC can provide useful information for further design and efficiency improvements.

  14. Graphene oxide for acid catalyzed-reactions: Effect of drying process

    Science.gov (United States)

    Gong, H. P.; Hua, W. M.; Yue, Y. H.; Gao, Z.

    2017-03-01

    Graphene oxides (GOs) were prepared by Hummers method through various drying processes, and characterized by XRD, SEM, FTIR, XPS and N2 adsorption. Their acidities were measured using potentiometric titration and acid-base titration. The catalytic properties were investigated in the alkylation of anisole with benzyl alcohol and transesterification of triacetin with methanol. GOs are active catalysts for both reaction, whose activity is greatly affected by their drying processes. Vacuum drying GO exhibits the best performance in transesterification while freezing drying GO is most active for alkylation. The excellent catalytic behavior comes from abundant surface acid sites as well as proper surface functional groups, which can be obtained by selecting appropriate drying process.

  15. PET-modified red mud as catalysts for oxidative desulfurization reactions.

    Science.gov (United States)

    do Prado, Nayara T; Heitmann, Ana P; Mansur, Herman S; Mansur, Alexandra A; Oliveira, Luiz C A; de Castro, Cinthia S

    2017-07-01

    This work describes the synthesis of catalysts based on red mud/polyethylene terephthalate (PET) composites and their subsequent heat treatment under N 2 atmosphere. The materials were characterized by scanning electron microscopy (SEM), temperature programmed reduction (TPR), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric (TG) analysis and N 2 adsorption/desorption. The catalysts were evaluated in the oxidative desulfurization reaction of dibenzothiophene (DBT) in a biphasic system. The results indicated that the PET impregnation on red mud increased the affinity of the catalyst with the nonpolar phase (fuel), in which the contaminant was dissolved, allowing a higher conversion (up to 80%) and selectivity to the corresponding dibenzothiophene sulfone. The sulfone compound is more polar than DBT and diffused into the polar solvent as indicated by the data obtained via gas chromatography-mass spectrometry (GC-MS). Copyright © 2017. Published by Elsevier B.V.

  16. Coherent diffractive imaging of solid state reactions in zinc oxide crystals

    Science.gov (United States)

    Leake, Steven J.; Harder, Ross; Robinson, Ian K.

    2011-11-01

    We investigated the doping of zinc oxide (ZnO) microcrystals with iron and nickel via in situ coherent x-ray diffractive imaging (CXDI) in vacuum. Evaporated thin metal films were deposited onto the ZnO microcrystals. A single crystal was selected and tracked through annealing cycles. A solid state reaction was observed in both iron and nickel experiments using CXDI. A combination of the shrink wrap and guided hybrid-input-output phasing methods were applied to retrieve the electron density. The resolution was 33 nm (half order) determined via the phase retrieval transfer function. The resulting images are nevertheless sensitive to sub-angstrom displacements. The exterior of the microcrystal was found to degrade dramatically. The annealing of ZnO microcrystals coated with metal thin films proved an unsuitable doping method. In addition the observed defect structure of one crystal was attributed to the presence of an array of defects and was found to change upon annealing.

  17. Phosphine-functionalized graphene oxide, a high-performance electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Ensafi, Ali A.; Golbon Haghighi, Mohsen; Jafari-Asl, Mehdi

    2018-01-01

    Here, a new approach for the synthesis of phosphine-functionalized graphene oxide (GO-PPh2) was developed. Using a simple method, diphenylphosphine group was linked to the hydroxyl group of OH-functionalized graphene that existing at the graphene surface. The electrochemical activity of GO-PPh2 for electrochemical oxygen reduction was checked. The results demonstrated that the new carbon hybrid material has a powerful potential for electrochemical oxygen reduction reaction (ORR). Moreover, GO-PPh2 as an electrocatalyst for ORR exhibited tolerance for methanol or ethanol as a result of crossover effect. In comparison with commercial Pt/C and Pt/rGO electrocatalysts, results showed that GO-PPh2 has a much higher selectivity, better durability, and much better electrochemical stability towards the ORR. The proposed method based on GO-PPh2 introduce an efficient electrocatalyst for further application in fuel cells.

  18. A novel differential electrochemical mass spectrometry method to determine the product distribution from parasitic Methanol oxidation reaction on oxygen reduction reaction catalysts

    Science.gov (United States)

    Jurzinsky, Tilman; Kurzhals, Philipp; Cremers, Carsten

    2018-06-01

    The oxygen reduction reaction is in research focus since several decades due to its importance for the overall fuel cell performance. In direct methanol fuel cells, the crossover of methanol and its subsequent parasitic oxidation are main issues when it comes to preventing fuel cell performance losses. In this work, we present a novel differential electrochemical mass spectrometry method to evaluate oxygen reduction reaction catalysts on their tolerance to methanol being present at the cathode. Besides this, the setup allows to measure under more realistic fuel cell conditions than typical rotating disc electrode measurements, because the oxygen reduction reaction is evaluated in gaseous phase and a gas diffusion electrode is used as working electrode. Due to the new method, it was possible to investigate the oxygen reduction reaction on two commonly used catalysts (Pt/C and Pt3Co/C) in absence and presence of methanol. It was found, that Pt3Co/C is less prone to parasitic current losses due to methanol oxidation reaction. By connecting a mass spectrometer to the electrochemical cell, the new method allows to determine the products formed on the catalysts due to parasitic methanol electrooxidation.

  19. Kinetics of solid-gas reactions characterized by scanning AC nano-calorimetry with application to Zr oxidation

    International Nuclear Information System (INIS)

    Xiao, Kechao; Lee, Dongwoo; Vlassak, Joost J.

    2014-01-01

    Scanning AC nano-calorimetry is a recently developed experimental technique capable of measuring the heat capacity of thin-film samples of a material over a wide range of temperatures and heating rates. Here, we describe how this technique can be used to study solid-gas phase reactions by measuring the change in heat capacity of a sample during reaction. We apply this approach to evaluate the oxidation kinetics of thin-film samples of zirconium in air. The results confirm parabolic oxidation kinetics with an activation energy of 0.59 ± 0.03 eV. The nano-calorimetry measurements were performed using a device that contains an array of micromachined nano-calorimeter sensors in an architecture designed for combinatorial studies. We demonstrate that the oxidation kinetics can be quantified using a single sample, thus enabling high-throughput mapping of the composition-dependence of the reaction rate.

  20. Continuous Flow Aerobic Alcohol Oxidation Reactions Using a Heterogeneous Ru(OH)x/Al2O3 Catalyst

    Science.gov (United States)

    2015-01-01

    Ru(OH)x/Al2O3 is among the more versatile catalysts for aerobic alcohol oxidation and dehydrogenation of nitrogen heterocycles. Here, we describe the translation of batch reactions to a continuous-flow method that enables high steady-state conversion and single-pass yields in the oxidation of benzylic alcohols and dehydrogenation of indoline. A dilute source of O2 (8% in N2) was used to ensure that the reaction mixture, which employs toluene as the solvent, is nonflammable throughout the process. A packed bed reactor was operated isothermally in an up-flow orientation, allowing good liquid–solid contact. Deactivation of the catalyst during the reaction was modeled empirically, and this model was used to achieve high conversion and yield during extended operation in the aerobic oxidation of 2-thiophene methanol (99+% continuous yield over 72 h). PMID:25620869

  1. The adsorption and reaction of halogenated volatile organic compounds (VOC's) on metal oxides. 1998 annual progress report

    International Nuclear Information System (INIS)

    Goodman, D.W.; Haw, J.F.; Lunsford, J.

    1998-01-01

    'The goal of the research is to elucidate the properties of the materials responsible for the activation of halocarbons and the nature of the intermediates formed in the dissociative adsorption of this class of compounds. This information is essential for interpreting and predicting stoichiometric and catalytic pathways for the safe destruction of halocarbon pollutants. The specific objectives are: (1) to study the adsorption and reactivity of chloromethanes and chloroethanes on metal oxides; (2) to identify the reaction intermediates using spectroscopic methods; and (3) to develop kinetic models for the reaction of these halocarbons with oxide surfaces. This report summarizes work after 20 months of a 36-month project. Emphasis has been placed understanding the surfaces phases, as well as the bulk phases that are present during the reactions of chlorinated hydrocarbons with strongly basic metal oxides. Most of the research has been carried out with carbon tetrachloride.'

  2. Enhanced photocatalytic degradation of methylene blue by ZnO-reduced graphene oxide composite synthesized via microwave-assisted reaction

    Energy Technology Data Exchange (ETDEWEB)

    Lv Tian [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, 200062 (China); Pan Likun, E-mail: lkpan@phy.ecnu.edu.cn [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, 200062 (China); Liu Xinjuan; Lu Ting; Zhu Guang; Sun Zhuo [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, 200062 (China)

    2011-10-13

    Highlights: > ZnO-reduced graphene oxide composite is synthesized via microwave assisted reaction. > The method allows a facile, safe and rapid reaction in aqueous media. > A high dye degradation efficiency is achieved under UV light irradiation. - Abstract: A quick and facile microwave-assisted reaction is used to synthesize ZnO-reduced graphene oxide (RGO) hybrid composites by reducing graphite oxide dispersion with zinc nitrate using a microwave synthesis system. Their photocatalytic performance in degradation of methylene blue is investigated and the results show that the RGO plays an important role in the enhancement of photocatalytic performance and the ZnO-RGO composite with 1.1 wt. % RGO achieves a maximum degradation efficiency of 88% in a neutral solution under UV light irradiation for 260 min as compared with pure ZnO (68%) due to the increased light absorption, the reduced charge recombination with the introduction of RGO.

  3. Controlled nitric oxide production via O(1D  + N2O reactions for use in oxidation flow reactor studies

    Directory of Open Access Journals (Sweden)

    A. Lambe

    2017-06-01

    Full Text Available Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O3 is photolyzed at 254 nm to produce O(1D radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA formation pathways. Simple addition of nitric oxide (NO results in fast conversion of NOx (NO + NO2 to nitric acid (HNO3, making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2 radicals as a sink for organic peroxy (RO2 radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(1D + N2O  →  2NO, followed by the reaction NO + O3  →  NO2 + O2. Laboratory measurements coupled with photochemical model simulations suggest that O(1D + N2O reactions can be used to systematically vary the relative branching ratio of RO2 + NO reactions relative to RO2 + HO2 and/or RO2 + RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS measurements with nitrate (NO3− reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.

  4. Reaction Ensemble Molecular Dynamics: Direct Simulation of the Dynamic Equilibrium Properties of Chemically Reacting Mixtures

    Czech Academy of Sciences Publication Activity Database

    Brennan, J.K.; Lísal, Martin; Gubbins, K.E.; Rice, B.M.

    2004-01-01

    Roč. 70, č. 6 (2004), 0611031-0611034 ISSN 1063-651X R&D Projects: GA ČR GA203/03/1588 Grant - others:NSF(US) CTS-0211792 Institutional research plan: CEZ:AV0Z4072921 Keywords : reacting systems * simulation * molecular dynamics Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.352, year: 2004

  5. The multichannel n-propyl + O2 reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism

    Science.gov (United States)

    Bartlett, Marcus A.; Liang, Tao; Pu, Liang; Schaefer, Henry F.; Allen, Wesley D.

    2018-03-01

    The n-propyl + O2 reaction is an important model of chain branching reactions in larger combustion systems. In this work, focal point analyses (FPAs) extrapolating to the ab initio limit were performed on the n-propyl + O2 system based on explicit quantum chemical computations with electron correlation treatments through coupled cluster single, double, triple, and perturbative quadruple excitations [CCSDT(Q)] and basis sets up to cc-pV5Z. All reaction species and transition states were fully optimized at the rigorous CCSD(T)/cc-pVTZ level of theory, revealing some substantial differences in comparison to the density functional theory geometries existing in the literature. A mixed Hessian methodology was implemented and benchmarked that essentially makes the computations of CCSD(T)/cc-pVTZ vibrational frequencies feasible and thus provides critical improvements to zero-point vibrational energies for the n-propyl + O2 system. Two key stationary points, n-propylperoxy radical (MIN1) and its concerted elimination transition state (TS1), were located 32.7 kcal mol-1 and 2.4 kcal mol-1 below the reactants, respectively. Two competitive β-hydrogen transfer transition states (TS2 and TS2') were found separated by only 0.16 kcal mol-1, a fact unrecognized in the current combustion literature. Incorporating TS2' in master equation (ME) kinetic models might reduce the large discrepancy of 2.5 kcal mol-1 between FPA and ME barrier heights for TS2. TS2 exhibits an anomalously large diagonal Born-Oppenheimer correction (ΔDBOC = 1.71 kcal mol-1), which is indicative of a nearby surface crossing and possible nonadiabatic reaction dynamics. The first systematic conformational search of three hydroperoxypropyl (QOOH) intermediates was completed, uncovering a total of 32 rotamers lying within 1.6 kcal mol-1 of their respective lowest-energy minima. Our definitive energetics for stationary points on the n-propyl + O2 potential energy surface provide key benchmarks for future studies

  6. Oxygen reduction reaction catalysts of manganese oxide decorated by silver nanoparticles for aluminum-air batteries

    International Nuclear Information System (INIS)

    Sun, Shanshan; Miao, He; Xue, Yejian; Wang, Qin; Li, Shihua; Liu, Zhaoping

    2016-01-01

    In this paper, the hybrid catalysts of manganese oxide decorated by silver nanoparticles (Ag-MnO x ) are fully investigated and show the excellent oxygen reduction reaction (ORR) activity. The Ag-MnO 2 is synthesized by a facile strategy of the electroless plating of silver on the manganese oxide. The catalysts are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Then, the ORR activities of the catalysts are systematically investigated by the rotating disk electrode (RDE) and aluminum-air battery technologies. The Ag nanoparticles with the diameters at about 10 nm are anchored on the surface of α-MnO 2 and a strong interaction between Ag and MnO 2 components in the hybrid catalyst are confirmed. The electrochemical tests show that the activity and stability of the 50%Ag-MnO 2 composite catalyst (the mass ratio of Ag/MnO 2 is 1:1) toward ORR are greatly enhanced comparing with single Ag or MnO 2 catalyst. Moreover, the peak power density of the aluminum-air battery with 50%Ag-MnO 2 can reach 204 mW cm −2 .

  7. Nitric oxide reduction in coal combustion: role of char surface complexes in heterogeneous reactions.

    Science.gov (United States)

    Arenillas, Ana; Rubiera, Fernando; Pis, José J

    2002-12-15

    Nitrogen oxides are one of the major environmental problems arising from fossil fuel combustion. Coal char is relatively rich in nitrogen, and so this is an important source of nitrogen oxides during coal combustion. However, due to its carbonaceous nature, char can also reduce NO through heterogeneous reduction. The objectives of this work were on one hand to compare NO emissions from coal combustion in two different types of equipment and on the other hand to study the influence of char surface chemistry on NO reduction. A series of combustion tests were carried out in two different scale devices: a thermogravimetric analyzer coupled to a mass spectrometer and an FTIR (TG-MS-FTIR) and a fluidized bed reactor with an on line battery of analyzers. The TG-MS-FTIR system was also used to perform a specific study on NO heterogeneous reduction reactions using chars with different surface chemistry. According to the results obtained, it can be said that the TG-MS-FTIR system provides valuable information about NO heterogeneous reduction and it can give good trends of the behavior in other combustion equipments (i.e., fluidized bed combustors). It has been also pointed out that NO-char interaction depends to a large extent on temperature. In the low-temperature range (800 degrees C), a different mechanism is involved in NO heterogeneous reduction, the nature of the carbon matrix being a key factor.

  8. Electrocatalytic performance evaluation of cobalt hydroxide and cobalt oxide thin films for oxygen evolution reaction

    Science.gov (United States)

    Babar, P. T.; Lokhande, A. C.; Pawar, B. S.; Gang, M. G.; Jo, Eunjin; Go, Changsik; Suryawanshi, M. P.; Pawar, S. M.; Kim, Jin Hyeok

    2018-01-01

    The development of an inexpensive, stable, and highly active electrocatalyst for oxygen evolution reaction (OER) is essential for the practical application of water splitting. Herein, we have synthesized an electrodeposited cobalt hydroxide on nickel foam and subsequently annealed in an air atmosphere at 400 °C for 2 h. In-depth characterization of all the films using X-ray diffraction (XRD), X-ray photoelectron emission spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) techniques, which reveals major changes for their structural, morphological, compositional and electrochemical properties, respectively. The cobalt hydroxide nanosheet film shows high catalytic activity with 290 mV overpotential at 10 mA cm-2 and 91 mV dec-1 Tafel slope and robust stability (24 h) for OER in 1 M KOH electrolyte compared to cobalt oxide (340 mV). The better OER activity of cobalt hydroxide in comparison to cobalt oxide originated from high active sites, enhanced surface, and charge transport capability.

  9. Controlled Synthesis of Pt Nanowires with Ordered Large Mesopores for Methanol Oxidation Reaction

    Science.gov (United States)

    Zhang, Chengwei; Xu, Lianbin; Yan, Yushan; Chen, Jianfeng

    2016-08-01

    Catalysts for methanol oxidation reaction (MOR) are at the heart of key green-energy fuel cell technology. Nanostructured Pt materials are the most popular and effective catalysts for MOR. Controlling the morphology and structure of Pt nanomaterials can provide opportunities to greatly increase their activity and stability. Ordered nanoporous Pt nanowires with controlled large mesopores (15, 30 and 45 nm) are facilely fabricated by chemical reduction deposition from dual templates using porous anodic aluminum oxide (AAO) membranes with silica nanospheres self-assembled in the channels. The prepared mesoporous Pt nanowires are highly active and stable electrocatalysts for MOR. The mesoporous Pt nanowires with 15 nm mesopores exhibit a large electrochemically active surface area (ECSA, 40.5 m2 g-1), a high mass activity (398 mA mg-1) and specific activity (0.98 mA cm-2), and a good If/Ib ratio (1.15), better than the other mesoporous Pt nanowires and the commercial Pt black catalyst.

  10. Interfacial reactions between indium tin oxide and triphenylamine tetramer layers induced by photoirradiation

    International Nuclear Information System (INIS)

    Satoh, Toshikazu; Fujikawa, Hisayoshi; Yamamoto, Ichiro; Murasaki, Takanori; Kato, Yoshifumi

    2008-01-01

    The effects of photoirradiation on the interfacial chemical reactions between indium tin oxide (ITO) films and layers of triphenylamine tetramer (TPTE) were investigated by using in situ x-ray photoelectron spectroscopy (XPS). Thin TPTE layers deposited onto sputter-deposited ITO films were irradiated with violet light-emitting diodes (peak wavelength: 380 nm). Shifts in the peak positions of spectral components that originated in the organic layer toward the higher binding-energy side were observed in the XPS profiles during the early stages of irradiation. No further peak shifts were observed after additional irradiation. An increase in the ratio of the organic component in the O 1s spectra was also observed during the photoirradiation. The ratio of the organic component increased in proportion to the cube root of the irradiation time. These results suggest that photoirradiation induces an increase in the height of the carrier injection barrier at the interface between TPTE and ITO in the early stages of the irradiation, possibly due to the rapid diffusion controlled formation and growth of an oxidized TPTE layer, which is considered to act as a high resistance layer

  11. Tuning the two-dimensional electron liquid at oxide interfaces by buffer-layer-engineered redox reactions

    DEFF Research Database (Denmark)

    Chen, Yunzhong; Green, Robert J.; Sutarto, Ronny

    2017-01-01

    Polar discontinuities and redox reactions provide alternative paths to create two-dimensional electron liquids (2DELs) at oxide interfaces. Herein, we report high mobility 2DELs at interfaces involving SrTiO3 (STO) achieved using polar La7/8Sr1/8MnO3 (LSMO) buffer layers to manipulate both...... polarities and redox reactions from disordered overlayers grown at room temperature. Using resonant x-ray reflectometry experiments, we quantify redox reactions from oxide overlayers on STO as well as polarity induced electronic reconstruction at epitaxial LSMO/STO interfaces. The analysis reveals how...... these effects can be combined in a STO/LSMO/disordered film trilayer system to yield high mobility modulation doped 2DELs, where the buffer layer undergoes a partial transformation from perovskite to brownmillerite structure. This uncovered interplay between polar discontinuities and redox reactions via buffer...

  12. Review on modeling development for multiscale chemical reactions coupled transport phenomena in solid oxide fuel cells

    International Nuclear Information System (INIS)

    Andersson, Martin; Yuan, Jinliang; Sunden, Bengt

    2010-01-01

    A literature study is performed to compile the state-of-the-art, as well as future potential, in SOFC modeling. Principles behind various transport processes such as mass, heat, momentum and charge as well as for electrochemical and internal reforming reactions are described. A deeper investigation is made to find out potentials and challenges using a multiscale approach to model solid oxide fuel cells (SOFCs) and combine the accuracy at microscale with the calculation speed at macroscale to design SOFCs, based on a clear understanding of transport phenomena, chemical reactions and functional requirements. Suitable methods are studied to model SOFCs covering various length scales. Coupling methods between different approaches and length scales by multiscale models are outlined. Multiscale modeling increases the understanding for detailed transport phenomena, and can be used to make a correct decision on the specific design and control of operating conditions. It is expected that the development and production costs will be decreased and the energy efficiency be increased (reducing running cost) as the understanding of complex physical phenomena increases. It is concluded that the connection between numerical modeling and experiments is too rare and also that material parameters in most cases are valid only for standard materials and not for the actual SOFC component microstructures.

  13. Solvent 1H/2H isotopic effects in the reaction of the L-Tyrosine oxidation catalyzed by Tyrosinase

    International Nuclear Information System (INIS)

    Kozlowska, M.; Kanska, M.

    2006-01-01

    Tyrosinase is well known catalyst in the oxidation of L-Tyrosine to L-DOPA and following oxidation of L-DOPA to dopachinone. The aim of communication is to present the results of studies on the solvent isotopic effects (SIE) in the above reactions for the 1 H/ 2 H in the 3',5' and 2',6' substituted tyrosine. Obtained dependence of the reaction rate on the substrate concentration were applied for optimization of the kinetic parameters, k cat and k cat /K m , in the Michaelis-Menten equation. As a result - better understanding of the L-DOPA creation can be achieved

  14. Effect of temperature towards lipid oxidation and non-enzymatic browning reactions in krill oil upon storage

    DEFF Research Database (Denmark)

    Lu, Henna Fung Sieng; Bruheim, I.; Haugsgjerd, B.O.

    2014-01-01

    was assessed by peroxide value and anisidine value, measurement of lipid derived volatiles, lipid classes and antioxidants. The non-enzymatic browning reactions were assessed through the measurement of pyrroles, free amino acids content and Strecker-derived volatiles. The increase of incubation temperature......The main objective of this study was to investigate the effect of temperature towards lipid oxidation and non-enzymatic browning reactions in krill oil upon storage. Krill oil was incubated at two different temperatures (20 and 40°C) for 28 or 42 days. The oxidative stability of krill oil...

  15. Preparation of Cu@Cu2O Nanocatalysts by Reduction of HKUST-1 for Oxidation Reaction of Catechol

    Directory of Open Access Journals (Sweden)

    Seongwan Jang

    2016-11-01

    Full Text Available HKUST-1, a copper-based metal organic framework (MOF, has been investigated as a catalyst in various reactions. However, the HKUST-1 shows low catalytic activity in the oxidation of catechol. Therefore, we synthesized Fe3O4@HKUST-1 by layer-by layer assembly strategy and Cu@Cu2O by reduction of HKUST-1 for enhancement of catalytic activity. Cu@Cu2O nanoparticles exhibited highly effective catalytic activity in oxidation of 3,5-di-tert-butylcatechol. Through this method, MOF can maintain the original core-shell structure and be used in various other reactions with enhanced catalytic activity.

  16. Preparation of Cu@Cu₂O Nanocatalysts by Reduction of HKUST-1 for Oxidation Reaction of Catechol.

    Science.gov (United States)

    Jang, Seongwan; Yoon, Chohye; Lee, Jae Myung; Park, Sungkyun; Park, Kang Hyun

    2016-11-02

    HKUST-1, a copper-based metal organic framework (MOF), has been investigated as a catalyst in various reactions. However, the HKUST-1 shows low catalytic activity in the oxidation of catechol. Therefore, we synthesized Fe₃O₄@HKUST-1 by layer-by layer assembly strategy and Cu@Cu₂O by reduction of HKUST-1 for enhancement of catalytic activity. Cu@Cu₂O nanoparticles exhibited highly effective catalytic activity in oxidation of 3,5-di- tert -butylcatechol. Through this method, MOF can maintain the original core-shell structure and be used in various other reactions with enhanced catalytic activity.

  17. Effect of strain on bond-specific reaction kinetics during the oxidation of H-terminated (111) Si

    International Nuclear Information System (INIS)

    Gokce, Bilal; Aspnes, David E.; Gundogdu, Kenan

    2011-01-01

    Although strain is used in semiconductor technology for manipulating optical, electronic, and chemical properties of semiconductors, the understanding of the microscopic phenomena that are affected or influenced by strain is still incomplete. Second-harmonic generation data obtained during the air oxidation of H-terminated (111) Si reveal the effect of compressive strain on this chemical reaction. Even small amounts of strain manipulate the reaction kinetics of surface bonds significantly, with tensile strain enhancing oxidation and compressive strain retarding it. This dramatic change suggests a strain-driven charge transfer mechanism between Si-H up bonds and Si-Si back bonds in the outer layer of Si atoms.

  18. Full Dynamic Reactions in the Basic Shaft Bearings of Big Band Saw Machines

    Science.gov (United States)

    Marinov, Boycho

    2013-03-01

    The band saws machines are a certain class woodworking machines for longitudinal or transversal cutting as well as for curvilinear wood cutting. These machines saw the wood through a band-saw blade and two feeding wheels. These wheels usually are very large and they are produced with inaccuracies. The centre of mass of the disc is displaced from the axis of rotation of the distance e (eccentricity) and the axis of the disk makes an angle with the axis of rotation. In this paper, the dy- namic reactions in the bearings of the basic shaft, which drives the band saw machines, are analyzed. These reactions are caused by the external loading and the kinematics and the mass characteristics of the rotating disk. The expressions for the full dynamic reactions are obtained. These expressions allow the parameters of the machines to be chosen in such a way that the loading in the shaft and the bearings to be minimal.

  19. Incident angle dependence of reactions between graphene and hydrogen atom by molecular dynamics simulation

    International Nuclear Information System (INIS)

    Saito, Seiki; Nakamura, Hiroaki; Ito, Atsushi

    2010-01-01

    Incident angle dependence of reactions between graphene and hydrogen atoms are obtained qualitatively by classical molecular dynamics simulation under the NVE condition with modified Brenner reactive empirical bond order (REBO) potential. Chemical reaction depends on two parameters, i.e., polar angle θ and azimuthal angle φ of the incident hydrogen. From the simulation results, it is found that the reaction rates strongly depend on polar angle θ. Reflection rate becomes larger with increasing θ, and the θ dependence of adsorption rate is also found. The θ dependence is caused by three dimensional structure of the small potential barrier which covers adsorption sites. φ dependence of penetration rate is also found for large θ. (author)

  20. Dynamics of the F(-) + CH3I → HF + CH2I(-) Proton Transfer Reaction.

    Science.gov (United States)

    Zhang, Jiaxu; Xie, Jing; Hase, William L

    2015-12-17

    Direct chemical dynamics simulations, at collision energies Erel of 0.32 and 1.53 eV, were performed to obtain an atomistic understanding of the F(-) + CH3I reaction dynamics. There is only the F(-) + CH3I → CH3F + I(-) bimolecular nucleophilic substitution SN2 product channel at 0.32 eV. Increasing Erel to 1.53 eV opens the endothermic F(-) + CH3I → HF + CH2I(-) proton transfer reaction, which is less competitive than the SN2 reaction. The simulations reveal proton transfer occurs by two direct atomic-level mechanisms, rebound and stripping, and indirect mechanisms, involving formation of the F(-)···HCH2I complex and the roundabout. For the indirect trajectories all of the CH2I(-) is formed with zero-point energy (ZPE), while for the direct trajectories 50% form CH2I(-) without ZPE. Without a ZPE constraint for CH2I(-), the reaction cross sections for the rebound, stripping, and indirect mechanisms are 0.2 ± 0.1, 1.2 ± 0.4, and 0.7 ± 0.2 Å(2), respectively. Discarding trajectories that do not form CH2I(-) with ZPE reduces the rebound and stripping cross sections to 0.1 ± 0.1 and 0.7 ± 0.5 Å(2). The HF product is formed rotationally and vibrationally unexcited. The average value of J is 2.6 and with histogram binning n = 0. CH2I(-) is formed rotationally excited. The partitioning between CH2I(-) vibration and HF + CH2I(-) relative translation energy depends on the treatment of CH2I(-) ZPE. Without a CH2I(-) ZPE constraint the energy partitioning is primarily to relative translation with little CH2I(-) vibration. With a ZPE constraint, energy partitioning to CH2I(-) rotation, CH2I(-) vibration, and relative translation are statistically the same. The overall F(-) + CH3I rate constant at Erel of both 0.32 and 1.53 eV is in good agreement with experiment and negligibly affected by the treatment of CH2I(-) ZPE, since the SN2 reaction is the major contributor to the total reaction rate constant. The potential energy surface and reaction dynamics for F

  1. Computing the Free Energy along a Reaction Coordinate Using Rigid Body Dynamics.

    Science.gov (United States)

    Tao, Peng; Sodt, Alexander J; Shao, Yihan; König, Gerhard; Brooks, Bernard R

    2014-10-14

    The calculations of potential of mean force along complex chemical reactions or rare events pathways are of great interest because of their importance for many areas in chemistry, molecular biology, and material science. The major difficulty for free energy calculations comes from the great computational cost for adequate sampling of the system in high-energy regions, especially close to the reaction transition state. Here, we present a method, called FEG-RBD, in which the free energy gradients were obtained from rigid body dynamics simulations. Then the free energy gradients were integrated along a reference reaction pathway to calculate free energy profiles. In a given system, the reaction coordinates defining a subset of atoms (e.g., a solute, or the quantum mechanics (QM) region of a quantum mechanics/molecular mechanics simulation) are selected to form a rigid body during the simulation. The first-order derivatives (gradients) of the free energy with respect to the reaction coordinates are obtained through the integration of constraint forces within the rigid body. Each structure along the reference reaction path is separately subjected to such a rigid body simulation. The individual free energy gradients are integrated along the reference pathway to obtain the free energy profile. Test cases provided demonstrate both the strengths and weaknesses of the FEG-RBD method. The most significant benefit of this method comes from the fast convergence rate of the free energy gradient using rigid-body constraints instead of restraints. A correction to the free energy due to approximate relaxation of the rigid-body constraint is estimated and discussed. A comparison with umbrella sampling using a simple test case revealed the improved sampling efficiency of FEG-RBD by a factor of 4 on average. The enhanced efficiency makes this method effective for calculating the free energy of complex chemical reactions when the reaction coordinate can be unambiguously defined by a

  2. ¹⁹F magnetic resonance probes for live-cell detection of peroxynitrite using an oxidative decarbonylation reaction.

    Science.gov (United States)

    Bruemmer, Kevin J; Merrikhihaghi, Sara; Lollar, Christina T; Morris, Siti Nur Sarah; Bauer, Johannes H; Lippert, Alexander R

    2014-10-21

    We report a newly discovered oxidative decarbonylation reaction of isatins that is selectively mediated by peroxynitrite (ONOO(-)) to provide anthranilic acid derivatives. We have harnessed this rapid and selective transformation to develop two reaction-based probes, 5-fluoroisatin and 6-fluoroisatin, for the low-background readout of ONOO(-) using (19)F magnetic resonance spectroscopy. 5-fluoroisatin was used to non-invasively detect ONOO(-) formation in living lung epithelial cells stimulated with interferon-γ (IFN-γ).

  3. Ab initio molecular dynamics of the reaction of quercetin with superoxide radical

    International Nuclear Information System (INIS)

    Lespade, Laure

    2016-01-01

    Highlights: • Ab initio molecular dynamics is performed to describe the reaction of quercetin and superoxide. • The reaction occurs near the sites 4′ and 7 when the system contains sufficiently water molecules. • The difference of reactivity of superoxide compared to commonly used radicals as DPPH · or ABTS ·+ is explained. - Abstract: Superoxide plays an important role in biology but in unregulated concentrations it is implicated in a lot of diseases such as cancer or atherosclerosis. Antioxidants like flavonoids are abundant in plant and are good scavengers of superoxide radical. The modeling of superoxide scavenging by flavonoids from the diet still remains a challenge. In this study, ab initio molecular dynamics of the reaction of the flavonoid quercetin toward superoxide radical has been carried out using Car–Parrinello density functional theory. The study has proven different reactant solvation by modifying the number of water molecules surrounding superoxide. The reaction consists in the gift of a hydrogen atom of one of the hydroxyl groups of quercetin to the radical. When it occurs, it is relatively fast, lower than 100 fs. Calculations show that it depends largely on the environment of the hydroxyl group giving its hydrogen atom, the geometry of the first water layer and the presence of a certain number of water molecules in the second layer, indicating a great influence of the solvent on the reactivity.

  4. Heavy ion collision dynamics of 10,11B+10,11B reactions

    Directory of Open Access Journals (Sweden)

    Singh BirBikram

    2015-01-01

    Full Text Available The dynamical cluster-decay model (DCM of Gupta and collaborators has been applied successfully to the decay of very-light (A ∼ 30, light (A ∼ 40−80, medium, heavy and super-heavy mass compound nuclei for their decay to light particles (evaporation residues, ER, fusion-fission (ff, and quasi-fission (qf depending on the reaction conditions. We intend to extend here the application of DCM to study the extreme case of decay of very-light nuclear systems 20,21,22Ne∗ formed in 10,11B+10,11B reactions, for which experimental data is available for their binary symmetric decay (BSD cross sections, i.e., σBSD. For the systems under study, the calculations are presented for the σBSD in terms of their preformation and barrier penetration probabilities P0 and P. Interesting results are that in the decay of such lighter systems there is a competing reaction mechanism (specifically, the deep inelastic orbiting of non-compound nucleus (nCN origin together with ff. We have emipirically estimated the contribution of σnCN. Moreover, the important role of nuclear structure characteristics via P0 as well as angular momentum ℓ in the reaction dynamics are explored in the study.

  5. Ab initio molecular dynamics of the reaction of quercetin with superoxide radical

    Energy Technology Data Exchange (ETDEWEB)

    Lespade, Laure, E-mail: l.lespade@ism.u-bordeaux1.fr

    2016-08-22

    Highlights: • Ab initio molecular dynamics is performed to describe the reaction of quercetin and superoxide. • The reaction occurs near the sites 4′ and 7 when the system contains sufficiently water molecules. • The difference of reactivity of superoxide compared to commonly used radicals as DPPH{sup ·} or ABTS{sup ·+} is explained. - Abstract: Superoxide plays an important role in biology but in unregulated concentrations it is implicated in a lot of diseases such as cancer or atherosclerosis. Antioxidants like flavonoids are abundant in plant and are good scavengers of superoxide radical. The modeling of superoxide scavenging by flavonoids from the diet still remains a challenge. In this study, ab initio molecular dynamics of the reaction of the flavonoid quercetin toward superoxide radical has been carried out using Car–Parrinello density functional theory. The study has proven different reactant solvation by modifying the number of water molecules surrounding superoxide. The reaction consists in the gift of a hydrogen atom of one of the hydroxyl groups of quercetin to the radical. When it occurs, it is relatively fast, lower than 100 fs. Calculations show that it depends largely on the environment of the hydroxyl group giving its hydrogen atom, the geometry of the first water layer and the presence of a certain number of water molecules in the second layer, indicating a great influence of the solvent on the reactivity.

  6. Study of dynamics of glucose-glucose oxidase-ferricyanide reaction

    Science.gov (United States)

    Nováková, A.; Schreiberová, L.; Schreiber, I.

    2011-12-01

    This work is focused on dynamics of the glucose-glucose oxidase-ferricyanide enzymatic reaction with or without sodium hydroxide in a continuous-flow stirred tank reactor (CSTR) and in a batch reactor. This reaction exhibits pH-variations having autocatalytic character and is reported to provide nonlinear dynamic behavior (bistability, excitability). The dynamical behavior of the reaction was examined within a wide range of inlet parameters. The main inlet parameters were the ratio of concentrations of sodium hydroxide and ferricyanide and the flow rate. In a batch reactor we observed an autocatalytic drop of pH from slightly basic to medium acidic values. In a CSTR our aim was to find bistability in the presence of sodium hydroxide. However, only a basic steady state was found. In order to reach an acidic steady state, we investigated the system in the absence of sodium hydroxide. Under these conditions the transition from the basic to the acidic steady state was observed when inlet glucose concentration was increased.

  7. Molecular-dynamics analysis of mobile helium cluster reactions near surfaces of plasma-exposed tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Lin; Maroudas, Dimitrios, E-mail: maroudas@ecs.umass.edu [Department of Chemical Engineering, University of Massachusetts, Amherst, Massachusetts 01003-9303 (United States); Hammond, Karl D. [Department of Chemical Engineering, University of Missouri, Columbia, Missouri 65211 (United States); Wirth, Brian D. [Department of Nuclear Engineering, University of Tennessee, Knoxville, Tennessee 37996 (United States)

    2015-10-28

    We report the results of a systematic atomic-scale analysis of the reactions of small mobile helium clusters (He{sub n}, 4 ≤ n ≤ 7) near low-Miller-index tungsten (W) surfaces, aiming at a fundamental understanding of the near-surface dynamics of helium-carrying species in plasma-exposed tungsten. These small mobile helium clusters are attracted to the surface and migrate to the surface by Fickian diffusion and drift due to the thermodynamic driving force for surface segregation. As the clusters migrate toward the surface, trap mutation (TM) and cluster dissociation reactions are activated at rates higher than in the bulk. TM produces W adatoms and immobile complexes of helium clusters surrounding W vacancies located within the lattice planes at a short distance from the surface. These reactions are identified and characterized in detail based on the analysis of a large number of molecular-dynamics trajectories for each such mobile cluster near W(100), W(110), and W(111) surfaces. TM is found to be the dominant cluster reaction for all cluster and surface combinations, except for the He{sub 4} and He{sub 5} clusters near W(100) where cluster partial dissociation following TM dominates. We find that there exists a critical cluster size, n = 4 near W(100) and W(111) and n = 5 near W(110), beyond which the formation of multiple W adatoms and vacancies in the TM reactions is observed. The identified cluster reactions are responsible for important structural, morphological, and compositional features in the plasma-exposed tungsten, including surface adatom populations, near-surface immobile helium-vacancy complexes, and retained helium content, which are expected to influence the amount of hydrogen re-cycling and tritium retention in fusion tokamaks.

  8. Theory of the reaction dynamics of small molecules on metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Jackson, Bret [Univ. of Massachusetts, Amherst, MA (United States)

    2016-09-09

    The objective of this project has been to develop realistic theoretical models for gas-surface interactions, with a focus on processes important in heterogeneous catalysis. The dissociative chemisorption of a molecule on a metal is a key step in many catalyzed reactions, and is often the rate-limiting step. We have explored the dissociative chemisorption of H2, H2O and CH4 on a variety of metal surfaces. Most recently, our extensive studies of methane dissociation on Ni and Pt surfaces have fully elucidated its dependence on translational energy, vibrational state and surface temperature, providing the first accurate comparisons with experimental data. We have explored Eley-Rideal and hot atom reactions of H atoms with H- and C-covered metal surfaces. H atom interactions with graphite have also been explored, including both sticking and Eley-Rideal recombination processes. Again, our methods made it possible to explain several experiments studying these reactions. The sticking of atoms on metal surfaces has also been studied. To help elucidate the experiments that study these processes, we examine how the reaction dynamics depend upon the nature of the molecule-metal interaction, as well as experimental variables such as substrate temperature, beam energy, angle of impact, and the internal states of the molecules. Electronic structure methods based on Density Functional Theory are used to compute each molecule-metal potential energy surface. Both time-dependent quantum scattering techniques and quasi-classical methods are used to examine the reaction or scattering dynamics. Much of our effort has been directed towards developing improved quantum methods that can accurately describe reactions, as well as include the effects of substrate temperature (lattice vibration).

  9. Effect of Thermal Processing towards Lipid Oxidation and Non-enzymatic Browning Reactions of Antartic Krill (Euphausia superba) Meal.

    Science.gov (United States)

    Liu, Yanzi; Cong, Peixu; Li, Beijia; Song, Yu; Liu, Yanjun; Xu, Jie; Xue, Changhu

    2018-04-13

    Antarctic krill is a huge source of biomass and prospective high-quality lipid source. Eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), nutritionally important lipid components with poor oxidative stability, were used as markers of oxidation during thermal processing of Antarctic krill (Euphausia superba) meal by evaluating the lipolysis, lipid oxidation, and non-enzymatic browning reactions. Liquid chromatography-mass spectrometry of the phospholipids (PLs) and the main oxidation products of free fatty acids (FFAs) and phosphatidylcholine (PC) was effective for evaluating the oxidation of EPA and DHA. During boiling, oxidation of EPA and DHA in the FFA and PC fractions and hydrolysis of the fatty acids at the sn-2 position of the PLs were predominant. The changes in PC during drying were mainly attributed to the oxidation of EPA and DHA. Heat treatment increased the oxidation products and concentration of hydrophobic pyrrole owing to pyrrolization between phosphatidylethanolamine (PE) and the lipid oxidation products. The lipid oxidation level of Antarctic krill increased after drying, owing to prolonged heating under the severe conditions. This article is protected by copyright. All rights reserved.

  10. CO oxidation on PtSn nanoparticle catalysts occurs at the interface of Pt and Sn oxide domains formed under reaction conditions

    KAUST Repository

    Michalak, William D.; Krier, James M.; Alayoglu, Selim; Shin, Jae-Yoon; An, Kwangjin; Komvopoulos, Kyriakos; Liu, Zhi; Somorjai, Gabor A.

    2014-01-01

    The barrier to CO oxidation on Pt catalysts is the strongly bound adsorbed CO, which inhibits O2 adsorption and hinders CO2 formation. Using reaction studies and in situ X-ray spectroscopy with colloidally prepared, monodisperse ∼2 nm Pt and PtSn

  11. Optimization of reaction conditions in selective oxidation of styrene over fine crystallite spinel-type CaFe2O4 complex oxide catalyst

    International Nuclear Information System (INIS)

    Pardeshi, Satish K.; Pawar, Ravindra Y.

    2010-01-01

    The CaFe 2 O 4 spinel-type catalyst was synthesized by citrate gel method and well characterized by thermogravimetric analysis, atomic absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The crystallization temperature of the spinel particle prepared by citrate gel method was 600 o C which was lower than that of ferrite prepared by other methods. CaFe 2 O 4 catalysts prepared by citrate gel method show better activity for styrene oxidation in the presence of dilute H 2 O 2 (30%) as an oxidizing agent. In this reaction the oxidative cleavage of carbon-carbon double bond of styrene takes place selectively with 38 ± 2 mol% conversion. The major product of the reaction is benzaldehyde up to 91 ± 2 mol% and minor product phenyl acetaldehyde up to 9 ± 2 mol%, respectively. The products obtained in the styrene oxidation reaction were analyzed by gas chromatography and mass spectroscopy. The influence of the catalyst, reaction time, temperature, amount of catalyst, styrene/H 2 O 2 molar ratio and solvents on the conversion and product distribution were studied.

  12. Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(III) amine-bis(phenolate) complex.

    Science.gov (United States)

    Dean, Rebecca K; Devaine-Pressing, Katalin; Dawe, Louise N; Kozak, Christopher M

    2013-07-07

    A diamine-bis(phenolate) chromium(III) complex, {CrCl[O2NN'](BuBu)}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.

  13. Dynamical Dipole and Equation of State in N/Z Asymmetric Fusion Reactions

    Directory of Open Access Journals (Sweden)

    Giaz Agnese

    2014-03-01

    Full Text Available In heavy ion reactions, in the case of N/Z asymmetry between projectile and target, the process leading to complete fusion is expected to produce pre-equilibrium dipole γ-ray emission. It is generated during the charge equilibration process and it is known as Dynamical Dipole. A new measurement of the dynamical dipole emission was performed by studying 16O + 116Sn at 12 MeV/u. These data, together with those measured at 8.1 MeV/u and 15.6 MeV/u for the same reaction, provide the dependence on the Dynamical Dipole total emission yield with beam energy and they can be compared with theoretical expectations. The experimental results show a weak increase of the Dynamical Dipole total yield with beam energies and are in agreement with the prediction of a theoretical model based on the Boltzmann–Nordheim–Vlasov (BNV approach. The measured trend with beam energy does not confirm the rise and fall behavior previously reported for the same fused compound but with a much higher dipole moment.

  14. Oxygen dependency of neutrophilic Fe(II) oxidation by Leptothrix differs from abiotic reaction

    NARCIS (Netherlands)

    Vollrath, S.; Behrends, T.; Van Cappellen, P.

    2012-01-01

    Neutrophilic Fe(II) oxidizing microorganisms are found in many natural environments. It has been hypothesized that, at low oxygen concentrations, microbial iron oxidation is favored over abiotic oxidation. Here, we compare the kinetics of abiotic Fe(II) oxidation to oxidation in the presence of

  15. Chemiluminescence from an oxidation reaction of rhodamine B with cerium(IV) in a reversed micellar medium of cetyltrimethylammonium chloride in 1-hexanol-cyclohexane/water.

    Science.gov (United States)

    Hasanin, Tamer H A; Tsunemine, Yusuke; Tsukahara, Satoshi; Okamoto, Yasuaki; Fujiwara, Terufumi

    2011-01-01

    The chemiluminescence (CL) emission, observed when rhodamine B (RB) in 1-hexanol-cyclohexane was mixed with cerium(IV) sulfate in sulfuric acid dispersed in a reversed micellar medium of cetyltrimethylammonium chloride (CTAC) in 1-hexanol-cyclohexane/water, was investigated using a flow-injection system. The CL emission from the oxidation reaction of RB with Ce(IV) was found to be stronger in the CTAC reversed micellar solution compared with an aqueous solution. Bearing on the enhancement effect of the CTAC reverse micelles on the RB-Ce(IV) CL, several studies including stopped-flow, fluorescence and electron spin resonance (ESR) spectrometries were performed. Rapid spectral changes of an intermediate in the RB-Ce(IV) reaction in the aqueous and reversed micellar solutions were successfully observed using a stopped-flow method. The effect of the experimental variables, i.e., oxidant concentration, sulfuric acid concentration, the mole fraction of 1-hexanol, water-to-surfactant molar concentration ratio, flow rate, upon the CL intensity was evaluated. Under the experimental conditions optimized for a flow-injection determination of RB based on the new reversed micellar-mediated CL reaction with Ce(IV), a detection limit of 0.08 µmol dm(-3) RB was achieved, and a linear calibration graph was obtained with a dynamic range from 0.5 to 20 µmol dm(-3). The relative standard deviation (n = 6) obtained at an RB concentration of 3 µmol dm(-3) was 3%.

  16. A comparative DFT study on CO oxidation reaction over Si-doped BC2N nanosheet and nanotube

    Science.gov (United States)

    Nematollahi, Parisa; Neyts, Erik C.

    2018-05-01

    In this study, we performed density functional theory (DFT) calculations to investigate different reaction mechanisms of CO oxidation catalyzed by the Si atom embedded defective BC2N nanostructures as well as the analysis of the structural and electronic properties. The structures of all the complexes are optimized and characterized by frequency calculations at the M062X/6-31G∗ computational level. Also, The electronic structures and thermodynamic parameters of adsorbed CO and O2 molecules over Si-doped BC2N nanostructures are examined in detail. Moreover, to investigate the curvature effect on the CO oxidation reaction, all the adsorption and CO oxidation reactions on a finite-sized armchair (6,6) Si-BC2NNT are also studied. Our results indicate that there can be two possible pathways for the CO oxidation with O2 molecule: O2(g) + CO(g) → O2(ads) + CO(ads) → CO2(g) + O(ads) and O(ads) + CO(g) → CO2(g). The first reaction proceeds via the Langmuir-Hinshelwood (LH) mechanism while the second goes through the Eley-Rideal (ER) mechanism. On the other hand, by increasing the tube diameter, the energy barrier increases due to the strong adsorption energy of the O2 molecule which is related to its dissociation over the tube surface. Our calculations indicate that the two step energy barrier of the oxidation reaction over Si-BC2NNS is less than that over the Si-BC2NNT. Hence, Si-BC2NNS may serve as an efficient and highly activated substrate to CO oxidation rather than (4,4) Si-BC2NNT.

  17. Global dynamics of a nonlocal delayed reaction-diffusion equation on a half plane

    Science.gov (United States)

    Hu, Wenjie; Duan, Yueliang

    2018-04-01

    We consider a delayed reaction-diffusion equation with spatial nonlocality on a half plane that describes population dynamics of a two-stage species living in a semi-infinite environment. A Neumann boundary condition is imposed accounting for an isolated domain. To describe the global dynamics, we first establish some a priori estimate for nontrivial solutions after investigating asymptotic properties of the nonlocal delayed effect and the diffusion operator, which enables us to show the permanence of the equation with respect to the compact open topology. We then employ standard dynamical system arguments to establish the global attractivity of the nontrivial equilibrium. The main results are illustrated by the diffusive Nicholson's blowfly equation and the diffusive Mackey-Glass equation.

  18. Role of rotational energy component in the dynamics of 16O+198Pt reaction

    Directory of Open Access Journals (Sweden)

    Sharma Manoj K.

    2017-01-01

    Full Text Available The role of rotational energy is investigated in reference to the dynamics of 16O+198Pt →214Rn∗ reaction using the sticking (IS and the non-sticking (INS limits of moment of inertia within the framework of dynamical cluster decay model. The decay barrier height and barrier position get significantly modified for the use of sticking or non-sticking choice, which in turn reproduce the evaporation residue and the fusion-fission cross-sections nicely by the IS approach, while the INS approach provides feasible addressal of data only for evaporation residue channel. Moreover, the fragmentation path of decaying fragments of 214Rn∗ compound nucleus gets influenced for different choices of moment of inertia. Beside this, the role of nuclear deformations i.e. static, dynamic quadurpole (β2 and higher order static deformation up to β4 are duly investigated for both choices of the moment of inertia.

  19. Bending localization of nitrous oxide under anharmonicity and Fermi coupling: the dynamical potential approach

    International Nuclear Information System (INIS)

    Zhang Chi; Wu Guo-Zhen; Fang Chao

    2010-01-01

    This paper studies the vibrational nonlinear dynamics of nitrous oxide with Fermi coupling between the symmetric stretching and bending coordinates by classical dynamical potential approach. This is a global approach in the sense that the overall dynamics is evidenced by the classical nonlinear variables such as the fixed points and the focus are on a set of levels instead of individual ones. The dynamics of nitrous oxide is demonstrated to be not so much dependent on the excitation energy. Moreover, the localized bending mode is shown to be ubiquitous in all the energy range studied

  20. The lithiation and acyl transfer reactions of phosphine oxides, sulfides and boranes in the synthesis of cyclopropanes

    DEFF Research Database (Denmark)

    Clarke, Celia; Fox, David J; Pedersen, Daniel Sejer

    2009-01-01

    Phosphine oxides are lithiated much faster than phosphine sulfides and phosphine boranes. Phosphine sulfides are in turn lithiated much more readily than phosphine boranes. It was possible to trap a phosphine sulfide THF in one case which upon treatment with t-BuOK gave cyclopropane, showing...... that phosphine sulfides readily undergo both phosphinoyl transfer and cyclopropane ring closure just like their phosphine oxide counterparts. The obtained data show that phosphine oxides are easily lithiated and undergo phosphoryl transfer much more readily and faster than phosphine sulfides and phosphine...... boranes. The observations suggest that it would be possible to perform reactions involving phosphine oxides in the presence of phosphine boranes or phosphine sulfides, potentially allowing regioselective alkylation of phosphine oxides in the presence of phosphine boranes or phosphine sulfides....

  1. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries.

    Science.gov (United States)

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-12-23

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn 4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g -1 based on solid-state redox reaction of oxide ions.

  2. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

    Science.gov (United States)

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-01-01

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions. PMID:28008955

  3. Selective catalytic oxidation of NO as a process stage in NOx separation from power plant and production systems off-gases. Catalyst development and reaction kinetics. Final report. Die selektive katalytische Oxidation des NO als Prozess-Stufe bei der Stickoxidabscheidung aus Abgasen von Kraftwerken und Produktionsanlagen. Katalysatorentwicklung und Reaktionskinetik. Abschlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Emig, G.; Seifert, J.

    1989-06-01

    The research project was to investigate the heterogeneously catalyzed oxidation of NO in flue gas using 1. metal oxide catalysts (commonly on a MnO{sub 2} basis), 2. ZSM5 zeolites (pentasil), and 3. noble metal catalysts. Apart from the reaction kinetics, also the activity and resistance to typical catalyst poisons (SO{sub 2}, HCl, HF, heavy metals) were investigated. A fully automatic, computer-controlled experimental apparatus was developed which apart from the analysis of reaction products permitted also dynamic experiments with time constants in the seconds range and experiments with cyclic variation of concentration, temperature, and time of residue. (RB).

  4. Nitric oxide formation from the reaction of nitrite with carp and rabbit hemoglobin at intermediate oxygen saturations

    DEFF Research Database (Denmark)

    Jensen, Frank Bo

    2008-01-01

    The nitrite reductase activity of deoxyhemoglobin has received much recent interest because the nitric oxide produced in this reaction may participate in blood flow regulation during hypoxia. The present study used spectral deconvolution to characterize the reaction of nitrite with carp and rabbit...... hemoglobin at different constant oxygen tensions that generate the full range of physiological relevant oxygen saturations. Carp is a hypoxia-tolerant species with very high hemoglobin oxygen affinity, and the high R-state character and low redox potential of the hemoglobin is hypothesized to promote...... NO generation from nitrite. The reaction of nitrite with deoxyhemoglobin leads to a 1 : 1 formation of nitrosylhemoglobin and methemoglobin in both species. At intermediate oxygen saturations, the reaction with deoxyhemoglobin is clearly favored over that with oxyhemoglobin, and the oxyhemoglobin reaction...

  5. Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air

    Directory of Open Access Journals (Sweden)

    M. Ehn

    2012-06-01

    Full Text Available High molecular weight (300–650 Da naturally charged negative ions have previously been observed at a boreal forest site in Hyytiälä, Finland. The long-term measurements conducted in this work showed that these ions are observed practically every night between spring and autumn in Hyytiälä. The ambient mass spectral patterns could be reproduced in striking detail during additional measurements of α-pinene (C10H16 oxidation at low-OH conditions in the Jülich Plant Atmosphere Chamber (JPAC. The ions were identified as clusters of the nitrate ion (NO3 and α-pinene oxidation products reaching oxygen to carbon ratios of 0.7–1.3, while retaining most of the initial ten carbon atoms. Attributing the ions to clusters instead of single molecules was based on additional observations of the same extremely oxidized organics in clusters with HSO4 (Hyytiälä and C3F5O2 (JPAC. The most abundant products in the ion spectra were identified as C10H14O7, C10H14O9, C10H16O9, and C10H14O11. The mechanism responsible for forming these molecules is still not clear, but the initial reaction is most likely ozone attack at the double bond, as the ions are mainly observed under dark conditions. β-pinene also formed highly oxidized products under the same conditions, but less efficiently, and mainly C9 compounds which were not observed in Hyytiälä, where β-pinene on average is 4–5 times less abundant than α-pinene. Further, to explain the high O/C together with the relatively high H/C, we propose that geminal diols and/or hydroperoxide groups may be important. We estimate that the night-time concentration of the sum of the neutral extremely oxidized products is on the order of 0.1–1 ppt (~10

  6. Dynamically adjustable foot-ground contact model to estimate ground reaction force during walking and running.

    Science.gov (United States)

    Jung, Yihwan; Jung, Moonki; Ryu, Jiseon; Yoon, Sukhoon; Park, Sang-Kyoon; Koo, Seungbum

    2016-03-01

    Human dynamic models have been used to estimate joint kinetics during various activities. Kinetics estimation is in demand in sports and clinical applications where data on external forces, such as the ground reaction force (GRF), are not available. The purpose of this study was to estimate the GRF during gait by utilizing distance- and velocity-dependent force models between the foot and ground in an inverse-dynamics-based optimization. Ten males were tested as they walked at four different speeds on a force plate-embedded treadmill system. The full-GRF model whose foot-ground reaction elements were dynamically adjusted according to vertical displacement and anterior-posterior speed between the foot and ground was implemented in a full-body skeletal model. The model estimated the vertical and shear forces of the GRF from body kinematics. The shear-GRF model with dynamically adjustable shear reaction elements according to the input vertical force was also implemented in the foot of a full-body skeletal model. Shear forces of the GRF were estimated from body kinematics, vertical GRF, and center of pressure. The estimated full GRF had the lowest root mean square (RMS) errors at the slow walking speed (1.0m/s) with 4.2, 1.3, and 5.7% BW for anterior-posterior, medial-lateral, and vertical forces, respectively. The estimated shear forces were not significantly different between the full-GRF and shear-GRF models, but the RMS errors of the estimated knee joint kinetics were significantly lower for the shear-GRF model. Providing COP and vertical GRF with sensors, such as an insole-type pressure mat, can help estimate shear forces of the GRF and increase accuracy for estimation of joint kinetics. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Microwave-irradiation polyol synthesis of PVP-protected Pt–Ni electrocatalysts for methanol oxidation reaction

    CSIR Research Space (South Africa)

    Mathe, Ntombizodwa R

    2017-01-01

    Full Text Available ://doi.org/10.1007/s12678-017-0441-3 Microwave-Irradiation Polyol Synthesis of PVP-Protected Pt–Ni Electrocatalysts for Methanol Oxidation Reaction Ntombizodwa R. Mathe Manfred R. Scriba Rirhandzu S. Rikhotso Neil J. Coville ABSTRACT: Bimetallic Pt...

  8. Non-noble metal graphene oxide-copper (II) ions hybrid electrodes for electrocatalytic hydrogen evolution reaction

    KAUST Repository

    Muralikrishna, S.; Ravishankar, T.N.; Ramakrishnappa, T.; Nagaraju, Doddahalli H.; Krishna Pai, Ranjith

    2015-01-01

    Non-noble metal and inexpensive graphene oxide-copper (II) ions (GO-Cu2+) hybrid catalysts have been explored for the hydrogen evolution reaction (HER). We were able to tune the binding abilities of GO toward the Cu2+ ions and hence their catalytic

  9. The reaction of 1-tetralones with thallium trinitrate supported on clay: ring contraction vs a-oxidation

    Directory of Open Access Journals (Sweden)

    Ferraz Helena M. C.

    2001-01-01

    Full Text Available The reaction of a series of 1-tetralones with thallium trinitrate supported on Montmorillonite K-10 clay led to products of ring contraction (methyl indan-1-carboxylates and/or alpha-oxidation (2-methoxy-1-tetralones, in variable yields.

  10. Diverse Reactions of Thiophenes, Selenophenes, and Tellurophenes with Strongly Oxidizing I(III) PhI(L)2 Reagents.

    Science.gov (United States)

    Egalahewa, Sathsara; Albayer, Mohammad; Aprile, Antonino; Dutton, Jason L

    2017-02-06

    We report the outcomes of the reactions of aromatic group 16 thiophene, selenophene, and tellurophene rings with the I(III) oxidants PhI(OAc)(OTf) and [PhI(Pyr) 2 ][OTf] 2 (Pyr = pyridine). In all reactions, oxidative processes take place, with generation of PhI as the reduction product. However, with the exception of tellurophene with PhI(OAc)(OTf), +4 oxidation state complexes are not observed, but rather a variety of other processes occur. In general, where a C-H unit is available on the 5-membered ring, an electrophilic aromatic substitution reaction of either -IPh or pyridine onto the ring occurs. When all positions are blocked, reactions with PhI(OAc)(OTf) give acetic and triflic anhydride as the identifiable oxidative byproducts, while [PhI(Pyr) 2 ][OTf] 2 gives pyridine electrophilic aromatic substitution onto the peripheral rings. Qualitative mechanistic studies indicate that the presence of the oxidizable heteroatom is required for pyridine to act as an electrophile in a substantial manner.

  11. Influence of Ligand Architecture in Tuning Reaction Bifurcation Pathways for Chlorite Oxidation by Non-Heme Iron Complexes

    NARCIS (Netherlands)

    Barman, Prasenjit; Faponle, Abayomi S; Vardhaman, Anil Kumar; Angelone, Davide; Löhr, Anna-Maria; Browne, Wesley R; Comba, Peter; Sastri, Chivukula V; de Visser, Sam P

    2016-01-01

    Reaction bifurcation processes are often encountered in the oxidation of substrates by enzymes and generally lead to a mixture of products. One particular bifurcation process that is common in biology relates to electron transfer versus oxygen atom transfer by high-valent iron(IV)-oxo complexes,

  12. ReaDDy--a software for particle-based reaction-diffusion dynamics in crowded cellular environments.

    Directory of Open Access Journals (Sweden)

    Johannes Schöneberg

    Full Text Available We introduce the software package ReaDDy for simulation of detailed spatiotemporal mechanisms of dynamical processes in the cell, based on reaction-diffusion dynamics with particle resolution. In contrast to other particle-based reaction kinetics programs, ReaDDy supports particle interaction potentials. This permits effects such as space exclusion, molecular crowding and aggregation to be modeled. The biomolecules simulated can be represented as a sphere, or as a more complex geometry such as a domain structure or polymer chain. ReaDDy bridges the gap between small-scale but highly detailed molecular dynamics or Brownian dynamics simulations and large-scale but little-detailed reaction kinetics simulations. ReaDDy has a modular design that enables the exchange of the computing core by efficient platform-specific implementations or dynamical models that are different from Brownian dynamics.

  13. Kinetics and reaction mechanism for aminolysis of benzyl 4-pyridyl carbonate in H2O: Effect of modification of nucleofuge from 2-pyridyl oxide to 4-pyridyl oxide on reactivity and reaction mechanism

    International Nuclear Information System (INIS)

    Kang, Ji Sun; Um, Ikhwan

    2012-01-01

    Pseudo-first-order rate constants k amine have been measured spectrophotometrically for the reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in H 2 O at 25.0.deg.C. The plots of k amine vs. [amine] curve upward, indicating that the reactions proceed through a stepwise mechanism with two intermediates, a zwitterionic tetrahedral intermediate T ± and its deprotonated form T - . This contrasts to the report that the corresponding reactions of benzyl 2-pyridyl carbonate 5 proceed through a forced concerted pathway. The k amine values for the reactions of 6 have been dissected into the second-order rate constant Kk 2 and the third order rate constant Kk 3 . The Brφnsted-type plots are linear with β nuc = 0.94 and 1.18 for Kk 2 and Kk 3 , respectively. The Kk 2 for the reaction of 6 is smaller than the second-order rate constant k N for the corresponding reaction of 5, although 4-pyridyl oxide in 6 is less basic and a better nucleofuge than 2-pyridyl oxide in 5

  14. Mechanisms of LiCoO2 Cathode Degradation by Reaction with HF and Protection by Thin Oxide Coatings.

    Science.gov (United States)

    Tebbe, Jonathon L; Holder, Aaron M; Musgrave, Charles B

    2015-11-04

    Reactions of HF with uncoated and Al and Zn oxide-coated surfaces of LiCoO2 cathodes were studied using density functional theory. Cathode degradation caused by reaction of HF with the hydroxylated (101̅4) LiCoO2 surface is dominated by formation of H2O and a LiF precipitate via a barrierless reaction that is exothermic by 1.53 eV. We present a detailed mechanism where HF reacts at the alumina coating to create a partially fluorinated alumina surface rather than forming AlF3 and H2O and thus alumina films reduce cathode degradation by scavenging HF and avoiding H2O formation. In contrast, we find that HF etches monolayer zinc oxide coatings, which thus fail to prevent capacity fading. However, thicker zinc oxide films mitigate capacity loss by reacting with HF to form a partially fluorinated zinc oxide surface. Metal oxide coatings that react with HF to form hydroxyl groups over H2O, like the alumina monolayer, will significantly reduce cathode degradation.

  15. Reaction mechanisms and evaluation of effective process operation for catalytic oxidation and coagulation by ferrous solution and hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H.; Moon, H.J.; Kim, Y.M. [Dept. of Environmental Engineering, Sangmyung Univ., Cheonan (Korea); Bae, W.K. [Dept. of Civil and Environmental Engineering, Hanyang Univ., Ansan, Kyounggi (Korea)

    2003-07-01

    This research was carried out to evaluate the removal efficiencies of COD{sub cr} and colour for the dyeing wastewater by ferrous solution and the different dosage of H{sub 2}O{sub 2} in Fenton process. In the case of H{sub 2}O{sub 2} divided dosage, 7:3 was more effective than 3:7 to remove COD{sub cr} and colour. The results showed that COD was mainly removed by Fenton coagulation, where the ferric ions are formed in the initial step of Fenton reaction. On the other hand colour was removed by Fenton oxidation rather than Fenton coagulation. This paper also aims at pursuing to investigate the effective removal mechanisms using ferrous ion coagulation, ferric ion coagulation and Fenton oxidation process. The removal mechanism of COD{sub cr} and colour was mainly coagulation by ferrous ion, ferric ion and Fenton oxidation. The removal efficiencies were dependent on the ferric ion amount at the beginning of the reaction. However the final removal efficiency of COD and colour was in the order of Fenton oxidation, ferric ion coagulation and ferrous ion coagulation. The reason of the highest removal efficiency by Fenton oxidation can be explained by the chain reactions with ferrous solution, ferric ion and hydrogen peroxide. (orig.)

  16. Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol.

    Science.gov (United States)

    Liu, Chang; Ma, Qingxin; Liu, Yongchun; Ma, Jinzhu; He, Hong

    2012-02-07

    Sulfate is one of the most important aerosols in the atmosphere. A new sulfate formation pathway via synergistic reactions between SO(2) and NO(2) on mineral oxides was proposed. The heterogeneous reactions of SO(2) and NO(2) on CaO, α-Fe(2)O(3), ZnO, MgO, α-Al(2)O(3), TiO(2), and SiO(2) were investigated by in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) at ambient temperature. Formation of sulfate from adsorbed SO(2) was promoted by the coexisting NO(2), while surface N(2)O(4) was observed as the crucial oxidant for the oxidation of surface sulfite. This process was significantly promoted by the presence of O(2). The synergistic effect between SO(2) and NO(2) was not observed on other mineral particles (such as CaCO(3) and CaSO(4)) probably due to the lack of the surface reactive oxygen sites. The synergistic reaction between SO(2) and NO(2) on mineral oxides resulted in the formation of internal mixtures of sulfate, nitrate, and mineral oxides. The change of mixture state will affect the physicochemical properties of atmospheric particles and therefore further influence their environmental and climate effects.

  17. Ultrafine Iridium Oxide Nanorods Synthesized by Molten Salt Method toward Electrocatalytic Oxygen and Hydrogen Evolution Reactions

    International Nuclear Information System (INIS)

    Ahmed, Jahangeer; Mao, Yuanbing

    2016-01-01

    Highlights: • Ultrafine iridium oxide nanorods were synthesized by a molten salt method at 650 °C. • They show enhanced electrocatalytic activity to oxygen and hydrogen evolution reactions. • These results are comparable with, and in most cases, higher than reported data in the literature. • This study reports a novel synthetic process for IrO_2 but also a high efficient IrO_2 nanostructure. • These IrO_2 NRs are expected to serve as a benchmark to develop active electrocatalysts. - Abstract: Ultrafine iridium oxide nanorods (IrO_2 NRs) were successfully synthesized using a molten salt method at 650 °C. The structural and morphological characterizations of these IrO_2 NRs were carried out by powder X-ray diffraction, Raman spectroscopy and electron microscopic techniques. Compared to commercial IrO_2 nanoparticles (IrO_2 NPs) and previous reports, these IrO_2 NRs show enhanced electrocatalytic activity to oxygen and hydrogen evolution reactions by passing either N_2 or O_2 gas in a 0.5 M KOH electrolyte before electrochemical measurements, including cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Specifically, the current densities from the as-synthesized IrO_2 NRs and commercial IrO_2 NPs were measured in 0.5 M KOH electrolyte to be 70 and 58 (OER, deaerated, at 0.6 V versus Ag/AgCl), 71 and 61 (OER, O_2, from −0.10 to 1.0 V versus Ag/AgCl at 50 mV/s), and 25 and 14 (HER, deaerated, at −1.4 V versus Ag/AgCl) mA/cm"2, respectively. These results are comparable with, and in most cases, higher than reported data in the literature. Therefore, the current study reports not only a novel synthetic process for IrO_2 but also a high efficient IrO_2 nanostructure, and it is expected that these IrO_2 NRs can serve as a benchmark in the development of active OER and HER (photo)electrocatalysts for various applications.

  18. Toluene removal by oxidation reaction in spray wet scrubber: experimental, modeling and optimization

    Directory of Open Access Journals (Sweden)

    Roumporn Nikom

    2006-11-01

    Full Text Available Toluene, an important volatile organic compound (VOC, is used in many kinds of industries, such as painting, printing, coating, and petrochemical industries. The emission of toluene causes serious air pollution, odor problem, flammability problem and affects human health. This paper proposes the removal of toluene from waste air using a spray wet scrubber combining the absorption and oxidation reaction. Aqueous sodium hypochlorite (NaOCl solution was used as the scrubbing liquid in the system. NaOCl, the strongest oxidative agent, presents an effective toluene removal. As the scrubbed toluene is reacted, recirculation of the scrubbing liquid could be operated with a constant removal efficiency throughout the operting time. The investigated variables affecting the removal efficiency were air flow rate, inlet toluene concentration, NaOCl concentration, scrubbing liquid flow rate and size of spray nozzle. Influence of the scrubbing parameters was experimentally studied to develop a mathematical model of the toluene removal efficiency. The removal model reveals that the increase of scrubbing liquid flow rate, toluene concentration, and NaOCl concentration together with the decrease of air flow rate and size of spray nozzle can increase the toluene removal efficiency. Optimization problem with an objective function and constraints was set to provide the maximum toluene removal efficiency and solved by Matlab optimization toolbox. The optimization constraints were formed from the mathematical model and process limitation. The solution of the optimization was an air flow rate of 100 m3/h, toluene concentration of 1500 ppm, NaOCl concentration of 0.02 mol/l, NaOCl solution feed rate of 0.8 m3/h, and spray nozzle size of 0.5 mm. Solution of the optimization gave the highest toluene removal efficiency of 91.7%.

  19. Probing Local Ionic Dynamics in Functional Oxides: From Nanometer to Atomic Scale

    Science.gov (United States)

    Kalinin, Sergei

    2014-03-01

    Vacancy-mediated electrochemical reactions in oxides underpin multiple applications ranging from electroresistive memories, to chemical sensors to energy conversion systems such as fuel cells. Understanding the functionality in these systems requires probing reversible (oxygen reduction/evolution reaction) and irreversible (cathode degradation and activation, formation of conductive filaments) electrochemical processes. In this talk, I summarize recent advances in probing and controlling these transformations locally on nanometer level using scanning probe microscopy. The localized tip concentrates the electric field in the nanometer scale volume of material, inducing local transition. Measured simultaneously electromechanical response (piezoresponse) or current (conductive AFM) provides the information on the bias-induced changes in material. Here, I illustrate how these methods can be extended to study local electrochemical transformations, including vacancy dynamics in oxides such as titanates, LaxSr1-xCoO3, BiFeO3, and YxZr1-xO2. The formation of electromechanical hysteresis loops and their bias-, temperature- and environment dependences provide insight into local electrochemical mechanisms. In materials such as lanthanum-strontium cobaltite, mapping both reversible vacancy motion and vacancy ordering and static deformation is possible, and can be corroborated by post mortem STEM/EELS studies. In ceria, a broad gamut of electrochemical behaviors is observed as a function of temperature and humidity. The possible strategies for elucidation ionic motion at the electroactive interfaces in oxides using high-resolution electron microscopy and combined ex-situ and in-situ STEM-SPM studies are discussed. In the second part of the talk, probing electrochemical phenomena on in-situ grown surfaces with atomic resolution is illustrated. I present an approach based on the multivariate statistical analysis of the coordination spheres of individual atoms to reveal

  20. Experimental and theoretical study of the reactions between neutral vanadium oxide clusters and ethane, ethylene, and acetylene.

    Science.gov (United States)

    Dong, Feng; Heinbuch, Scott; Xie, Yan; Rocca, Jorge J; Bernstein, Elliot R; Wang, Zhe-Chen; Deng, Ke; He, Sheng-Gui

    2008-02-13

    Reactions of neutral vanadium oxide clusters with small hydrocarbons, namely C2H6, C2H4, and C2H2, are investigated by experiment and density functional theory (DFT) calculations. Single photon ionization through extreme ultraviolet (EUV, 46.9 nm, 26.5 eV) and vacuum ultraviolet (VUV, 118 nm, 10.5 eV) lasers is used to detect neutral cluster distributions and reaction products. The most stable vanadium oxide clusters VO2, V2O5, V3O7, V4O10, etc. tend to associate with C2H4 generating products V(m)O(n)C2H4. Oxygen-rich clusters VO3(V2O5)(n=0,1,2...), (e.g., VO3, V3O8, and V5O13) react with C2H4 molecules to cause a cleavage of the C=C bond of C2H4 to produce (V2O5)(n)VO2CH2 clusters. For the reactions of vanadium oxide clusters (V(m)O(n)) with C2H2 molecules, V(m)O(n)C2H2 are assigned as the major products of the association reactions. Additionally, a dehydration reaction for VO3 + C2H2 to produce VO2C2 is also identified. C2H6 molecules are quite stable toward reaction with neutral vanadium oxide clusters. Density functional theory calculations are employed to investigate association reactions for V2O5 + C2H(x). The observed relative reactivity of C2 hydrocarbons toward neutral vanadium oxide clusters is well interpreted by using the DFT calculated binding energies. DFT calculations of the pathways for VO3+C2H4 and VO3+C2H2 reaction systems indicate that the reactions VO3+C2H4 --> VO2CH2 + H2CO and VO3+C2H2 --> VO2C2 + H2O are thermodynamically favorable and overall barrierless at room temperature, in good agreement with the experimental observations.